METHOD STATUS TABLE
SW-846, THIRD EDITION, UPDATES I, II, AND IIA
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.
-------
SW-846 METHOD STATUS TABLE
September 1994
NETH NO.
THIRD ED
DATED
9/86
0010
0020
0030
1010
1020
1110
1310
~ —
™ ~
NETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
"
"
~ ~
1020A
~ ~
1310A
1311
"
NETH NO.
FINAL
UPDT. II
DATED
9/94
~ ™
"
"* ~
~ ~
— —
— •
~ ~
1312
METHOD 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
SW-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
NETH NO.
THIRD ED
DATED
9/86
1320
1330
3005
3010
— ~
3020
3040
3050
METH NO.
FINAL
UPDATE I
DATED
7/92
~ ™
1330A
3005A
3010A
3020A
— ~
3050A
METH 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 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
_ _
3500
3510
3520
3540
~ ~
3550
3580
3600
NETH 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
METHOD 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
METHOD
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
NETH NO.
THIRD ED
DATED
9/86
3610
3611
3620
3630
3640
3650
3660
~ ~
3810
HETH NO.
FINAL
UPDATE I
DATED
7/92
3610A
3611A
3620A
3630A
™ ™
3650A
3660A
™ ~
NETH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
" ~
~ ~
3630B
3640A
"
"
3665
NETHOD 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
NETHOD
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
-------
SU-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 (Atomic1
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
-------
SU-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
~ ~
7090
7091
7130
7131
7140
7190
7191
7195
METH NO.
FINAL
UPDATE I
DATED
7/92
7081
— ~
~ ~
•" ~
~ ~
"
~ ~
~ ~
"
METH NO.
FINAL
UPDT. II
DATED
9/94
" ™
™ ™
™ ~
«. V
7131A
"
~ ™
~ «•
"
METHOD TITLE
Barium (Atomic
Absorption, Furnace
Technique)
Beryllium (Atomic
Absorption, Direct
Aspiration)
Beryllium (Atomic
Absorption, Furnace
Technique)
Cadmium (Atomic
Absorption, Direct
Aspiration)
Cadmium (Atomic
Absorption, Furnace
Technique)
Calcium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Furnace
Technique)
Chromium, Hexavalent
(Coprecipitation)
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
7081
Rev 0
7/92
7090
Rev 0
9/86
7091
Rev 0
9/86
7130
Rev 0
9/86
7131A
Rev 1
9/94
7140
Rev 0
9/86
7190
Rev 0
9/86
7191
Rev 0
9/86
7195
Rev 0
9/86
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7196
7197
7198
7200
7201
7210
~ ~
7380
"
METH NO.
FINAL
UPDATE I
DATED
7/92
7196A
~ ™
~ ™
•"
~ ~
"
7211
"• ~
7381
METH NO.
FINAL
UPDT. II
DATED
9/94
— ~
~ ••
~ ™*
"
™ ~
"
~ ~
** ~
"
METHOD TITLE
Chromium, Hexavalent
(Colorimetric)
Chromium, Hexavalent
(Chelation/Extrac-
tion)
Chromium, Hexavalent
(Differential Pulse
Polarography)
Cobalt (Atomic
Absorption, Direct
Aspiration)
Cobalt (Atomic
Absorption, Furnace
Technique)
Copper (Atomic
Absorption, Direct
Aspiration)
Copper (Atomic
Absorption, Furnace
Technique)
Iron (Atomic
Absorption, Direct
Aspiration)
Iron (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
7196A
Rev 1
7/92
7197
Rev 0
9/86
7198
Rev 0
9/86
7200
Rev 0
9/86
7201
Rev 0
9/86
7210
Rev 0
9/86
7211
Rev 0
7/92
7380
Rev 0
9/86
7381
Rev 0
7/92
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7420
7421
~ ~
7450
7460
r
7470
7471
7480
NETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
. v
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
-------
SM-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
7481
7520
7550
7610
7740
7741
~ ~
7760
"
NETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
™ ™*
~ —
"
— ""
~ **
~ ~
7760A
7761
NETH NO.
FINAL
UPDT. II
DATED
9/94
V V
• w
~ ~
~ ""
"• —
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 HETHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7770
~ —
7840
7841
7870
7910
7911
7950
"
METH NO.
FINAL
UPDATE I
DATED
7/92
™ ~
7780
~ ~
~ ~
"
"
"
~ "•
7951
METH 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
METH NO.
THIRD ED
DATED
9/86
8000
8010
8015
8020
8030
"
METH NO.
FINAL
UPDATE I
DATED
7/92
8000A
801 OA
8011
8015A
~ ~
8021
8030A
~ ~
METH 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
8015A
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
NETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
8040A
"
8070
NETH NO.
FINAL
UPDT. II
DATED
9/94
8032
™ "
™ ™
8061
~ ~
8080A
8081
"
METHOD 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
-------
SM-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
8100
_ .•
8120
8140
8150
NETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
8110
~ ~
~ ~
8141
8150A
NETH 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 Methylation or
Pentaf 1 uorobenzyl -
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)
Semi volatile Organic
Compounds
by Gas
Chromatography/Mass
Spectrometry (GC/MS)
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry
(GC/MS): Capillary
Column Technique
Semi volatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry
(GC/MS): Capillary
Column Technique
Thermal
Chromatography/Mass
Spectrometry (TC/MS)
for Screening
Semi volatile 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
NETH NO.
THIRD ED
DATED
9/86
8310
~ ~
NETH NO.
FINAL
UPDATE I
DATED
7/92
"
™" ~"
NETH NO.
FINAL
UPDT. II
DATED
9/94
8290
«• •
8315
8316
8318
METHOD TITLE
Polychlorinated
Dibenzodioxins
(PCDDs) and
Polychlorinated
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
JHPLC)
Acryl amide,
Acrylonitrile and
Acrolein by High
Performance Liquid
Chromatography
(HPLC)
N-Methylcarbamates
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
METH NO.
THIRD ED
DATED
9/86
9010
9012
METH NO.
FINAL
UPDATE I
DATED
7/92
9010A
~ ~
METH NO.
FINAL
UPDT. II
DATED
9/94
8321
8330
8331
8410
*" •"
*• ~
METHOD 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
Semivolatile
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
NETH NO.
THIRD ED
DATED
9/86
~ ~
9020
™ ~
9022
9030
"
9035
9036
9038
NETH NO.
FINAL
UPDATE I
DATED
7/92
9013
9020A
9021
~ ~
9030A
9031
_ _
"
NETH 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
"
"
~ "*
"
NETHOD TITLE
pH Electrometric
Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Determination of
Inorganic Anions 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
NETH NO.
THIRD ED
DATED
9/86
9070
9071
9080
9081
HETH NO.
FINAL
UPDATE I
DATED
7/92
"
HETH 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)
SH-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
METH NO.
FINAL
UPDATE I
DATED
7/92
9090A
~ ~
"
"'
"
"
*" **
"
METH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
~ ~
9096
~ ™
"
f
** ~
"
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
Ferricyanide AAI)
Chloride
(Colorimetric,
Automated
Ferricyanide AAII)
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
-------
SH-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
•» V
"
_ .
"• "•
~ ~
HCN Test
Method
H2S Test
Method
METH NO.
FINAL
UPDT. II
DATED
9/94
9252A
9253
•• ~
~ ~
V V
HCN Test
Method
H2S Test
Method
METHOD 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
-------
1020A
-------
METHOD 1020A
i , ' •
SETAFLASH CLOSED-CUP METHOD FOR DETERMINING IGNITABILITY
1.0 SCOPE AND APPLICATION , .
1.1 Method 1020 makes use of the Setaflash Closed Tester to determine
the flash point of liquids that have flash points between 0' and 110'C (32" and
230°F) and viscosities lower than 150 stokes at 25'C (77°F).
' • '
1.2 The procedure may be used to determine whether a material will or
will not flash at a specified temperature.or to determine the finite temperature
at which a material will flash. , „
i
1.3 Liquids that tend to form surface films under test conditions or
those that contain non-filterable suspended solids shall be tested for'
ignitability usijng Method 1010 (Pensky-Martens Closed-Cup).
2.0 SUMMARY OF ^METHOD ,
i . . - .
2.1 Byimeans of a syringe, 2-mL of sample is introduced through a leak-
proof entry port into the tightly closed Setaflash Tester or directly into the
cup which has been brought to within 3'C (5'F) below the expected flash point.
2.2 Asja flash/no-flash test, the expected flash-point temperature may
be a specification (e.g., 60'C). For specification testing, the temperature of
the apparatus is raised to the precise temperature of the specification flash
point by slight adjustment of the temperature dial. After 1 minute, 'a test flame
is applied inside the cup and note is-taken as to whether the test sample flashes
or not. If a repeat test is necessary, a fresh sample should be used.
I . •
2.3 For a finite .flash management, the temperature is sequentially
increased through th'e anticipated range, the test flame being applied at 5°C
(9°F) intervals until a flash is observed. A repeat determination is then made
using a fresh sample,, starting the test at the temperature of the last interval
before the flash| point of the material and making tests at increasing 0.5°C (1'F)
•intervals. -
For further information on how. to conduct a test with this method, see
Reference 1 below. l , - ,
3.0 METHOD PERFORMANCE . , :
See Method 1010.
4.0 REFERENCES ,
1. D-3278-78,, Test Method for Flash Point of Liquids by Setaflash Closed
Tester, American Society for Testing and Materials, 1916 Race Street,
Philadelphia, PA 19103.
2. Umana, M., Gutknecht, W., Salmons, C., et al., Evaluation of Ignitability
Methods (Liquids), EPA/600/S4-85/053, 1985.
1' ' 1020A - 1 Revision 1
I July 1992
-------
3. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
1020A - 2 Revision 1
July 1992
-------
METHOD 1110
CORROSIVITY TOWARD STEEL
1.0 SCOPE AND APPLICATION
1.1 Method 1110 1s used to measure the corroslvlty toward steel of both
aqueous and nonaqueous liquid wastes.
2.0 SUMMARY OF METHOD , '.'•'''
i ...
2.1 This test exposes coupons of SAE Type 1020 steel to the liquid waste
to be evaluated and, by measuring the degree to which the coupon has been
dissolved, determines the corroslvlty of the waste.
3.0 INTERFERENCES ,
3.1 In laboratory tests, such as this one, corrosion of duplicate
coupons 1s usually reproducible to within 10%. However, large differences 1n
corrosion rates may occasionally occur under conditions where the metal
surfaces become passlvated. Therefore, at least duplicate determinations of
corrosion rate should be made.
4.0 APPARATUS AND MATERIALS
^•! • • •
i - •
4.1 An apparatus should be used, consisting of a kettle or flask of
suitable size (usually 500 to 5,000 mL), a reflux condenser, a thermowell and
temperature regulating device, a heating device (mantle, hot plate, or bath),
and a specimen support system. A typical resin flask set up for this type of
test 1s shown 1n Figure 1.
i •
4.2 The supporting device and container shall be constructed of
materials that are not affected by, or cause contamination of, the waste under
test. i.
4.3 The method of supporting the coupons will vary with the apparatus
used for conducting the test, but 1t should be designed to Insulate the
coupons from each other physically and electrically and to Insulate the
coupons from any metallic container or other device used In the test. Some
common support materials Include glass, fluorpcarbon, or coated metal.
4.4 The shape and form of the coupon support should ensure free contact
with the waste. >
1110 - 1
Revision
Date September 1986
-------
Figure 1. Typical resin flask that can be used as a versatile and
convenient apparatus to conduct simple Immersion tests. Configuration of the
flask top 1s such that more sophisticated apparatus can be added as required
by the specific test being conducted. A =. thermowell, B * resin flask, C =
specimens hung on supporting device, D = heating mantle, E = liquid Interface,
F = opening in flask for additional apparatus that may be required, and G =
reflux condenser.
1110 - 2
Revision 0
Date September 1986
-------
4.5 A circular specimen of SAE 1020 steel of about 3.75 cm (1.5 1n.)
diameter 1s a convenient shape for a coupon. With a thickness of
approximately 0.32 cm (0.125 1n.) and a 0.80-cra (0.4-1n.)-diameter hole for
mounting, these specimens will readily pass through a 45/50 ground-glass Joint
of a distillation kettle. The total ,surface area of a circular specimen Is.
given by the following equation:
A = 3.14/2(p2-d2) + (t)(3.14)(D) + (t)(3.14)(d)
where:
t = thickness.
0 = diameter of the specimen.
d = diameter of the mounting hole.
If the hole 1s completely covered by the mounting support, the last term in
the equation, (t)(3.14)(d), Is omitted.
4.5.1 All coupons should be measured carefully to permit accurate
calculation of the exposed areas. An area calculation accurate to +1X 1s
usually adequate.
i , ' _
4.5.2 More uniform results may be expected If a substantial layer
of metal Is removed from the coupons prior to testing the corroslvlty of
the waste. This can be accomplished by chemical treatment (pickling), by
electrolytic removal, or by grinding with a coarse abrasive. At least
0.254 mm (0.0001 1n.) or 2-3 mg/cm2 should be removed. Final surface
treatment should Include finishing with 1120 abrasive paper or cloth.
Final cleaning consists of scrubbing with bleach-free scouring powder,
followed by rinsing 1n distilled water and then 1n acetone or methanol,
and finally by a1r-dry1ng. After final cleaning, the coupon should be
stored 1n a desiccator until used.
4.5.3 The minimum ratio of volume of waste to area of the metal
coupon to be used 1n this test 1s 40 ml/cm2.
5.0 REAGENTS
5.1 Sodium hydroxide (NaOH). (20%): Dissolves 200 g NaOH 1n 800 ml Type
II water and mix well.
5.2 Zinc dust.
5.3 Hydrochloric add (HC1); Concentrated.
5.4 Stannous chloride (SnCl2).
5.5 Antimony chloride
1110 - 3
Revision
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples should be collected using a sampling plan that addresses
the considerations discussed 1n Chapter Nine of this manual.
7.0 PROCEDURE
7.1 Assemble the test apparatus as described 1n Paragraph 4.0, above.
7.2 Fill the container with the appropriate amount of waste.
7.3 Begin agitation at a rate sufficient to ensure that the liquid is
kept well mixed and homogeneous. ' \ . .
1 . r
7.4 Using the heating device, bring the temperature of the waste to 55*C
(130*F).
7.5 An accurate rate of corrosion 1s not required; only a determination
as to whether the rate of corrosion 1s less than or greater than 6.35 mm per
year 1s required. A 24-hr test period should be ample to determine whether or
not the rate of corrosion 1s >6.35 mm per year.
7.6 In order to determine accurately the amount of material lost to
corrosion, the coupons have to be cleaned after Immersion and prior to
weighing. The cleaning procedure should remove all products of corrosion
while removing a minimum of sound metal. Cleaning methods can be divided Into
three general categories: mechanical, chemical, and electrolytic.
7.6.1 Mechanical cleaning Includes scrubbing, scraping, brushing,
and ultrasonic procedures. Scrubbing with a bristle Brush and mild
*'• abrasive 1s the most popular of these methods. The others are used 1n
cases of heavy corrosion as a first step In removing heavily encrusted
corrosion products prior to scrubbing. Care should be taken to avoid
removing sound metal.
7.6.2 Chemical cleaning Implies the removal of material from the
surface of the coupon by dissolution 1n an appropriate solvent. Solvents
such as acetone, dichloromethane, and alcohol are used to remove oil,
grease, or resinous materials and are used prior to Immersion to remove
the products of corrosion. Solutions suitable for removing corrosion
from the steel coupon are:
Solution Soaking Time Temperature
20% NaOH + 200 g/L zinc dust 5 m1n Boiling
• . . • • or ' ''_•.•_' •. ' ' .
Cone. HC1 + 50 g/L SnCl2 + 20 g/L SbCIa Until clean Cold
1110 - 4
Revision
Date September 1986
-------
7.6.3 Electrolytic cleaning should be preceded by scrubbing to
remove loosely adhering corrosion products. One method of electrolytic
cleaning that can be employed uses:
Solution: 50 g/L H2S04
Anode: . Carbon or lead
Cathode: Steel coupon
Cathode current density: 20 amp/cm2 (129 amp/1n.2)
Inhibitor: 2 cc organic Inhibitor/liter
Temperature: 74*C (165*F)
• - i . .
Exposure Period: 3 m1n.
NOTE: Precautions must be taken to ensure good electrical contact with
the coupon to avoid contamination of the cleaning solution with easily
reducible metal tons and to ensure that Inhibitor decomposition has not
occurred. Instead of a proprietary Inhibitor, 0.5 g/L of either
dlorthotolyl thlourea or qu1nol1n ethIodide can be used.
7.7 Whatever treatment 1s employed to clean the coupons, Its effect In
removing sound metal should be determined by using a blank (I.e., a coupon
that has not been exposed to the waste). The blank should be cleaned along
with the test coupon and Its waste loss subtracted from that calculated for.
the test coupons.
7.8 After corroded specimens have been cleaned and dried, they are
rewelghed. The weight loss Is employed as the principal measure of corrosion.
Use of weight loss as a measure of corrosion requires making the assumption
that all weight loss has been due to generalized corrosion and not localized
pitting. In order to determine the corrosion rate for the purpose of this
regulation, the following formula Is used:
Corrosion Rate (•»)'. "t1qgtia;'tj[j1'145 .
where: weight loss 1s 1n milligrams,
area 1n square centimeters,
time 1n hours, and
corrosion rate 1n millimeters per year (mmpy).
8.0 QUALITY CONTROL
8.1 All quality control data should be filed and available for auditing.
8.2 Duplicate samples should.be analyzed on a routine basis.
1110-5
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. National Association, of Corrosion Engineers, "Laboratory Corrosion
Testing of Metals for the Process Industries," NACE Standard TM-01-69 (1972
Revision), NACE, 3400 West Loop South, Houston, TX 77027.
1110 .- 6
Revision
Date September 1986
-------
fit i nww i i * -
COAAOSXVXTY TOMARO STCCL
7.1
test
epperetue
7.2
Pill .conteiner
with weete '
7.3
lAgitete
7.4
Meet
0
o
7.6 i Clean
1 coupon*
by necnenicel.
chemical and/or
electrolytic
•rat hod*
7.7 I Check
1 effect,
of cleaning
treatment on
removing touno
•etei
_LlJ
Determine
corrosion rete
( Stop J
1110 - 7
Revision 0
Date September 1986
•» U.S. GOVERNMFMT PPIMTIWR OPFir.E:1993-342-139«3251
-------
1310A
-------
METHOD 1310A
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST ,
1.0 SCOPE AND APPLICATION
1.1 This method is an interim method to determine whether a waste
exhibits the characteristic of Extraction Procedure Toxicity.
1.2 The procedure may also be used to simulate the leaching which a
waste may undergo if disposed of in a sanitary landfill. Method 1310 is
applicable to liquid, solid, and multiphase samples.
2.0 SUMMARY OF METHOD
\.
2.1 If a representative sample of the waste contains > 0.5% solids, the
solid phase of the sample is ground to pass a 9.5 mm sieve and extracted with
deionized water which is maintained at a pH of 5 ± 0.2, with acetic acid. Wastes
that contain < 0.5% filterable solids are, after filtering, considered to be the
EP extract for this method. Monolithic wastes which can be formed into a
cylinder 3.3 cm (dia) x 7.1 cm, or from which such a cylinder can be formed
which is representative of the waste, may be evaluated using the Structural
Integrity Procedure instead of being ground to pass a 9.5-mm sieve.
3.0 INTERFERENCES :
3,1 Potential interferences that may be encountered during analysis are
discussed in the individual analytical methods.
4.0 APPARATUS AND MATERIALS
1 4.1 Extractor - For purposes of this test, an acceptable extractor is
one that will impart sufficient agitation to the mixture to (1) prevent
stratification of the sample and extraction fluid,and (2) ensure that all. sample
surfaces are continuously brought into contact with .well-mixed extraction fluid.
Examples of suitable extractors are shown in FJgures 1-3 of this method and are
availaoie from: Associated Designs & Manufacturing Co., Alexandria, Virginia;
Glas-Col Apparatus Co., Terre Haute, Indiana; Millipore, Bedford, Massachusetts;
and Rexnard, Milwaukee, Wisconsin.
4.2 pH meter or pH controller - Accurate to 0.05 pH units with
temperature compensation. .- ' v •
\ '
4.3 Filter holder - Capable of supporting a 0.45-/im filter membrane and
of withstanding the pressure needed to accomplish separation. Suitable filter.
holders range from simple vacuum units to relatively complex systems that can
exert up to 5.3 kg/cm3 (75 psi) of pressure. The type, of fi-1-ter holder used
depends upon the properties of the mixture to be filtered. Filter holders known
to EPA and deemed suitable for u.se are listed in Table 1.
1310A - 1 Revision 1
July 1992.
-------
. 4.4 Filter membrane - Filter membrane suitable for conducting the
required filtration shall be fabricated from a material that (1) is not
physically changed by the waste material to be filtered and (2) does not absorb
or leach the chemical species for which a waste's EP extract will be analyzed.
Table 2 lists filter media known to the agency to be suitable for solid waste
testing. . .
4.4.1 In cases of doubt about physical effects on the filter,
contact the filter manufacturer to determine if the membrane or the
prefilter is adversely affected by the particular waste. If no
information is available, submerge the filter in the waste's liquid phase.
A filter that undergoes visible physical change after 48 hours (i.e..
curls, dissolves, shrinks, or swells) is unsuitable for use.
'4.4.2 To test for absorption or leaching by the filter: -
4.4.2.1 Prepare a standard solution of the chemical
species of interest.
4.4.2.2 Analyze the standard for its concentration of
the chemical species.
4.4.2.3 Filter the standard and reanalyze. If the
concentration of the filtrate differs from that of the original
standard, then the filter membrane leaches or absorbs one or more
of the chemical species and is not usable in this test method.
4.5 Structural integrity tester - A device meeting the specifications
shown in Figure 4 and having a 3.18-cm (1.25-in) diameter hammer weighing 0.33
kg (0.73 Tb) with a free fall of 15.24 cm (6 in) shall be used. This device is
available from Associated Design and Manufacturing Company, Alexandria, VA
22314, as Part No. 125, or it may be fabricated to meet these specifications.
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
sped fictions 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. All references to water in this method refer to
reagent water, as defined in Chapter One. .
5.3 Acetic acid (0.5N), CH,COOH, This can be made by diluting
concentrated glacial acetic acid (17.5N) by adding 57 ml glacial acetic acid to
1,000 ml of water and diluting to 2 liters. The glacial acetic acid must be of
high purity .and monitored for impurities.
5.4 Analytical standards should be prepared according to the applicable
analytical methods.
1310A'- 2 ' ' Revision 1
• . : ' July 1992
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
i ' .
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.
6.2 Preservatives must not be added to samples.
6.3 Samples can be refrigerated if it is determined that refrigeration
will not affect the integrity of the sample. .
7.0 PROCEDURE
7.1 If the waste does not contain any free liquid, go to Step 7.9. If
the sample is liquid or multiphase, continue as follows. Weigh filter membrane
and prefilter to + 0.01 g. Handle membrane and prefliters with blunt curved-tip
forceps or vacuum tweezers, or by applying suction with a pipet.
7.2 Assemble filter holder, membranes, and prefiHers following the
manufacturer's instructions. Place the 0.45-Mm membrane on the support screen
and add prefilters in ascending order of pore size. Do not prewet filter
membrane.
i • • '.
7.3 Weigh out a representative subsample of the waste (100 g minimum).
7.4 Allow slurries to stand, to permit the solid phase, to settle.
Wastes that settle slowly may be centrifuged prior to filtration.
7.5 Wet the filter with a small portion of the liquid phase from the
waste r-r from the extraction mixture. Transfer the remaining material to .the
filter holder and apply vacuum or gentle pressure (10-15 psi) until all liquid
passes through the filter. Stop filtration when air or pressurizing gas moves
through the membrane. If this point is not reached under vacuum or gentle
pressure, s.lowly increase the pressure in 10-psi increments to 75 psi. Halt
filtration when liquid flow stops. This liquid will constitute part or all of
the extract (refer to Step 7.16). The liquid should be refrigerated until time
of analysis. , • . . ,
NOTE: °n samples or samples containing oil are treated in exactly the same way
as any other sample. The liquid portion of the sample is filtered and
treated as part of the EP extractl If the liquid portion of the sample
will not pass through the filter (usually the case with heavy oils or
greases), it should be carried through the EP extraction as a solid.
7.6 Remove the solid phase and filter media and, while not allowing
them to dry, weigh to + 0.01 g. The wet weight of the residue is determined by
calculating the weight difference between1 the weight of the filters (Step 7.1)
and the weight of the solid phase and the filter media.
7.7. The waste will be handled differently from this'point.on, depending
on whether it contains more or less than 0.5% solids. If the sample appears to
have < 0.5% solids, determine the percent solids exactly (see Note below) by the
following procedure: ,
1310A - 3 ' Revision 1>
July 1992
-------
7.7.1 Dry the filter and residue at 80'C until two successive
weighings yield the same value.
\
7.7.2 Calculate the percent solids, using the following
equation:
weight of tared weight
filtered solid - of filters
and filters
initial weight of waste material
x 100 = % solids
NOTE: This procedure is used only to determine whether the solid must be
extracted or whether it can be discarded unextracted. It is not used in
calculating the amount of water or acid to use in the extraction step. Do
not extract solid material that has been dried at 80°C. A new sample will
have to be used for extraction if a percent solids determination is
performed.
7.8 If the solid constitutes < 0.5% of the waste, discard the solid and
proceed immediately to Step 7.17, treating the liquid phase as the extract.
7.9 , The solid material obtained from Step 7.5 and all materials that
do not contain free liquids shall be evaluated for particle size. If the solid
material has a surface area per g of material > 3.1 cm2 or passes through a 9.5-
mm (0.375-in.) .standard sieve, the operator shall proceed to Step 7.11. If the
surface area is smaller or the particle size larger than specified above, the
solid material shall be prepared for extraction by crushing, cutting, or grinding
the material so that it passes through a 9.5-mm (0.375-in.) sieve or, if the
material is in a single piece, by subjecting the material to the "Structural
Integrity Procedure" described in Step 7.10. >
7.10 Structural Integrity Procedure (SIP)
7.10.1 Cut a 3.3-cm diameter by 7.1-cm long cylinder from the
waste material. If the waste has been treated using a fixation process,
the waste may be cast in the form of a cylinder and allowed to cure for 30
days prior to testing.
7.10.2 Place waste into sample holder and assemble the tester.
Raise the hammer to its maximum height and drop. Repeat 14 additional
times. •
7.10.3 .Remove solid material from tester and scrape off any
particles adhering to sample holder. ' Weigh the waste to the nearest 0.01
g and transfer it to the extractor.
7.11 If the sample contains > 0.5% solids, use the wet weight of the
solid phase (obtained in Step 7.6) to calculate the amount of liquid andvacid to
.employ for extraction by using the following equation:
W = Wf - Wt ,
1310A - 4 Revision. 1
July 1992
-------
where :
W = Wet .weight in g of solid to be charged to extractor.'
Wf = Wet weight in g of filtered solids and filter media.
Wt = Weight in g of tared filters.
If the waste does not contain any free liquids, 100 g of the material will be
subjected to the extraction procedure.
7.12 Place the appropriate amount of material (refer to Step 7,11) into
the extractor and add 16 times its weight with water.
7.13 After the solid material and water are placed in the extractor, the
operator shall begin agitation and measure the pH of the solution in the
extractor. If the pH is > 5.0, the pH of the solution should be decreased to 5.0
± 0.2 by slowly adding 0.5N acetic acid. If the pH is < 5.0, no acetic acid
should be added. The pH of the solution should be monitored, as described below,
during the course of the extraction, and, if the pH rises above 5.2, 0.5N acetic
acid should be added to bring the pH down to 5.0 ± 0.2. However, in no event
shall the aggregate amount of acid added to the solution exceed 4 mL of acid per
g of solid. The mixture should be agitated for 24 hours and maintained at 20-
40eC (68-104'F) during this time. It fs recommended that the operator monitor
and adjust the pH during the course of the extraction with a device such as the
Type 45-A.pH Controller, manufactured by Ghemtrix, Inc., .Hillsboro, Oregon
97123, or its equivalent, in conjunction with a metering pump and reservoir of
0.5N acetic acid. If such a system is not available, the following manual
procedure shall be employed.
NOTE: Do not add acetic acid too quickly. Lowering the pH to below the target
concentration of 5.0 could ,affect the metal concentrations in the,
leachate. .
7.13.1 ;A pH meter should be calibrated in accordance with the
manufacturer's specifications.
7.13.2 The pH of .the solution should be checked, and, if
ntxessary, 0.5 N acetic acid should be manually added to the extractor
until the pH reaches 5.0 + 0.2. The pH of the solution should be adjusted
at 15-, 30-, and 60-minute intervals, moving to the next longer interval
if the pH does not have to be adjusted > 0.5 pH units.
7.13.3 The adjustment procedure should be continued for at least
6 hours. ' ,
7.13.4 If, at,the end of the 24-hour extraction period, the pH
of the solution is not below 5.2 and the maximum amount of acid (4 ml per
g of solids) has not been added, the pH should be adjusted to 5.0 + 0.2
and the extraction continued for an additional 4 hours, during.which the
pH should be adjusted, at lrhour intervals, -v
1310A - 5 Revision 1
. July 1992
-------
'. 7.14 At the end of the extraction period, water should be added to the
extractor in an amount determined by the following equation:
V = .(20) (W) - 16(W) - A
where: .
V = mL water to be added. ' ,
.W = Weight in g of solid charged to extractor.
A = ml of 0.5N acetic acid added during extraction. ,
7.15 The material in the extractor should be separated into its
component liquid and solid phases in the following manner:
7.15.1 Allow slurries to stand to permit the solid phase to
settle (wastes that are slow to settle may be centrifuged prior to
filtration) and set up the filter apparatus (refer to Steps 4.3 and 4.4).
"••
7.15.2 Wet the filter with a .small portion of the liquid phase
, from the waste or from the extraction mixture. Transfer the remaining
material to the filter holder and apply vacuum or gentle pressure (10-
15 psi) until all liquid passes through the filter. Stop filtration when
air or pressurizing gas moves through the membrane. If this point is not
reached under vacuum or gentle pressure, slowly increase the pressure in
10-psi increments to 75 psi. Halt filtration when liquid flow stops.
7.16 The liquids resulting from Steps 7.5 and 7.15 should be combined.
This combined liquid (or waste itself, if it has < Oi5% solids, as noted in Step
7.8) is the extract. _ ' '-
7.17 The, extract is then prepared and analyzed using the appropriate
analytical methods described.in Chapters Three and Four of this manual.
NOTE: If the EP extract includes two phases, concentration of contaminants is
determined by using a simple weighted average. ~ For example: An EP
extract contains 50 ml of oil, and 1,000 mL of an aqueous phase.
Contaminant concentrations are determined for each phase. The final.
contamination concentration is taken to be:
50 x contaminant cone.
in oil
1,000 x contaminant cone.
of aqueous phase
1050 .
NOTE: In cases where a contaminant was not detected, use the MDL in the
calculation. For example, if the MDL in the oily phase is 100 mg/L and 1
mg/L in the aqueous phase, the reporting limit would be 6 mg/L (rounded to
the nearest mg). If the regulatory threshold is 5 mg/L, the waste may be
EP toxic and results of the analysis are inconclusive.
1310A - 6 Revision 1
July 1992
-------
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring. , .
8.3 All quality control measures described in Cnapter One and in the
referenced analytical methods should be followed.
9.0 METHOD PERFORMANCE
9.1 The data tabulated in Table 3 were obtained from records of state
and contractor laboratories and are intended to show the precision of the entire
method (1310 plus analysis method). ; .
10.0 REFERENCES
1. Rohrbpugh, 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. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,.
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
. ' ' . . \
1310A - 7 Revision 1
July 1992
-------
TABLE 1. ERA-APPROVED FILTER HOLDERS
Manufacturer
Nuclepqre
Mi 11ipore
Pressure Filters
Nuclepore
Size
Model No.
Comments
Vacuum Filters
Gel man
Nalgene
47 mm
500 ml
4011 . .
44-0045 Disposable plastic unit,
including prefliter, filter
pads, and reservoir; can be
used when solution is to be
analyzed for inorganic
constituents.
Micro Filtration
Systems
Millipore
47 mm
47 mm
142 mm
142 mm
142 mm
410400
XX10 047 00
425900
302300
YT30 142 HW
1310A - 8
Revision 1
July 1992
-------
TABLE 2. ERA-APPROVED FILTRATION MEDIA
Supplier
Filter to be used
for aqueous systems
F'ilter to be used
for organic systems
Coarse prefilter
Gel man
i •
Nuclepore
Mi Hi pore
Medium prefliters
Gelman
Nuclepore
Millipore
Fine prefilters
Gelman
Nuclepore
Millipore
Fine filters (0.45 urn)
Gelman
Pall
Nuclepore
Millipore
61631, 61635
.210907, 211707
AP25 035 00,
AP25 127 50
61654, 61655
210905, 211705
AP20 035 00,
AP20 124 50
64798, 64803
210903, 211703
APIS 035 00,
APIS 124 50
63069, 66536
NX04750, NX14225
142218
HAWP 047 00,
HAWP 142 50
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
Selas
83485-02,
83486-02
210905, 211705
AP20 035 00,
AP20 124 50
64798, 64803
210903, 211703
AP15 035 00,
AP15 124 50
60540 or 66149,
66151
1422183
FHUP 047 00,
FHLP 142 50
83485-02,
83486-02
Susceptible to decomposition by certain polar organic solvents.
1310A - 9
Revision 1
July 1992
-------
TABLE 3. PRECISIONS OF EXTRACTION-ANALYSIS
PROCEDURES FOR SEVERAL ELEMENTS
Element
Arsenic
Barium
Cadmium
Sample Matrix
1.
2.
3,
1.
2.
3.
1.
2.
3.
4.
s 5.
Auto fluff
Barrel sludge
Lumber treatment
company sediment
Lead smelting emission
control dust
Auto fluff
Barrel sludge
Lead smelting emission
control dust
Wastewater treatment
sludge from
electroplating
Auto fluff
.Barrel sludge
Oil refinery
tertiary pond sludge
Analysis
Method
7060
7060
7060
6010
7081
- 7081.
3010/7130
3010/7130
7131
7131
7131
Laboratory
Replicates
1.8,
0.9,
28,
0.12
791,
422,
120,
360,
470,
1.5 MgA
2.6 Mg/L
42 mg/L
, 0.12 mg/L
780 Mg/L
380 Mg/L
120 mg/L
' 290 mg/L
610 Mg/L
1100, 890 Mg/L
3.2,
1.9 Mg/L
Chromium
Mercury
1. Wastewater treatment 3010/7190
sludge from
electroplating
2. Paint primer 7191
3. Paint primer filter . 7191
4. Lumber treatment 7191
company sediment
5..Oil refinery 7191
tertiary pond sludge
• • - < •
1. Barrel sludge 7470
2. Wastewater treatment . 7470
sludge from *
electroplating
3. Lead smelting emission 7470
control dust
1.1, 1.2 mg/L
61, 43
0.81, 0.89 mg/L
0.15, 0.09 M
1.4, 0.4 M9/L
0.4, 0.4 M9/L
1310A - 10
Revision 1
July 1992
-------
TABLE 3 (Continued)
Element
Sample Matrix
Analysis
Method
Laboratory
Replicates
Lead
Nickel
Chromium(VI)
1. Lead smelting emission 3010/7420
control dust \
2. Auto fluff . 7421
3. Incinerator ash 7421
4. Barrel sludge 7421
5. Oil refinery 7421
tertiary pond sludge
1. Sludge 7521
2. Wastewater treatment 3010/7520
sludge from
electroplating
1. Wastewater treatment 7196
sludge from
electroplating
940, 920 mg/L
1540, 1490
1000, 974
2550, 2800
31, 29
2260, 1720
130, 140 mg/L
18, 19
1310A - 11
Revision 1
July 1992
-------
FIGURE 1.
EXTRACTOR
: -H
L-^HBBmVVd
sl \
1
4.0
t ,
5.0 »•
1—0.25 j
|iATnUEVf*vn('
1 '
J—
1
9
,
1
^•••i
•»
i
.0
»
IB
Non-Clogging Support Bushing
1-Inch Blade at 30* to Horizontal
1310A - 12
Revision 1
July 1992
-------
2-Liter Plastic or Glass Bottles
1/15-Horsepower Electric Motor
29RPM
U)
u>
§
o
70
Screws for Holding Bottles
C-i-30
C 0>
VO O
VO 3
-------
FIGURE 3.
EPRI EXTRACTOR
1-Gallon Plastic
or Glass Bottle
Totally Enclosed
Fan Cooled Motor
30rpm, 1/8 HP
Foam Bonded to Cover
Box Assembly
Plywood Consuuction
1310A.- 14
Revision 1
July 1992
-------
FIGURE 4.
COMPACTION TESTER
Combined Weight
0.33 kg (0.73 Ib)
Sample
Elastomeric
Sample Holder
1310A - 15
Revision 1
July 1992
-------
, METHOD 1310A
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST
7.1 Weigh filter
membrane and
prafilt«r
7 2 Assemble filter
Kolder, membranes:
and profi1 tecs
7 3 Weigh out-
subsample of wast*
7 4 Let jolid phase
settle; centn.fuge
if - necessary.
7.5 Filter out'
liquid phase and
refrigerate it
76 Heigh wet solid
phase
7 7 Does
aste appear
to contain
<0 5*
soilds?
7 7 1 Dry filter
and weigh
772 Calculate '
percent solids
1310A - 16
Revision 1
July 1992
-------
METHOD 1310A
(Continued)
7.8 Discard solids
Area >
3.1 cm2/g
or passes
thr ough
9 5 mm
siave
Area < 3.1
cm2/g or
particle
size > 9 5
mm siave
7.9 What is
surface area or
particle size of
the mater
Material is
in single .
place
7. 10 1 Cut or cast '
cylinder from waste
ma terlal for.
Structural
Integrity Procedure"
7,9 Prepare
•ma ter ia 1 "for
ex trac 11on by
crushing, cutting.
o r gr J. nd ing
7 10 2 Assemble
tester; drop hammer
IS Lim«s
7 10 3 Remove solid
material; weigh;
transfer to
,ext racto r
1310A - 17
Revision 1
July 1992
-------
METHOD 1310A
(Continued)
7 15 Allow slurries
to stand; set up
filter apparatus;
filter
7 11 Calculate
amount -of liquid
and acid to use for
extraction
7 . 12 Place material
i/nto extractor: add
deioniied »at«r
7 11 Use 100 9 of
' .material far
extraction
procedure
7 16 Combine
liquids from
Section* -75 and
7.IS to analyse for
contaminants
.7 13 Agitate for 24
hours and monitor
pH of solution
o
7 17 Obtain
analytical method
fran Chapters 3 and
7 13 Calibrate and
adjust pH meter.
7 18 Compare
extract .
conce-.lration to
.Ta N imum
contamination
limit* to de.larminfl
EP t=«icity
7 14 At end of
extraction period.
add deionized xater
STOP
1310A - 18
Revision 1
July 1992
-------
1311
-------
METHOD 1311
TOXICITY CHARACTERISTIC LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION
1.1 The TCLP is designed to determine the mobility of both organic and
inorganic analytes present in liquid, solid, and multiphasic wastes.
1.2 If a total analysis of the waste demonstrates that individual
analytes are not present in the waste, or that they are present but at such'low
concentrations that the appropriate regulatory levels could not possibly be
exceeded, the TCLP need not be run. ,
1.3 If an analysis of any one of the liquid fractions of the TCLP
extract indicates that a regulated compound is present at such high concentra-
tions that, even after accounting for dilution from the other fractions of the
extract, the concentration would be above the regulatory level for that compound,
then the waste is hazardous and it is not necessary to analyze the remaining
fractions of the extract.
1.4; If an analysis of extract obtained using a bottle extractor shows
that the concentration of any regulated volatile analyte exceeds the regulatory
level for that compound, then the waste is1 hazardous and extraction using the ZHE
is not necessary. However, extract from a bottle extractor cannot be used to
demonstrate that the concentration of volatile compounds is below the regulatory
level.
2.0 SUMMARY OF METHOD '
2.1 For liquid wastes (i.e.. those containing less than 0.5% dry solid
material), the waste, after filtration through a 0.6 to 0.8 /im glass fiber
filter, is defined as .the TCLP extract. /
., 2.2 For wastes containing greater than or equal to 0.5% solids, the
liquid, if any, is separated from the solid phase and stored for later analysis;
the particle size of the solid phase is reduced, if necessary. The solid phase
is extracted with an amount of extraction fluid equal to 20 times the weight of
the solid phase. Jhe extraction fluid employed is a function of the alkalinity
of the solid phase of the waste.. A special extractor vessel is used when testing
'for volatile analytes (see Table 1 for a list of volatile compounds). Following
extraction, the liquid extract is separated from the solid phase by filtration
through a 0.6 to 0.8 /zm glass fiber filter. .
2.3 If compatible (i.e., multiple phases will not form on combination),
the initial liquid phase of the,waste is added to the liquid extract, and these
are analyzed together. If incompatible, the liquids are analyzed separately and
the results are mathematically combined to yield a volume-weighted average
concentration. .
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3.0 INTERFERENCES ,
3.1 Potential interferences that may be encountered during analysis are.
discussed in the individual analytical methods.
4.0 APPARATUS AND MATERIALS ,
\
4.1 Agitation apparatus: The agitation apparatus must be capable of
rotating the extraction vessel in an end-over-end fashion (see Figure 1) at
30 + 2 rpm. Suitable devices known to EPA are identified in Table 2.
4.2 Extraction Vessels
4.2.1 Zero-Headspace Extraction Vessel (ZHE). This device is
for use only when the waste is being tested for the.mobility of volatile
analytes (i.e.. those listed in Table 1). The ZHE (depicted in Figure 2)
.'• allows for liquid/solid separation within the device, and effectively
precludes headspace. This type of vessel allows for initial liquid/solid
separation, extraction, and final extract filtration without opening the
vessel (see Section 4;3.1). The vessels shall have an internal volume of
500-600 ml, and be equipped to accommodate a 90-110 mm filter. The devices
contain VITON*1 0-rings which should be replaced frequently. Suitable ZHE
devices known, to EPA are identified in Table 3.
For the ZHE to be acceptable for use, the piston within the ZHE
should be able to be moved with approximately 15 psi or less. If it takes
more pressure to move the piston, the 0-rings in the device should be
replaced, if this does not solve the problem, the ZHE i.s unacceptable for
TCLP analyses and the manufacturer should be contacted^
The ZHE should be checked for leaks after every extraction." If the
device contains a built-in pressure gauge, pressurize the device to
50 psi, allow it to stand unattended for 1 hour, and recheck the pressure.
If the device does not have a built-in pressure gauge, pressurize the
device to 50 psi, submerge it in water, and check for the presence of air
bubbles escaping from any of the fittings. If pressure is lost, check all
fittings and inspect and replace 0-rings, if necessary. Retest the
device. If leakage problems cannot be solved, the manufacturer should be
contacted.
Some ZHEs use gas pressure to actuate the ZHE piston, while others
use mechanical pressure (see Table 3). Whereas the volatiles procedure
(see Section 7.3) refers to pounds per square inch (psi), for the
mechanically actuated piston, the pressure applied is measured in
torque-inch-pounds. , Refer to the manufacturer's instructions as to the
proper conversion;.
1 VITON* is a trademark of Du Pont.
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4.2.2 Bottle Extraction Vessel. When the waste is being
evaluated using the nonvolatile extraction, a jar with sufficient capacity
to hold the sample and the extraction fluid is needed. Headspace is
allowed in this vessel.
The extraction bottles may be constructed from various materials>,
depending on the analytes to be analyzed and the nature of the waste (see
Section 4.3.3). It is recommended that borosilicate glass bottles be used
instead of other types of glass, especially when inorganics are of
concern. Plastic bottles, other than polytetrafluoroethylene, shall not
be used if organics are to be investigated. Bottles are available from a
number of laboratory suppliers. When this type of extraction vessel is
used, the filtration device discussed in Section 4.3.2 is used for initial
liquid/solid separation and final extract filtration.
4.3 Filtration Devices: It is recommended that all filtrations be
performed in a hood. .
4.3.1 Zerp-Headspace Extractor Vessel (ZHE): When the waste is
evaluated for volatiles, the zero-headspace extraction vessel described in
( Section 4.2.1 is used for filtration. The device shall be capable of
supporting and keeping in place the glass fiber filter and be able to
withstand the pressure needed to accomplish .separation (50 psi).
NOTE: '. When it is suspected that the glass fiber filter has .been ruptured,
.an in-line glass fiber filter may be used to filter the material
within the ZHE.
4.3.2 Filter Holder: When the waste is evaluated for other than
volatile analytes, any filter holder capable of supporting a glass fiber
filter and able to withstand the pressure needed to accomplish separation
may be used. Suitable filter holders range from simple vacuum units to
relatively complex systems capable of exerting pressures of up to 50 psi
or more. The type of filter holder used depends on the properties of the
material to be filtered (see Section 4.3.3). These devices shall have a
minimum internal volume of 300 ml and be equipped to accommodate a minimum
filter size of 47 mm (filter holders having an internal capacity of 1.5 L
''~f greater, and equipped to accommodate a 142 mm diameter .filter, are
recommended). Vacuum filtration can only be used for wastes with low
solids content (<10%) and for highly granular, liquid-containing wastes.
All other types of wastes should be filtered using positive pressure
filtration. Suitable filter holders known to EPA are shown in Table 4.
4.3.3 Materials of Construction: Extraction vessels and
filtration devices shall be made of inert materials which will not leach
or absorb waste components. Glass, pplytetrafluoroethylene (PTFE), or
type 316 stainless steel equipment may be used when evaluating the
mobility of both organic and inorganic components. Devices made of high
density polyethylene (HOPE), polypropylene (PP), or polyvinyl chloride
(PVC) may be used only when evaluating the mobility of metals. Borosili-
cate glass bottles are recommended for use over other types of glass
bottles, especially when inorganics are analytes of concern.
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4.4 Filters: Filters shall be made of borosilicate glass fiber, shall
contain no binder materials, and shall have an effective pore size of 0.6 to
0.8 urn, or equivalent. Filters known to EPA which meet these specifications are
identified in Table 5. Pre-filters must not be used. When evaluating the
mobility of metals, filters shall be acid-washed prior to use by rinsing with IN
nitric acid followed by three consecutive rinses'with deionized distilled water
(a minimum of 1 L per rinse is recommended). Glass fiber filters are fragile and
should be handled with care.
i • ,
4.5 pH Meters: The meter should be accurate to * 0.05 units at 25 °C.
4.6 ZHE Extract Collection Devices: TEDLAR*2 bags or glass, stainless
steel or PTFE gas-tight syringes are used to collect the initial liquid phase and
the final extract of the waste when using the ZHE device. The devices listed are
recommended for use under the following conditions:
4.6.1 If a waste contains an aqueous^liquid phase or if a waste
does not contain a significant amount of nonaqueous liquid (i.e.. <1% of
total waste), the TEDLAR* bag or a 600 ml syringe should be used to collect
and combine the initial liquid and solid extract.
4 6.2 If a waste contains a significant amount of nonaqueous
liquid in the^initial liquid phase (i.e., >1% of total waste), the syringe
or the TEDLAR* bag may be used for both the initial solid/liquid separation
and the final extract filtration. However, analysts should use one or the
other, not both. .
4.6.3 If the waste contains no initial liquid phase (is 100%
solid)sor has no significant solid phase (is 100% liquid), either the
TEDLAR* bag or the syringe may be used. If the syringe is used, discard
the first 5 mL of liquid expressed from the device. The remaining
aliquots are used for analysis.
4.7 ZHE Extraction Fluid Transfer Devices: Any device capable of
transferring the extraction fluid into the ZHE without changing the nature of the
extraction fluid is acceptable (e.g.. a positive displacement 'or peristaltic
pump, a oas tight syringe, pressure filtration unit (see Section 4.3.2), or other
ZHE device).
4.8 Laboratory Balance: Any laboratory balance accurate to within
+ 0.01 grams may be used (all weight measurements are to be within ±'0.1 grams).
4.9 Beaker or Erlenmeyer flask, glass, 500 mL.
4.10 Watchglass, appropriate diameter to cover beaker or Erlenmeyer
flask.
TEDLAR* is a registered trademark of Du Pont,
^ 4 Revision 0
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4.11 Magnetic stirrer.
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/defined as water in which an
interferant is not observed .at or above the method's detection limit of the
analyte(s) of interest. For nonvolatile extractions, ASTM Type II water or
equivalent meets the definition of reagent water. For volatile extractions, it
is recommended that reagent water be generated by any of the following methods.
Reagent water should be monitored periodically .for impurities.
5.2.1 Reagent water for volatile extractions may be generated
by passing tap water through a carbon filter bed containing about 500
grams of activated carbon (Calgoh Corp., Filtrasorb-300 or equivalent).
5.2.2 A water purification system (Millipore Super-Q or
equivalent) may also be used .to-generate reagent water for volatile
extractions.
5.2.3 Reagent water for volatile extractions may also be
prepared by boiling water for 15 minutes. Subsequently, while maintaining
the water temperature at 90 + 5 degrees C, bubble a contaminant-free inert
gas (e.g. nitrogen) through the water for 1 hour. While still hot,
transfer the water to a narrow mouth screw-cap bottle under zerp-headspace
and seal with a Teflon-lined septum and cap.
5.3 Hydrochloric acid (IN), HC1, made from ACS reagent grade.
5.4 Nitric acid (IN), HN03, made from ACS reagent grade.
5.j Sodium hydroxide (IN), NaOH, made from ACS reagent grade.
5.6 Glacial acetic acid, CH3CH2OOH, ACS reagent grade.
5.7 ' Extraction fluid.
5.7.1 Extraction fluid #1: Add 5.7 ml glacial CH3CH2OOH to
500 ml of reagent water (See Section 5.2), add 64.3 ml of IN NaOH, and
dilute to a volume of 1 liter. .When correctly prepared, the pH of this
fluid will be 4.93 ± 0.05.
' 5.7.2 Extraction fluid # 2:. Dilute 5.7 ml glacial CH3CH2OOH with
reagent water (See Section 5.2) to a volume of 1 liter,. When correctly
prepared, the pH of this fluid will be 2.88 ± 0.05.
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NOTE: These extraction fluids should be monitored frequently for
impurities. The pH should be checked prior to use to ensure that
these fluids are made up accurately. If impurities are found or
the pH is not within the above specifications, the fluid shall be
.discarded and fresh extraction fluid prepared.
5.8 Analytical standards shall be prepared according to the appropriate
analytical method. ,
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples shall be collected using an appropriate sampling plan.
6.2 The TCLP may place requirements on the minimal size of the field
sample, depending upon the physical state or states of the waste and the analytes
of concern. An aliquot is needed for preliminary evaluation of which extraction
fluid is to be used for the nonvolatile analyte extraction procedure. Another
aliquot may be needed to actually conduct the nonvolatile extraction (see Section
1.4 concerning the use of this .extract for volatile organics). If volatile
organics are of concern, another aliquot may be needed. Quality control measures
may require additional aliquots. Further, it is always wise to collect more
sample just in case something goes wrong with the initial attempt to conduct the
test.
6.3 ^Preservatives;shall'not be added to samples before extraction.
6.4 Samples may be refrigerated unless refrigeration results, in
irreversible physical change to the waste. If precipitation occurs, the entire
sample (including precipitate) should be extracted.
6.5 When the waste is to be evaluated for volatile analytes, care shal.l
be taken to minimize the loss of volatiles. Samples shall be collected and
stored in.a manner .intended to prevent the-loss of volatile analytes (e.g.,
samples should be collected in Teflon-lined septum capped vials and stored at 4
8C. Samples should be opened only immediately prior to extraction).
6.6 TCLP extracts should be prepared for analysis and analyzed as soon
as possible following extraction. Extracts,or portions of extracts for metallic
analyte determinations must be acidified with nitric acid to a p.Hv< 2, unless
precipitation occurs (see Section 7.2.14 if precipitation occurs). Extracts
should be preserved for other analytes according to the guidance given in the
individual' analysis methods. Extracts or portions of extracts for organic
analyte determinations shall not be allowed to .come into contact with the
atmosphere (i.e.. no headspace) to prevent Tosses. See Section 8.0 (QA
requirements) for acceptable sample and extract holding times.
7.0 PROCEDURE . ^
7.1 Preliminary Evaluations
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Perform preliminary TCLP evaluations on a minimum 100 gram aliquot of
waste. This aliquot may not actually undergo TCLP extraction. These preliminary
evaluations include: (1) determination of the percent solids (Section 7.1.1);
(2) determination of whether the waste contains insignificant solids and is,
therefore, its own extract after filtration (Section 7.1.2); (3) determination
of whether the solid portion 'of the waste requires particle size reduction
(Section 7.1.3); and (4) determination of which of the two extraction fluids are
to be used for the nonvolatile TCLP extraction of the,waste (Section 7.1.4).
7.1.1. Preliminary determination of percent solids: Percent
solids is defined as that fraction of a waste sample (as a percentage of
the total sample) from which no liquid may be forced out by an applied
pressure, as described below.
7.1.1.1 If the waste will obviously yield no liquid when
subjected to pressure filtration (i.e., is 100% solids) proceed to
Section 7.1.3.
7.1.1.2 If thex sample is liquid or multiphasic,
. , liquid/solid separation to make a preliminary determination of
. percent solids is required. This involves the filtration device
described in Section 4.3.2 and is outlined 'in Sections 7.1.1.3
through 7.1.1.9.
7.1.1.3 Pre-weigh the filter and the container that will
receive the filtrate.
7.1.1.4 Assemble the filter holder and filter following
the manufacturer'^ instructions. Place the filter on the support
screen and secure.
7.1.1.5 Weigh out a subsample of the waste (100 gram
minimum) and record the weight.
7.1.1.6 Allow slurries to stand to permit the solid
phase to settle. Wastes that settle slowly may .be centrifuged
prior to-filtration. "Centrifugation is to be used only as an aid
to filtration. flf used, the liquid should be decanted and filtered
followed by filtration of the 'solid portion of the waste through
the same filtration system. • . ' '
7.1.1.7 Quantitatively transfer the waste sample to the
filter holder (liquid and solid phases). Spread the waste sample
evenly over the surface of the filter. If filtration of the waste
at 4 "C reduces the amount of expressed liquid.over- what would be
expressed at room temperature then allow the sample to warm up to
room temperature in the device before filtering'. ,
NOTE: If waste material (>1% of original: sample Weight) has obviously
adhered to the container used to transfer the sample to the
filtration apparatus, determine the weight of this residue and
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subtract it from the sample weight determined in Section 7.1.1.5 to
determine the weight of the waste sample that will be filtered.
Gradually apply vacuum or gentle pressure of 1-10 psi,
until air or pressurizing gas moves through the filter. If this
point is not reached under 10 psi, and if no additional liquid has
passed.through the filter in any 2 minute interval, slowly increase
the pressure in 10 psi increments to a maximum of 50 psi. After
each incremental increase of 10 psi, if the pressurizing gas has
not moved through the filter, and if -no additional liquid has
passed-,through the filter in any 2 minute interval,- proceed to the
next 10 psi increment. When the pressurizing gas begins to move
through the filter, or when liquid flow has ceased at 50 psi (i.e..
filtration does not result in any additional filtrate within any 2
minute period), stop the filtration. .
NOTE: Instantaneous application of high pressure can degrade the glass
fiber filter and may cause premature plugging.
7.1.1.8 The material in the filter holder is defined as
the solid phase of the waste, and the filtrate is.defined as the
liquid phase..
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in
Section 7.1.1.7, this material may not filter. If this is the
case, the material within the filtration device is defined as a
solid: Do not replace the original filter with, a fresh filter
under any circumstances. Use only one filter.
7.1.1..9 Determine the weight of the liquid phase by
N subtracting the weight of the filtrate container (see Section
7.1.1.3) from the total weight of the filtrate-filled container..
Determine the weight of the solid phase of the waste sample by
subtracting the weight of the liquid phase from the weight,of the
total waste sample, as determined in Section 7.1.1.5 or 7.1.1.7.
Record the weight of the liquid and solid phases.
Calculate the percent solids as follows:
Weight of solid.(Section 7.1.1.9)
Percent solids = : '•—=———: - x 100
Total weight of waste (Section 7.1.1.5 or. 7.1.1.7)
7.1.2 If the percent solids.determined in Section 7.1.1.9. is
equal to or greater than 0.5%, then proceed either to Section 7.1.3 to
determine whether the solid material requires particle size reduction or
to Section 7.1.2.1 if it is noticed that a small amount of the filtrate is
entrained in wetting of the filter. If the percent solids determined in
Section 7.1.1.9 is less than 0.5%, then proceed to Section 7.2.9 if the
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nonvolatile TCLP is to be performed and to Section 7.3 with a fresh
portion of the waste if the volatile TCLP is to be performed.
. 7.1.2.1 Remove the solid phase and filter from the
filtration apparatus.
: 7.1.2.2 Dry the filter and solid phase at 100 +• 20 °C
•< until two successive weighing yield the same value within ± 1%.
Record the final weight. ' ,
NOTE: Caution should be taken to ensure that the subject solid will not
flash upon heating. It is recommended that the drying oven be
vented to a hood or other appropriate device.
7.1.2.3 Calculate the percent dry solids as follows:
(Wt. of dry waste + filter) - tared wt. of filter
Percent dry solids = —— : x 100
, Initial wt. of waste (Section 7.1.1.5 or 7.1.1.7)
7.1.2.4 If the percent dry solids is less than 0.5%,
then proceed to Section 7.2.9 if the nonvolatile TCLP is to be
performed, and to Section 7.3 if the volatile TCLP. is to be
performed. If tjie percent dry solids is greater than or equal to
, 0.5%, and if the nonvolatile TCLP is to be performed, return to the
beginning of this Section (7'.1) and, with a fresh portion of waste,
determine whether particle size reduction is necessary (Section
7.1.3) and determine the appropriate extraction fluid (Section
7.1.4); If only the volatile TCLP is to be performed, see the note
in Section 7.1.4.
7.1.3 Determination of whether the waste requires particle size
reduction (particle size is reduced during this step): Using the solid
portion, of the waste, evaluate the solid for particle size. Particle size
reduction is required, unless the solid has a surface area per gram of
material equal to or greater than 3.1 cm2, or is smaller than 1 cm in its
narrowest dimension (i.e., is capable of passing through a 9.5 mm (0.375
•'•: l.} standard s.ieve). If the surface area is smaller or the particle
size larger' than described above, prepare the solid portion of the waste
for extraction by crushing, cutting, or grinding the waste to a surface
area or particle size as described above. If the solids are prepared for
'organic volatiles extraction, special precautions must be taken (see
Section 7.3.6).
NOTE: Surface area criteria are meant for filamentous (e.g.. paper, cloth, and
similar) waste materials. Actual measurement of surface area is not
required, nor is it recommended. For materials that do not obviously meet
the criteria, sample specific methods would need to be developed and
. .employed to measure the surface area. Such methodology is currently not
available.
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7.1.4 Determination of appropriate extraction fluid: If the
solid content of the waste is greater than or equal to 0.5% and if the
sample will be extracted for nonvolatile constituents (Section 7.2),
determine the. appropriate fluid (Section 5.7) for the nonvolatiles
extraction as follows:
NOTE: TCLP extraction for volatile constituents uses only extraction
fluid #1 (Section 5.7.1). Therefore, if TCLP extraction for
nonvolatiles is riot required, proceed to Section 7.3.
7.1.4.1 Weigh out a small subsample of the.sol id phase
of the waste, reduce the solid (if necessary) to ,a particle size of
approximately 1 mm in diameter or less, and transfer 5.0 grams of
the solid phase of the waste to a 500 ml beaker or Erlenmeyer
flask. •
7.1.4.2 Add 96.5 ml of reagent water to the beaker,
cover with a watchglass, and stir vigorously for 5 minutes using a
magnetic stirrer. Measure and record the pH. . If the pH is <5.0,
use extraction fluid #1. Proceed to Section 7.2.
1 s
7.1.4.3 If the pH from Section 7:1.4.2 is >5.0, add
3.5 mL IN HC1, slurry briefly, cover with a watchglass, heat to 50
°C, and hold at 50 'C for 10 minutes.
7.1.4.4 Let the solution cool to room temperature and
record the pH. If the pH is <5.0, use extraction fluid #1. If the
pH is >5,0, use extraction fluid #2. Proceed to Section 7.2.
7.1.5 If the aliquot of the waste used for the preliminary
evaluation (Sections 7.1.1 - 7.1.4) was determined to be 100% solid at
Section 7.1.1.1, then it can be used for the Section 7.2 extraction
(assuming at least 100 grams remain), and the Section 7.3 extraction
(assuming at least 25 grams remain). If the aliquot was subjected to the
procedure in Sect.ion 7.1.1.7, then another aliquot shall be used for the
volatile extraction procedure in Section 7.3. The aliquot of the waste
subjected to the procedure in Section 7.1.1.7 might be appropriate for use
f.:\' the Section 7.2 extraction if an adequate amount of solid (as
determined by Section 7.1.1.9) was obtained. The amount of solid
necessary is dependent upon whether a sufficient amount of extract will 'be
produced to support the analyses. If an adequate amount of solid remains,
proceed to Section 7.2.10 of the nonvolatile TCLP extraction.
\
7.2 Procedure When Volatiles are not Involved
A minimum sample size of 100 grams (solid and liquid phases)' is recommend-
ed. In some cases, a larger sample size may be appropriate, depending on the
solids content of the waste sample (percent solids, See Section 7.1.1), whether
the initial liquid phase of the waste will be miscible with the aqueous extract
of the solid, and whether inorganics, semi volatile organics, pesticides, and
herbicides are all analytes of concern. Enough solids should be generated for
extraction such that the volume of TCLP extract will, be sufficient to support all
- 1311- 10 Revision 0
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of the analyses required. If the amount of extract generated by a single TCLP
extraction will hot be sufficient to perform all of the analyses, more than one
extraction may be performed and the extracts from each combined and aliquoted for
analysis. /
7.2.1 If the waste will obviously yield no liquid when subjected
to pressure filtrationy(iJL-> is 100% solid, see Section 7.1.1), weigh out
a subsample.of the waste (100 gram minimum) and,proceed to Section 7.2.9.
7.2.2 If the sample is liquid or multiphasic, liquid/solid
separation is required. This involves the filtration device described in
Section 4.3.2 and is outlined in Sections 7.2.3 to 7.2.8.\
/ • • . .•''-.
7.2.3 Pre-weigh the container that will receive the filtrate.
7.2.4 Assemble the filter holder and filter following the
manufacturer's instructions. Place the filter on the support screen and
secure. Acid wash the filter if evaluating the mobility of metals (see
Section 4.4). , ' • :
NOTE: Acid washed filters may be used for all nonvolatile extractions
even when metals are not of concern. >-
7.2.5 Weigh out a subsample of the waste (100 gram minimum) and
record the weight. If the waste contains <0.5%, dry solids (Section
7.1.2), the liquid portion of the waste, after filtration, is defined as
the TCLP extract. Therefore, enough of. the sample should be filtered so
that the amount of filtered liquid will support all of the analyses
required of the TCLP extract. For wastes containing >0.5/i dry solids
(Sections 7.1.1 or 7.1.2), use the percent solids information obtained in
Section 7.1.1 to determine the optimum sample size (100 gram minimum) for
filtration. Enough solids should be generated by filtration to,support
the analyses to be performed on the TCLP^extract.
7.2.6 Allow slurries to stand to permit the solid phase to
settle. Wastes that settle slowly may be centrifuged prior to filtration.
Use centrifugation only as an aid to filtration. 'If the waste is
Ccidnfuged, the liquid should .be decanted and filtered followed by
filtration of the solid portion of the waste through the same filtration
system. , ,
7.2.7 , ; Quantitatively transfer the waste sample (liquid and solid
phases) to the filter holder (see Section 4.3.2). Spread the waste sample
evenly over the surface of the filter. If filtration of the waste at.4 °C
reduces the amount of expressed liquid over what would be expressed at
room .temperature, then allow the sample to warm up to room temperature in
the device before filtering.
' ' ' ' *
NOTE: " If waste material (>1% of the original sample weight) has obviously
adhered to the container used to transfer the sample to the
filtration apparatus, determine the weight of this residue and
1311,- 11 Revision 0
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subtract it from the sample weight determined in Section 7.2.5, to
determine the weight of the waste sample that will be filtered.
.Gradually apply vacuum or gentle pressure of 1-10 psi, until air or
pressurizing gas moves through the filter. If this point is not reached
under 10 psi, and if no additional liquid has passed through the filter.in
any 2 minute interval, slowly increase the pressure in 10 psi" increments
to a maximum of 50 psi. After each incremental increase of 10 psi, if the
pressurizing gas has not moved through the filter, and if no additional
liquid has passed through the filter in any 2 minute interval, proceed to
the next 10 psi increment. When the pressurizing gas begins to move
through the filter, or when the liquid flow has ceased at 50 psi (i.e..
filtration does not result in any additional filtrate within a 2 minute
period), stop 'the filtration.
NOTE: Instantaneous application of high pressure can degrade the glass
fiber filter and may cause premature plugging.
7.2.8 The material in the filter holder is defined as the solid
phase of the waste, and the filtrate is defined as the liquid phase.
Weigh the filtrate. The liquid phase may now be either analyzed (See
Section 7.2.12),or stored at 4 °C until time of analysis.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in
Section 7.2.7, this material may not filter. If this is the case,
the material within the filtration device is defined as a solid and
is carried through the extraction as a solid. Do not replace the
original filter with a fresh filter under any circumstances. Use
only one filter.
7.2.9 If the waste contains <0.5% dry solids (see Section
7.1.2), proceed to Section 7.2.13. If the waste contains >0.5% dry solids
(see Section 7.1.1 or 7.1.2), and if particle size
-------
7.2.11 Determine the amount of extraction fluid to add to the
extractor vessel as follows:
20 x percent solids (Section 7.1.1) x weight of waste
, filtered (Section 7.2.5 or 7.2.7)
Weight of = —: — ;—-—
extraction fluid 100,
Slowly add this amount of appropriate extraction fluid (see Section
7.1.4) to the extractor vessel. Close the extractor bottle tightly (it is
recommended that Teflon tape be used to ensure a tight seal), secure in
rotary agitation device, and rotate at 30 ± 2 rpm for 18 + 2 hours.
Ambient temperature (i.e.. temperature of room in which extraction takes
place) shall be maintained at 23 + 2 °C during the extraction period.
NOTE: As agitation continues, pressure may build up within, the extractor
bottle for some types of wastes (e..g.. limed or calcium carbonate
containing waste may evolve gases such as carbon dioxide). To
relieve excess pressure, the extractor bottle may be periodically
opened (e.g.. after 15 minutes, 30 minutes, and 1 hour) and vented.
into a hood. ,
7.2.12 Following the 18 + 2 hour extraction, separate the
material in the extractor vessel into its component liquid and solid
phases by filtering through a new glass fiber filter, as outlined in
Section 7.2.7. For final filtration of the TCLP extract, the glass fiber
filter may be changed, if necessary, to facilitate filtration. .Filter(s)
shall be acid-washed (see Section 4.4) if evaluating the mobility of
metals. .
7.2.13 Prepare the TCLP extract as follows:
7.2.13.1 If the waste contained no initial liquid
phase, the filtered liquid material ..obtained from Section 7.2.12 is
defined as the TCLP extract. Proceed to Section 7.2.14.
7.2.13.2 If compatible (e.g., multiple phases will not
•result.on combination), combine the filtered liquid resulting from
Section 7.2.12 with the initial liquid phase of the waste obtained
in Section 7\2.7. This combined liquid is defined as the TCLP
extract. Proceed to Section 7.2,14.
. 7.2.13.3 If the initial liquid phase of the waste, as
obtained from Section 7.2.7, is not or may not be compatible with
the filtered'liquid resulting from Section 7.2..12, do not combine
these liquids. Analyze these liquids, collectively defined as the
TCLP extract, and combine the results mathematically, as described
. in Section 7.2.14.
i •
7.2.14 Following collection of the TCLP extract, the pH of the
extract should be recorded. Immediately aliquot and preserve the extract
for analysis. Metals aliquots must be acidified with nitric acid to
1311- 13 Revision 0
' July 1992
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pH <2. If precipitation is observed upon addition of nitric acid, to a
small aliquot of the extract, then the remaining portion of the extract
for metals analyses shall not be acidified and the extract shall be
analyzed as soon as possible. All other aliquots must be stored under
refrigeration (4 °C) until analyzed. The TCLP extract shall be prepared
and analyzed according to appropriate analytical methods. TCLP extracts to
be analyzed for metals shall be acid digested except in those instances
where digestion causes loss of metallic analytes. If,an analysis of the
undigested extract shows that the concentration of any regulated metallic
analyte exceeds the regulatory level:,--then 'the waste is hazardous and
digestion of the extract is not necessary. However, data, on undigested
extracts alone cannot be used to demonstrate that the waste is not
hazardous. If the individual phases are to be analyzed separately,
determine the volume of the individual phases (to ± 0.5%), conduct the
appropriate analyses, and combine the results mathematically by using a
simple volume-weighted average:
, (V,) (C,) + (V2) (C2)
Final Analyte Concentration =
- v, + v2
where:
V, = The volume of the first phase (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L). ' ,
7.2.15 Compare the analyte concentrations in the TCLP extract
with the levels identified in the appropriate regulations. Refer to
Section 8.0(for quality assurance requirements.
7.3 Procedure When Volatiles are Involved
Use the ZHE device to obtain TCLP extract for analysis of volatile
compoun^ only. Extract resulting from the use of the ZHE shall not be used to
evaluate the mobility of nonvolatile analytes (e.g.. metals, pesticides, etc.).
The ZHE device has approximately a 500 mL internal capacity. The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional liquid may be forced out by lan applied pressure
of 50 psi), due to the need to add an amount of extraction fluid equal to 20
times the weight of the solid phase.
Charge the ZHE with sample only once and do not open the device until the
final extract (of the solid) has been collected. Repeated filling of the ZHE to
obtain 25 grams of solid is not permitted.
Do not allow the waste, the initial liquid phase, or the extract to be
exposed to the atmosphere for any more time than is absolutely necessary. Any
1311- 14 . Revision 0
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manipulation of these materials should be done when cold (4 °C) to minimize loss
of volatiles.
7.3.1 Pre-weigh the,(evacuated) filtrate collection container
(See Section 4.6) and set aside. If using a TEDLAR* bag, express all
liquid from the ZHE device into the bag, whether for the initial or final
liquid/solid separation, and take an aliquot from the.liquid in the bag
for analysis. The containers listed in Section 4.6 are recommended for
use under the conditions stated in Sections 4.6.1 - 4.6.3.
7l3.2 Place the ZHE piston within the body of the ZHE (it may be
helpful first to moisten the piston 0-rings slightly with extraction
.fluid). Adjust the piston within the ZHE body to a height that will
minimize the distance the piston will have to move once the ZHE is charged
with sample (based upon sample size requirements determined from Section
7.3, Section 7.1.1 and/or 7.1.2). Secure the gas inlet/outlet flange
(bottom flange) onto the ZHE body in accordance with the manufacturer's
instructions,. Secure the glass fiber filter between the support screens
and set aside. Set liquid inlet/outlet flange (top flange) aside.
7.3.3 If the waste is 100% solid (see Section 7.1.1), weigh out
a subsample (25 gram maximum) of the waste, record weight, and proceed to
Section 7.3.5. . „
7.3.4 If the waste contains < 0.5% dry solids (Section 7.1.2),
the liquid portion of waste, after filtration, is defined as the TCLP
extract. Filter enough of the sample so that the amount of filtered
liquid will support all of the volatile analyses required. For wastes
containing > 0.5% dry solids (Sections 7.1.1 and/or 7.1.2), use the
percent solids information obtained in Section 7.1.1 to determine the
optimum sample size to charge into the ZHE. The recommended.sample size
is .as follows:
7.3.4.1 For wastes containing < 5% solids (see Section
7.1.1), weigh out a-500' gram subsample of waste and record the
weight.
i /• ' .
7.3.4.2 For wastes containing > 5% solids (see Section
7.1.1), determine the amount of waste to charge into the ZHE as
follows:
.25
Weight of waste to charge ZHE = —— : x 100
percent solids (Section 7.1.1)
Weigh out a subsample of the waste of the appropriate size and
record the weight.
7.3.5 If particle size reduction of the solid portion of the
waste was required in Section 7.1.3, proceed to Section 7.3.6. If
1311- 15 > Revision 0
July 1992
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particle size reduction was not required in Section 7.1.3, proceed to
Section 7.3.7. .
7.3.6 Prepare the waste for extraction by crushing, cutting, or
grinding the solid portion of the waste to a surface area or particle size
as .described in Section 7.1.3. Wastes and appropriate reduction equipment
should be refrigerated, if possible, to 4 °C prior to particle size
reduction. The means used to effect particle size reduction must not
generate heat in and "of itself. If\reduction of the solid phase of the
waste is necessary, exposure of the waste to the atmosphere should be
avoided to the extent possible.
NOTE: Sieving of the waste is not recommended due to the possibility that
volatiles may be lost. The use of an appropriately graduated ruler
is recommended as an acceptable alternative. Surface area
requirements are meant for filamentous (e.g., paper,- cloth) and
similar waste materials. Actual measurement of surface area is not
recommended.
When the surface area or particle size has been appropriately
altered, proceed to Section 7.3.7.
7.3.7 Waste slurries need not be allowed to stand to permit the
solid phase to. settle. Do not centrifuge wastes prior to filtration.
7.3.8 Quantitatively transfer the entire sample (liquid and
solid phases) quickly to the ZHE.. Secure the filter and support screens
onto the top flange of the device and, secure the top flange "to the ZHE
body in accordance with the manufacturer's instructions. Tighten all ZHE
fittings and place the device in the vertical position (gas inlet/outlet
flange on the bottom). Do not attach the extract collection device to the
top plate.
NOTE: If waste material (>!%' of original sample weight) has obviously
adhered toNthe container used to transfer the sample to the ZHE,
determine- the weight of this residue- and subtract it from the
sample weight determined in,Section 7.3.4 to determine the weight
of the waste sample that will be filtered.
Attach a gas line to the gas inlet/outlet valve (bottom flange)
and, with the liquid inlet/outlet valve (top flange) open, begin applying
gentle pressure of 1-10 psi (or more if necessary) to force all headspace
slowly out of the ZHE device .into a hood. At the first appearance, of
. . liquid from the liquid inlet/outlet valve, quickly close, the valve and
discontinue pressure. If filtration 'of the waste at 4 "C reduces the
amount of expressed liquid over what would be expressed at room tempera-
ture, then allow the sample to warm up to room temperature in the device
before filtering. If the waste is 100% solid (see Section 7.1.1), slowly
increase the pressure to a maximum of 50 psi to force most of the
headspace out of the device and proceed to Section 7.3.12.
1311- 16 Revision 0
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7.3.9 Attach the evacuated pre-weighed filtrate collection
container to the liquid inlet/outlet valve and open the valve. Begin
applying gentle pressure of 1-10 psi to force the liquid phase of the
sample into the filtrate collection container. If no additional liquid
has passed through the filter in any 2 minute interval, slowly increase
the pressure in 10 psi increments to a maximum of 50 psi. After each
incremental increase of 10 psi, if no additional liquid has passed through
the filter in any 2 minute interval, proceed to the next 10 psi increment.
When liquid flow has ceased such that continued pressure filtration at 50
psi does not result in any additional filtrate within a 2 minute period,
stop the filtration. Close the liquid inlet/outlet valve, discontinue
pressure to the piston, and disconnect and weigh the filtrate collection
container.
NOTE: Instantaneous application of high pressure can degrade the glass
fiber filter and may cause premature plugging.
7.3.10 The material in the ZHE is defined as the solid phase of
the waste and the filtrate is defined as the liquid phase..
NOTE: " Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying pressure filtration, this material will not filter.
If this is the case, the material within the filtration device is
defined as a solid and is carried through the TCLP extraction as a
solid:
If the original waste contained <0.5% dry solids (see Section
7.1.2), this filtrate is. defined as the TCLP extract and is analyzed
directly. Proceed to Section 7.3.15.
7.3.11 The liquid ph'ase may now.be either analyzed immediately
(See Sections 7.3.13 through 7.3.15) or stored, at 4 "C under minimal
headspace conditions until time of' analysis'. Determine the weight of
extraction fluid #1 to add to the ZHE as follows:
20 x percent solids (Section 7.1.1) x weight .
of waste, filtered (Section 7.3.4 or 7.3.8)
Weight of extraction fluid = ——
100 -. .
7.3.12 The following Sections detail how to add the appropriate
amount of extraction fluid to the solid material within the ZHE and
agitation of the ZHE vessel. Extraction fluid #1 is used in all cases
(See Section 5.7).
7.3.12.1 With the ZHE in the vertical position, attach
a line from the extraction fluid reservoir to the liquid in-
let/outlet valve. The line used shall contain fresh extraction
fluid and should be preflushed with fluid to eliminate any air
pockets in the l,ine. Release gas pressure on the ZHE piston (from
the gas inlet/outlet valve), open the liquid inlet/outlet valve,
I
1311- 17 Revision 0
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and begin , transferring extraction fluid (by pumping or similar
means) into the ZHE. Continue pumping extraction fluid into the
ZHE until the appropriate amount of fluid has been introduced into
the device.
/-- , '
7.3.12.2 After the extraction fluid has been added,
immediately close the liquid inlet/outlet valve and disconnect the
extraction fluid line. Check the ZHE to ensure that all valves are
in their closed positions. Manually rotate the device in an
end-over-end fashion 2 or 3 times. Reposition the ZHE in the
vertical position with the liquid inlet/outlet valve on top.
Pressurize-the ZHE to 5-10 psi (if necessary) and slowly open the
liquid inlet/outlet valve1to bleed out any headspace (into.a hood)
that may have been introduced due to the addition of extraction
fluid. This bleeding shall be done quickly and shall be stopped at
the first appearance of liquid from the valve. Re-pressurize the
ZHE with 5-10 psi and check all ZHE fittings to ensure that they
are closed.
7.3.12.3 Place the ZHE in the rotary agitation appara-
tus (if it is not already there) and rotate at 30 + 2 rpm for 18 +
2 hours. Ambient temperature (i.e.. temperature ,of room in which
extraction occurs) shall be'maintained at 23 + 2 "C during agita-
tion. . .
7.3.13 Following the 18 + 2 hour agitation period, check the
pressure behind the ZHE piston by quickly opening and closing the gas
inlet/outlet valve and noting the escape of gas. If the pressure has not
been maintained (i.e.. no gas release observed), the device..is leaking.
Check the ZHE for leaking as specified in Section 4.2:1, and perform the
extraction again with a new sample of waste. If the pressure within the
device has been maintained, the material in the extractor vessel is once
again separated into its component liquid and solid phases. If the waste
contained an initial liquid phase, the liquid may be filtered directly
into the same filtrate collection container (i.e., TEDLAR* bag) holding the
initial liquid phase of the waste. A separate filtrate collection
container must be used if combining would create multiple phases, or there
i- not enough volume left within the filtrate collection container.
Filter through the glass fiber filter, using the ZHE device as discussed
in Section 7.3.9. All extract shall be filtered and collected if the
TEDLAR® bag.is used, if the extract is multiphasic, or if the waste
contained an initial liquid phase (see Sections 4.6 and 7.3.1).
NOTE: An in-line glass fiber filter,may be used to filter the material.
within the'ZHE if it is suspected that the glass fiber filter .has
been ruptured.
'.;-.' 7.3.14 If the original waste contained no initial liquid phase,
the filtered liquid material obtained from Section 7.3.13 is defined as
the TCLP extract. If the waste contained an initial liquid phase, the
1311- 18 Revision 0
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filtered liquid material obtained from Section 7.3.13 and the initial
liquid phase (Section 7.3.9) are collectively defined as the TCLP extract.
7.3.15 Following collection of the TCLP extract, immediately
prepare the extract for analysis and store with minimal headspace at 4 °C
until analyzed. Analyze the TCLP extract according to the appropriate
analytical methods. If the individual phases are to be analyzed
separately (i.e.. are not miscible), determine the volume of the
individual phases (to 0.5%), conduct the appropriate analyses, and combine
the results mathematically by using a simple volume-weighted average:
OM (CJ + (V2) (C2)
Final Analyte
Concentration V,+ V2
where:
VT = The volume of the first phases (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L),
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.3.16 Compare the analyte concentrations in the TCLP extract
with the levels identified in the appropriate regulations. Refer to
Section 8.0 for quality assurance requirements.
8.0 QUALITY ASSURANCE
8.1 A minimum of one blank (using the same extraction fluid as used for
the samples) must be analyzed for every 20 extractions that have been conducted
in an extraction vessel.
8.2 A matrix spike shall be performed, for each waste type (e.g.,
wastewater treatment sludge, contaminated soil, etc.) unless the result exceeds
the regulatory level and the data are being used solely to demonstrate that the
waste property exceeds the regulatory.level. A minimum of one matrix spike must
be analyzed for each analytical batch. As a minimum, follow the matrix spike
addition guidance provided in each analytical method.
8.2.1 Matrix spikes are to be added after filtration of the TCLP
extract and before preservation. Matrix spikes should not be added prior
to TCLP extraction of the sample. : x ; . ;
8.2.2 ." In most cases, matrix spikes should be added at a
concentration equivalent to the corresponding regulatory level. If the
analyte concentration is less than one half the regulatory level, the
spike concentration may be as low as one half of the analyte concentra-
tion, but may not be not less than five times the method detection limit.
In order to avoid differences in matrix effects, the matrix spikes must be
. 1311- 19 Revision 0
' . July 1992
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added to the same nominal .volume of TCLP extract as that which was.
analyzed for the unspiked sample.
V ' . '•-,'"
8.2.3 The purpose of the matrix spike is to monitor the
'. performance of the analytical methods used, and to determine whether
matrix .interferences exist. Use of other internal calibration methods,
modification of the analytical methods, or use of alternate analytical
methods may be needed to accurately measure the analyte concentration in
the TCLP extract when the recovery of the matrix spike is ^below the
expected analytical method performance.
8.2.4 Matrix spike recoveries are calculated by the following
formula:
%R (%Recovery) = 100 (X. - XJ/K
where:
Xs = measured value for the spiked sample,
Xu = measured value for the unspiked sample, and
K = known, value of the spike in the sample.
\ ' , '
8.3 All quality control measures described in the appropriate analytical
methods shall be followed. ' ,
. 8.4 The use of internal calibration quantitation methods shall be
employed for a metallic contaminant if: (1) Recovery of the contaminant from the
TCLP extract is not at least 50% and the concentration does not exceed the
regulatory level, and (2) The concentration of the contaminant measured in the
extract is within 20% of the appropriate regulatory level.
8.4.1. The method of standard additions shall be employed as the
internal calibration quantitation method for each metallic contaminant.
8.4.2 The .method of standard additions requires preparing
calibration standards in the sample matrix rather than reagent water or
blank solution. It requires .taking four identical aliquots of the
solution and adding known amounts of standard .to three of these aliquots.
The forth' aliquot is the unknown. • Preferably,.the first addition should
be prepared so that the resulting concentration is approximately 50% of
the expected concentration of the sample. The second»and third additions
should be prepared so that the concentrations are approximately 100% and
150% of the expected concentration of the sample. All four aliquots are
maintained at the same final volume by .adding reagent water or a blank
solution, and may need dilution adjustment to maintain the signals in the
linear range of the instrument technique. All four aliquots are analyzed.
8.4.3 Prepare a plot, or subject data to 1inear regression, of
instrument signals or external-calibration-derived concentrations as the
dependant variable (y-axis) versus concentrations of the additions of
standard as the independent variable (x-axis). Solve for the intercept of
1311- 20 Revision 0
July 1992
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the abscissa (the independent variable, x-axis) which is the concentration
in the unknown.
8.4.4 Alternately, subtract the instrumental signal or external-
calibration-derived concentration of the unknown (unspiked) sample from
the instrumental signals or external-calibration-derived concentrations of
the standard additions. Plot or subject to linear regression of the
corrected instrument signals or external-calibration-derived concentra-
tions as the dependant variable versus the independent variable. Derive
concentrations for unknowns using the internal calibration curve as if it
were an external calibration curve.
8.5
periods:
Samples must undergo TCLP extraction within the following time
, SAMPLE MAXIMUM HOLDING TIMES [Days]
'•'
Volatile*
Semi-volatiles
Mercury
Metals, except
mercury
From:
Field',
collection
To:
TCLP
extraction
14
14
28
180
From:
TCLP
extraction
To:
Preparative
extraction
NA
7
NA
NA
From:
Preparative
extraction
To:
Determinative
analysis
14
40
28
180
Total
elapsed
time
28
61
56
360
NA = Not applicable
If sample holding1, times .are exceeded, the values obtained will
minima"! concentrations. Exceeding the holding time is not
establishing that a waste does not exceed the regulatory level.
holding time will not invalidate characterization
regulatory.level.
be considered
acceptable in
Exceeding the
if the waste exceeds the
9.0 METHOD PERFORMANCE
9.1 Ruggedness. Two .ruggedness studies have been performed to determine
the effect of various perturbations on specific elements of the TCLP protocol.
Ruggedness testing determines the sensitivity of small procedural variations
which might be expected to occur during routine laboratory application.
9.1.1; Metals - The following conditions were used when leaching
i waste for metals analysis:
1311- 21
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. , Varying Conditions
Liquid/Solid ratio
Extraction time
Headspace
Buffer #2 acidity
Acid-washed filters
Filter type
Bottle type
^ 19:1- vs. 21:1
16 hours vs. 18 hours
20% vs. 60% .
190 meq vs. 210 meq
yes vs. no
0.7 /im glass fiber vs. 0.45 /urn
vs. polycarbonate
borosilicate vs. flint glass
Of the seven method variations examined, acidity of the extraction
fluid had the .greatest impact on the results. Four of 13 metals from an
API separator .sludge/electroplating waste (API/EW) mixture and two of
three metals from an ammonia lime still bottom waste were extracted at
higher levels by the more acidic buffer. Because of the sensitivity to pH
changes, the method requires that the extraction fluids be prepared so
that the final pH is within + 0.05'units as specified.
9.1.2 Volatile Organic Compounds - The following conditions were
used when leaching a waste for VOC analysis:
Varying Conditions
Liquid/Solid ratio
Headspace
Buffer #1 acidity
Methcr1 of storing extract
Aliquotting
Pressure behind piston
19:1 vs. 21:1
0% vs. 5%
60 meq vs. 80 meq .
Syringe vs. Tedlar* bag
yes vs. no
0 psi vs. 20 psi
None of the parameters had a significant effect on the results of
the ruggedness test.
9.2 Precision.Many TCLP precision (reproducibility) studieshave been
performed, and have shown that, in general, the precision of the TCLP is
comparable to or exceeds that of the EP toxicity test and that method precision
is adequate. One of the more significant contributions to poor precision appears
tov be related to sample homogeneity and inter-laboratory variation (due to the
nature of waste materials).
1311- 22
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9.2.1 Metals - The results of a multi-laboratory study are shown
in Table 6, ,and indicate that a single analysis of a waste may not be
adequate for waste characterization and identification requirements.
9.2.2 Semi-Volatile Organic Compounds - The results of two
studies, are shown in Tables 7 and 8. Single laboratory precision was
excellent with greater than 90 percent of the results exhibiting an RSD
less than 25 percent. Over 85 percent of all individual compounds in the
multi-laboratory study'fell in the RSD range of 20 - 120 percent. Both
studies concluded that the TCLP provides adequate precision. It was also
determined that the high acetate content of the extraction fluid did not
present problems (i .e., co.lumn degradation of the gas chromatograph) for
the analytical conditions used.
9.2.3 Volatile. Organic Compounds - Eleven laboratories
participated in a collaborative study of the use of the ZHE with two waste
types which were fortified with a mixture of VOCs. The results of the
collaborative study are shown in Table 9. Precision results for VOCs tend
to occur over a considerable range. However, the range and mean RSD
compared very closely to the same collaborative study metals results in
Table 6. Blackburn and Show concluded that at the 95% level of signifi-
cance: 1) recoveries among laboratories were statistically similar, 2)
recoveries did not vary significantly between the two sample types, and 3)
each laboratory showed the same pattern of recovery for each of the two
samples.
. " '•• i ' ... '
10.0 REFERENCES ./ ' . '
1. Blackburn, W.B. and Show,: I. "Collaborative Study of the Toxicity
Characteristics Leaching Procedure (TCLP)." Draft Final Report, Contract No! 68-
03-1958, S-Cubed, November 1986.
2. Newcomer, L.R., Blackburn, W.B., Kimmell, T..A. "Performance of the
Toxicity Characteristic Leaching Procedure." Wilson Laboratories, S-Cubed, U.S.
EPA, December 1986. . , .
3. Williams, L.R., Francis, C.W.; Maskarinec, M.P., Taylor D.R-., and Rothmai,
N. "Single-Laboratory Evaluation of Mobility Procedure for Solid Waste." EMSL,
ORNL, S-Cubed, ENSECO.
1311- 23 Revision 0
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Table 1.
Volatile Analytes1'2
Compound CAS No.
Acetone
Benzene
n-Butyl alcohol
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1,2-Dichloroethane :
1,1-Dichloroethylene
Ethyl acetate
Ethyl benzene
Ethyl ether
Isobutanol
Methanol
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Tetrachl oroethyl ene
Toluene ,
1,1,1,-Trichloroethane
Trichloroethylene ,
Tri chl prof 1 uoromethane
l,l,2-Trichloro-l,2,2-trifluoroethane
Vinyl chloride
Xylene
67-64-1
71-43-2
71-36-3
75-15-0
56-23-5
108-90-7
67-66-3,
107-06-2
75-35-4
141-78-6
100-41-4
60-29-7
78-83-1
67-56-1
75-09-2 .
78-93-3
108-10-1
127-18-4
108-88-3
71-55-6
79-01-6
75-69-4
76-13-1
75-01-4
1330-20-7
1 When testing for any or all of these analytes, the zero-headspace
extrx.Lo; vessel shall be used instead of the bottle extractor.
2 Benzene, carbon tetrachloride, chlorobenzene, chloroform,
1,2-dichloroethane, l,lTdichlproethylene, methyl ethyl ketone,
tetrachloroethylene, and vinyl chloride are toxicity characteristic
constituents.
1311- 24 Revision 0
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Table 2. ,••
Suitable Rotary Agitation Apparatus1
Company
Location
Model No.
Analytical Testing and
Consulting Services,
Inc.
Associated Design and
Manufacturing Company
Environmental Machine and
Design, Inc.
IRA Machine.Shop and
Laboratory
Lars Lande Manufacturing
Mi Hi pore Corp.
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Lynchburg, VA
(804) 845-6.424
Santurce, PR
(809) 752-4004
4-vessel extractor (DC20S)
8-vessel extractor (DC20)
12-vessel extractor (DC20B)
24-yessel extractor (DC24C)
2-vessel
4-vessel
6-vessel
8-vessel
12-vessel
24-vessel
(3740-2-BRE)
(3740-4-BRE)
(3740-6-BRE)
(3740-8-BRE)
(3740-12-BRE)
(3740-24-BRE)
8-vessel (08-00-00)
4-vessel (04-00-00)
8-vessel (011001)
Whitmore Lake, MI 10-vessel (10VRE)
(313) 449-4116 5-vessel (5VRE)
6-vesseT (6VRE)
Bedford, MA
(800) 225-3384
4-ZHE or
4 2-liter'bottle
. extractor (YT310RAHW)
1 Any device that rotates the.extraction vessel in an end-over-end fashion at 30
+ 2 rpTi ::•: acceptable. . . .','.'
1311- 25
Revision 0
July 1992
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Table 3.
Suitable Zero-Headspace Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
Consulting Services, Inc.
Associated Design and
Manufacturing Company
Lars Lande Manufacturing2
Millfpore Corporation
Environmental Machine
and Design, Inc.
Gelman Science
Harrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Whitmore Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
Lynchburg,, VA
(804) 845-6424
Ann Arbor, MI
(800) 521-1520
CT02, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
ZHE-11, Gas
Pressure Device
YT30090HW,.Gas
Pressure Device •
VOLA-TOX1, Gas
Pressure Device
15400 Gas Pressure
Device
1 Any device that meets the specifications listed in Section 4.2.1 of the method
is suitable.
2 This device use.s a 110 mm filter.
1311- 26
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July 1992
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Table 4.
Suitable Filter Holders1
Model/
Company
Nucleopore Corporation
Micro Filtration
Systems
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Catalogue No.
425910
410400
302400
311400
Size .
.142 mm
47 mm
142 mm
47 mm
Millipore Corporation Bedford, MA YT30142HW 142 mm
(800)225-3384 XX1004700 47mm
1 Any device capable of separating the liquid from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed. Plastic devices (not listed above) may be used when
only inorganic analytes are of concern. The 142 mm size filter holder is
recommended.
1311- 27 Revision 0
July 1992
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'Table 5.
Suitable Filter Media1
Company
Millipore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Gelman Science .
Location
Bedford, MA
(800) 225-3384
Pleasanton, CA
(415) 463-2530
Clifton, NJ
(201) 773-5800 >
Dublin, CA
(800) 334-7132
(415) 828-6010
Ann Arbor, MI
(800) 521-1520
Model
AP40
211625
GFF
GF75
66256 (90mm)
66257 (142mm)
Pore !
Sue
(urn)
, 0.7
0.7
0.7
0.7
0.7
1 Any filter that meets the specifications in Section 4.4 of the Method is
suitable.
1311- 28
Revision 0
July 1992
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Table 6. Multi-Laboratory TCLP Metals, Precision
Waste
Ammonia
Lime' Still
Bottoms
API/EW
Mixture
Fossil
Fuel Fly
Ash
Extraction
Fluid
#1 •
n
n
n
n
n
n
n
Ji
#2
#1
n
n
n
' #1
n
n
n
Metal
Cadmium
Chromium
Lead
Cadmium
Chromium
Lead
Cadmium
Chromium
Lead
1
X
0.053
0.023
0.015
0.0032
0.0030
0.0032
0.0046
0.0005
0.0561
0.105
0,0031
0.0124
0.080
0.093
0.017
0.070
0.0087
0.0457
S
0.031
0.017
. 0.0014
0.0037
0.0027
0.0028
0.0028
0.0004
0.0227
0.018
0.0031
0.0136
0:069
0.067
0.014
0.040
v 0.0074
0.0083
-
%RSD
60
76
93
118
90
87
61
77
40
17
100
110
86
72
85
57
85
.18
%RSD Range = 17 - 118
' • • Mean '%RSD = 74
NOTE: X = Mean results from 6 - 12 different laboratories
Units = mg/L
Extraction Fluid #1 = pH 4.9
n - pH 2.9
1311- 29
Revision 0
July 1992
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Table 7. Single-Laboratory Semi-Volatiles, Precision
Waste
Ammonia
Lime Still
Bottoms
'
„
_
API/EW
Mixt.ure
~"
.
" Compound
Phenol
2-Methyl phenol
4-Methyl phenol
2,4-Dimethylphenol
Naphthalene
2-Methyl naphthalene
Dibenzofuran
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
. Phenol
2,4-Dimethylphenol
Naphthalene
2-Methyl naphthalene
Extraction
Fluid
#1
• n .
n
n
n
• n
n
n
n .
n :
n
n
#1
•n
n .
n
n
n '
n .
J2 ..
#1
• n
• n ' •
n .'
#1
J2
#1-
, #2
n
n
n ' .
n
. X
19000
19400
2000
1860
7940
7490
321
307
3920
3827
290
273 /
187
187
703
663
151
156
241
.243
33.2
34.6
25.3
26.0
40'. 7
19.0
33.0
. 43.3
185
165
265
200
-S
2230
929
297
52.9
1380
200
46.8
45.8
413
176
44.8
19.3
22.7
7.2
89.2
20.1
17.6
2.1
22.7
7.9
, 6.19
1.55
• 1.8
1.8-
13.5
1.76
9.35
'8.61.
29.4
24.8
61.2
18.9
%RSO
11.6
4.8
14.9
2.8
17.4
2.7
14.6
14.9
10.5
4.6
15.5
7.1
12.1
3.9
12.7
3.0
11.7
1.3
9.4
3.3
18.6
4.5
7.1
7.1
33.0
9.3
28.3
19.9
15.8
15.0
23.1
9.5
%RSD Range =1-33
, . Mean %RSD = 12
NOTE: Units = M9/L
Extractions were performed in triplicate
All results were at least 2x the detection limit
Extraction Fluid #1 = pH 4.9
n = pH 2..9
1311- 30
Revision 0
July 1992
-------
Tables. Multi-Laboratory Semi-Volatiles, Precision
Waste
Ammonia Lime
Still Bottoms. (A)
API/EW
Mixture (B)
Fossil Fuel
Fly Ash (C)
Compound
- BNAs
BNAs
BNAs
Extraction
Fluid
"#1
. n .
• n
n
#1- ,
n
X
10043
10376
1624
2074
750
739
S
7680
6552
675
1463
175
342
%RSD
76.5
63.1
41.6
70.5 ,
23.4
46.3
' Mean %RSD = 54
NOTE: Units
X = Mean results from 3 - 10 labs
Extraction Fluid #1 = pH 4.9
n = pH 2.9 .
%RSD Range for Individual Compounds
A, #1
A, #2
B, #1
B, n
C, #1
C, n
0
28
20
49
36
61
113
108
156
.128
143
164
1311- 31
Revision 0
July 1992
-------
Table 9. -Multi-Laboratory (11 Labs) VOCs, Precision
\
Waste
Mine
Tailings
c
Ammonia
Lime Still
Bottoms
Compound
Vinyl chloride
Methyl ene chloride
Carbon disulfide
1,1-Dichlproethene ,
1, 1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1-Trichloroethane
Carbon tetrachloride
Trichloroethene
1,1,2-Trichloroethene
Benzene
1,1,2 , 2-Tetrachl oroethane
Toluene
Chlorobenzene , ' .
Ethyl benzene
Tri chl orof 1 uoromethane
Acryloni.trile
Vinyl chloride .
Methyl ene chloride
Carbon disulfide
1,1-Dichlorbethene
1, 1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1-Trichloroethane
Carbon tetrachloride
Trichloroethene
1 , 1 , 2-Tri chl oroethene
Benzene
1 , 1 ,-2 , 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
X
6.36
12.1
5.57
21.9
31.4
'46.6 ..
47.8
43.5
20.9
12.0
24.7
\ 19.6
37. ,9
34.9
29.3
35.6
4.27
3.82
76.7
5.00
14.3
3.37
52.1
52.8
64.7 "
4:3 . 1
59.0
53.. 6
'7.10
57.3
6.7
6.1.3
3.16
69.0
71.8
3.70
- 4.05
29.4.
S
6.36
11.8
2.83
27.7
25.4
29.2
33.6
36.9
20.9
8.2
21.2
10.9
28.7
25.6
11.2
19.3
2.80
4.40
110.8
\
4.71
13.1
2.07
38.8
25.6
28.4
31.5
39.6
40.9
6.1
34.2
4,7
26.8
2.1
18.5
12.0
2.2
4.8
34.8
%RSD
100
98
51
127
81
63
70
85
100
68
86
56
76
73
38
54
66
115
144
94
92
61.
75
49
44 .
73
67
76
86
60
70
44
• 66
27
17
58
119
118
- . • %RSD Range = 17 - 144 I
/ r . .: - Mean.%RSD = 75
NOTE:. Units = /ig/L-
1311- 32
Revision 0
July 1992
-------
Motor
(30± 2 rpm)
Extraction Vessel Holder
Figure 1. Rotary Agitation Apparatus
Liquid Inlet/Outlet Valve
Top Flange
Support Screen-
Filter
Support Screen
Vrton o-rings
Bottom Flange—^L
cLj
Pressurized Gas •
Inlet/Outlet Valve
Sample
Piston
Gas
L_J
Pressure
Gauge
Figure 2. Zero-Headspace Extractor (ZHE)
1311- 33 :
Revision 0
July 1992
-------
METHOD 1311.
TOx'lCITY CHARACTERISTIC LEACHATE PROCEDURE
START
sub
Us.
> a
-sample
of
vaste
!sepa
liquid]
solids •
• 0 8 un
fiber t
ate
from
ith 06
* glass
liter
Discard
solids
< 0 SX •
- >*wha
/ thi
solids
X. »*'
X X. > 0 5X
e? /
10 OX
• Examine
solids
Separate
liquids from
solids mth 0 6
• 0 8-um glass
fiber filter
«
Solid
Liquid
•l
YBJ,
•E>tract ./
appropriate fluid
1) Bottle entractor
for npn-volatiies
2) ZHE device for
volatiles
Reduce
particle size
to <9 5 mm
1311- 34
Revision 0
July 1992
-------
METHOD 1311 (CONTINUED)
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE
Discard
solids
Solid
liquid
compatible \. No
• ith the
extract'
Separate
••tract from
•olidi •/ 0 6
0 8 urn glass
fiber filter
Measure am
liquid and
(mathemat cal
combine re
result of
aha 1ys
nt of
na1yze
ly
ult »/
xtract
Combina
extract w/
liquid phase
'of was te
Analyze
1iquid
STOP
1311- 35
Revision 0
July 1992
-------
1312
-------
METHOD 1312
SYNTHETIC PRECIPITATION LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION
1.1 Method 1312 is designed to determine the mobility of both organic
and inorganic analytes present in liquids, soils, and wastes.
2.0 SUMMARY OF METHOD
2.1 For liquid samples (i .e.. those containing less than 0.5 % dry
solid material), the sample, after filtration through a 0.6 to 0.8 nm glass
fiber filter, is defined as the 1312 extract.
2.2 For samples containing greater than 0.5 % solids, the liquid phase,
if any, is separated from the solid phase and stored for later analysis; the
particle size of the solid phase is reduced, if necessary. The solid phase is
extracted with an amount of extraction fluid equal to 20 times the weight of the
solid phase. The extraction fluid employed is a function of the region of the
country where the sample site is located if the sample is a soil. If the sample
is a waste or wastewater, the extraction fluid employed is a pH 4.2 solution.
A special extractor vessel is used when testing for volatile analytes (see Table
1 for a list of volatile compounds). Following extraction, the liquid extract
is separated from the solid phase by filtration through a 0.6 to 0.8 /urn glass
fiber filter.
2.3 If compatible (i.e., multiple phases will not form on combination),
the initial liquid phase of the waste is added to the liquid extract, and these
are analyzed together. If incompatible, the liquids are analyzed separately and
the results are mathematically combined to yield a volume-weighted average
concentration.
3.0 INTERFERENCES
3.1 Potential interferences that may be encountered during analysis are
discussed in the individual analytical methods.
4.0 APPARATUS AND MATERIALS
4.1 Agitation apparatus: The agitation apparatus must be capable of
rotating the extraction vessel in an end-over-end fashion (see Figure 1) at 30
+ 2 rpm. Suitable devices known to EPA are identified in Table 2.
4.2 Extraction Vessels
4.2.1 Zero Headspace Extraction Vessel (ZHE). This device is for
use only when the sample is being tested for the mobility of volatile
analytes (i.e., those listed in Table 1). The ZHE (depicted in Figure 2)
allows for liquid/solid separation within the device and effectively
precludes headspace. This type of vessel allows for initial liquid/solid
separation, extraction, and final extract filtration without opening the
1312 - 1 Revision 0
September 1994
-------
vessel (see Step 4.3.1). These vessels shall have an internal volume of
500-600 ml and be equipped to accommodate a 90-110 mm filter. The devices
contain VITON*1 0-rings which should be replaced frequently. Suitable ZHE
devices known to EPA are identified in Table 3.
For the ZHE to be acceptable for use, the piston within the ZHE
should be able to be moved with approximately 15 psig or less. If it
takes more pressure to move the piston, the 0-rings in the device should
be replaced. If this does not solve the problem, the ZHE is unacceptable
for 1312 analyses and the manufacturer should be contacted.
The ZHE should be checked for leaks after every extraction. If the
device contains a built-in pressure gauge, pressurize the device to 50
psig, allow it to stand unattended for 1 hour, and recheck the pressure.
If the device does not have a built-in pressure gauge, pressurize the
device to 50 psig, submerge it in water, and check for the presence of air
bubbles escaping from any of the fittings. If pressure is lost, check all
fittings and inspect and replace 0-rings, if necessary. Retest the
device. If leakage problems cannot be solved, the manufacturer should be
contacted.
Some ZHEs use gas pressure to actuate the ZHE piston, while others
use mechanical pressure (see Table 3). Whereas the volatiles procedure
(see Step 7.3) refers to pounds-per-square-inch (psig), for the
mechanically actuated piston, the pressure applied is measured in torque-
inch-pounds. Refer to the manufacturer's instructions as to the proper
conversion.
4.2.2 Bottle Extraction Vessel. When the sample is being
evaluated using the nonvolatile extraction, a jar with sufficient capacity
to hold the sample and the extraction fluid is needed. Headspace is
allowed in this vessel.
The extraction bottles may be constructed from various materials,
depending on the analytes to be analyzed and the nature of the waste (see
Step 4.3.3). It is recommended that borosilicate glass bottles be used
instead of other types of glass, especially when inorganics are of
concern. Plastic bottles, other than polytetrafluoroethylene, shall not
be used if organics are to be investigated. Bottles are available from a
number of laboratory suppliers. When this type of extraction vessel is
used, the filtration device discussed in Step 4.3.2 is used for initial
liquid/solid separation and final extract filtration.
4.3 Filtration Devices: It is recommended that all filtrations be
performed in a hood.
4.3.1 Zero-Headspace Extraction Vessel (ZHE): When the sample
is evaluated for volatiles, the zero-headspace extraction vessel described
in Step 4.2.1 is used for filtration. The device shall be capable of
1VITON® is a trademark of Du Pont.
1312 - 2 Revision 0
September 1994
-------
supporting and keeping in place the glass fiber filter and be able to
withstand the pressure needed to accomplish separation (50 psig).
NOTE: When it is suspected that the glass fiber filter has been
ruptured, an in-line glass fiber filter may be used to filter the
material within the ZHE.
4.3.2 Filter Holder: When the sample is evaluated for other than
volatile analytes, a filter holder capable of supporting a glass fiber
filter and able to withstand the pressure needed to accomplish separation
may be used. Suitable filter holders range from simple vacuum units to
relatively complex systems capable of exerting pressures of up to 50 psig
or more. The type of filter holder used depends on the properties of the
material to be filtered (see Step 4.3.3). These devices shall have a
minimum internal volume of 300 ml and be equipped to accommodate a minimum
filter size of 47 mm (filter holders having an internal capacity of 1.5 L
or greater, and equipped to accommodate a 142 mm diameter filter, are
recommended). Vacuum filtration can only be used for wastes with low
solids content (<10 %) and for highly granular, liquid-containing wastes.
All other types of wastes should be filtered using positive pressure
filtration. Suitable filter holders known to EPA are listed in Table 4.
4.3.3 Materials of Construction: Extraction vessels and
filtration devices shall be made of inert materials which will not leach
or absorb sample components of interest. Glass, polytetrafluoroethylene
(PTFE), or type 316 stainless steel equipment may be used when evaluating
the mobility of both organic and inorganic components. Devices made of
high-density polyethylene (HOPE), polypropylene (PP), or polyvinyl
chloride (PVC) may be used only when evaluating the mobility of metals.
Borosilicate glass bottles are recommended for use over other types of
glass bottles, especially when inorganics are analytes of concern.
4.4 Filters: Filters shall be made of borosilicate glass fiber, shall
contain no binder materials, and shall have an effective pore size of 0.6 to
0.8-Mm . Filters known to EPA which meet these specifications are identified
in Table 5. Pre-filters must not be used. When evaluating the mobility of
metals, filters shall be acid-washed prior to use by rinsing with IN nitric acid
followed by three consecutive rinses with reagent water (a minimum of 1-L per
rinse is recommended). Glass fiber filters are fragile and should be handled
with care.
4.5 pH Meters: The meter should be accurate to + 0.05 units at 25°C.
4.6 ZHE Extract Collection Devices: TEDLAR*2 bags or glass, stainless
steel or PTFE gas-tight syringes are used to collect the initial liquid phase and
the final extract when using the ZHE device. These devices listed are
recommended for use under the following conditions:
4.6.1 If a waste contains an aqueous liquid phase or if a waste
does not contain a significant amount of nonaqueous liquid (i.e., <1 % of
^EDLAR* is a registered trademark of Du Pont.
1312 - 3 Revision 0
September 1994
-------
total waste), the TEDLAR9 bag or a 600 mL syringe should be used to collect
and combine the initial liquid and solid extract.
4.6.2 If a waste contains a significant amount of nonaqueous
liquid in the initial liquid phase (i.e., >1 % of total waste), the
syringe or the TEDLAR8 bag may be used for both the initial solid/liquid
separation and the final extract filtration. However, analysts should use
one or the other, not both.
4.6.3 If the waste contains no initial liquid phase (is 100 %
solidj^or has no significant solid phase (is <0.5% solid) , either the
TEDLAR* bag or the syringe may be used. If the syringe is used, discard
the first 5 mL of liquid expressed from the device. The remaining
aliquots are used for analysis.
4.7 ZHE Extraction Fluid Transfer Devices: Any device capable of
transferring the extraction fluid into the ZHE without changing the nature of the
extraction fluid is acceptable (e.g.. a positive displacement or peristaltic
pump, a gas-tight syringe, pressure filtration unit (see Step 4.3.2), or other
ZHE device).
4.8 Laboratory Balance: Any laboratory balance accurate to within ±
0.01 grams may be used (all weight measurements are to be within + 0.1 grams).
4.9 Beaker or Erlenmeyer flask, glass, 500 mL^
4.10 Watchglass, appropriate diameter to cover beaker or Erlenmeyer
flask.
4.11 Magnetic stirrer.
i
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 defined as water in which an
interferant is not observed at or above the method's detection limit of the
analyte(s) of interest. For nonvolatile extractions, ASTM Type II water or
equivalent meets the definition of reagent water. For volatile extractions, it
is recommended that reagent water be generated by any of the following methods.
Reagent water should be monitored periodically for impurities.
5.2.1 Reagent water for volatile extractions may be generated
by passing tap water through a carbon filter bed containing about 500
grams of activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).
1312 - 4 Revision 0
September 1994
-------
5.2.2 A water purification system (Millipore Super-Q or
equivalent) may also be used to generate reagent water for volatile
extractions.
5.2.3 Reagent water for volatile extractions may also be prepared
by boiling water for 15 minutes. Subsequently, while maintaining the
water temperature at 90 + 5 degrees C, bubble a contaminant-free inert gas
(e.g. nitrogen) through the water for 1 hour. While still hot, transfer
the water to a narrow mouth screw-cap bottle under zero-headspace and seal
with a Teflon-lined septum and cap.
5.3 Sulfuric acid/nitric acid (60/40 weight percent mixture)
Cautiously mix 60 g of concentrated sulfuric acid with 40 g of concentrated
nitric acid. If preferred, a more dilute H2S04/HN03 acid mixture may be
prepared and used in steps 5.4.1 and 5.4.2 making it easier to adjust the pH of
the extraction fluids.
5.4 Extraction fluids.
5.4.1 Extraction fluid #1: This fluid is made by adding the
60/40 weight percent mixture of sulfuric and nitric acids (or a suitable
dilution) to reagent water (Step 5.2) until the pH is 4.20 + 0.05. The
fluid is used to determine the Teachability of soil from a site that is
east of the Mississippi River, and the Teachability of wastes and
wastewaters.
NOTE: Solutions are unbuffered and exact pH may not be attained.
5.4.2 Extraction fluid #2: This fluid is made by adding the
60/40 weight percent mixture of sulfuric and nitric acids (or a suitable
dilution) to reagent water (Step 5.2) until the pH is 5.00 + 0.05. The
fluid is used to determine the Teachability of soil from a site that is
west of the Mississippi River.
5.4.3 Extraction fluid #3: This fluid is reagent water (Step
5.2) and is used to determine cyanide and volatiles Teachability.
NOTE: These extraction fluids should be monitored frequently for
impurities. The pH should be checked prior to use to ensure that
these fluids are made up accurately. If impurities are found or
the pH is not within the above specifications, the fluid shall be
discarded and fresh extraction fluid prepared.
5.5 Analytical standards shall be prepared according to the appropriate
analytical method.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples shall be collected using an appropriate sampling plan.
6.2 There may be requirements on the minimal size of the field sample
depending upon the physical state or states of the waste and the analytes of
concern. An aliquot is needed for the preliminary evaluations of the percent
1312 - 5 Revision 0
September 1994
-------
solids and the particle size. An aliquot may be needed to conduct the
nonvolatile analyte extraction procedure. If volatile organics are of concern,
another aliquot may be needed. Quality control measures may require additional
aliquots. Further, it is always wise to collect more sample just in case
something goes wrong with the initial attempt to conduct the test.
6.3 Preservatives shall not be added to samples before extraction.
6.4 Samples may be refrigerated unless refrigeration results in
irreversible physical change to the waste. If precipitation occurs, the entire
sample (including precipitate) should be extracted.
6.5 When the sample is to be evaluated for volatile analytes, care
shall be taken to minimize the loss of volatiles. Samples shall be collected and
stored in a manner intended to prevent the loss of volatile analytes (e.g.,
samples should be collected in Teflon-lined septum capped vials and stored at
4°C. Samples should be opened only immediately prior to extraction).
6.6 1312 extracts should be prepared for analysis and analyzed as soon
as possible following extraction. Extracts or portions of extracts for metallic
analyte determinations must be acidified with nitric acid to a pH < 2, unless
precipitation occurs (see Step 7.2.14 if precipitation occurs). Extracts should
be preserved for other analytes according to the guidance given in the individual
analysis methods. Extracts or portions of extracts for organic analyte
determinations shall not be allowed to come into contact with the atmosphere
(i .e.. no headspace) to prevent losses. See Step 8.0 (Quality Control) for
acceptable sample and extract holding times.
7.0 PROCEDURE
7.1 Preliminary Evaluations
Perform preliminary 1312 evaluations on a minimum 100 gram aliquot of
sample. This aliquot may not actually undergo 1312 extraction. These
preliminary evaluations include: (1) determination of the percent solids (Step
7.1.1); (2) determination of whether the waste contains insignificant solids and
is, therefore, its own extract after filtration (Step 7.1.2); and (3)
determination of whether the solid portion of the waste requires particle size
reduction (Step 7.1.3).
7.1.1 Preliminary determination of percent solids: Percent
solids is defined as that fraction of a waste sample (as a percentage of
the total sample) from which no liquid may be forced out by an applied
pressure, as described below.
7.1.1.1 If the sample will obviously yield no free
liquid when subjected to pressure filtration (i.e., is 100% solid),
weigh out a representative subsample (100 g minimum) and proceed
to Step 7.1.3.
7.1.1.2 If the sample is vliquid or multiphasic,
liquid/solid separation to make a preliminary determination of
percent solids is required. This involves the filtration device
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discussed in Step 4.3.2, and is outlined in Steps 7.1.1.3 through
7.1.1.9.
7.1.1.3 Pre-weigh the filter and the container that will
receive the filtrate.
7.1.1.4 Assemble filter holder and filter following the
manufacturer's instructions. Place the filter on the support
screen and secure.
7.1.1.5 Weigh out a subsample of the waste (100 gram
minimum) and record the weight.
7.1.1.6 Allow slurries to stand to permit the solid phase
to settle. Samples that settle slowly may be centrifuged prior to
filtration. Centrifugation is to be used only as an aid to
filtration. If used, the liquid should be decanted and filtered
followed by filtration of the solid portion of the waste through
the same filtration system.
7.1.1.7 Quantitatively transfer the sample to the filter
holder (liquid and solid phases). Spread the sample evenly over
the surface of the filter. If filtration of the waste at 4°C
reduces the amount of expressed liquid over what would be expressed
at room temperature, then allow the sample to warm up to room
temperature in the device before filtering.
Gradually apply vacuum or gentle pressure of 1-10 psig,
until air or pressurizing gas moves through the filter. If this
point is not reached under 10 psig, and if no additional liquid has
passed through the filter in any 2-minute interval, slowly increase
the pressure in 10 psig increments to a maximum of 50 psig. After
each incremental increase of 10 psig, if the pressurizing gas has
not moved through the filter, and if no additional liquid has
passed through the filter in any 2-minute interval, proceed to the
next 10-psig increment. When the pressurizing gas begins to move
through the filter, or when liquid flow has ceased at 50 psig
(i.e., filtration does not result in any additional filtrate within
any 2-minute period), stop the filtration.
NOTE: If sample material (>1 % of original sample weight) has
obviously adhered to the container used to transfer the sample to
the filtration apparatus, determine the weight of this residue and
subtract it from the sample weight determined in Step 7.1.1.5 to
determine the weight of the sample that will be filtered.
NOTE: Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
7.1.1.8 The material in the filter holder is defined as
the solid phase of the sample, and the filtrate is defined as the
liquid phase.
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NOTE: Some samples, such as oily wastes and some paint wastes,
will obviously contain some material that appears to be a liquid,
but even after applying vacuum or pressure filtration, as outlined
in Step 7.1.1.7, this material may not filter. If this is the
case, the material within the filtration device is defined as a
solid. Do not replace the original filter with a fresh filter
under any circumstances. Use only one filter.
7.1.1.9 Determine the weight of the liquid phase by
subtracting the weight of the filtrate container (see Step 7.1.1.3)
from the total weight of the filtrate-filled container. Determine
the weight of the solid phase of the sample by subtracting the
weight of the liquid phase from the weight of the total sample, as
determined in Step 7.1.1.5 or 7.1.1.7.
Record the weight of the liquid and solid phases.
Calculate the percent solids as follows:
Weight of solid (Step 7.1.1.9)
Percent solids = x 100
Total weight of waste (Step 7.1.1.5 or 7.1.1.7)
7.1.2 If the percent solids determined in Step 7.1.1.9 is equal
to or greater than 0.5%, then proceed either to Step 7.1.3 to determine
whether the solid material requires particle size reduction or to Step
7.1.2.1 if it is noticed that a small amount of the filtrate is entrained
in wetting of the filter. If the percent solids determined in Step
7.1.1.9 is less than 0.5%, then proceed to Step 7.2.9 if the nonvolatile
1312 analysis is to be performed, and to Step 7.3 with a fresh portion of
the waste if the volatile 1312 analysis is to be performed.
7.1.2.1 Remove the solid phase and filter from the
filtration apparatus.
7.1.2.2 Dry the filter and solid phase at 100 ± 20°C
until two successive weighings yield the same value within + 1 %.
Record the final weight.
Caution: The drying oven should be vented to a hood or other
appropriate device to eliminate the possibility of fumes from the
sample escaping into the laboratory. Care should be taken to
ensure that the sample will not flash or violently react upon
heating.
7.1.2.3 Calculate the percent dry solids as follows:
Percent (Weight of dry sample + filter) - tared weight of filter
dry solids = x 100
Initial weight of sample (Step 7.1.1.5 or 7.1.1.7)
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7.1.2.4 If the percent dry solids is less than 0.5%,
then proceed to Step 7.2.9 if the nonvolatile 1312 analysis is to
be performed, and to Step 7.3 if the volatile 1312 analysis is to
be performed. If the percent dry solids is greater than or equal
to 0.5%, and if the nonvolatile 1312 analysis is to be performed,
return to the beginning of this Step (7.1) and, with a fresh
portion of sample, determine whether particle size reduction is
necessary (Step 7.1.3).
7.1.3 Determination of whether the sample requires particle-size
reduction (particle-size is reduced during this step): Using the solid
portion of the sample, evaluate the solid for particle size. Particle-
size reduction is required, unless the solid has a surface area per gram
of material equal to or greater than 3.1 cm2, or is smaller than 1 cm in
its narrowest dimension (i.e., is capable of passing through a 9.5 mm
(0.375 inch) standard sieve). If the surface area is smaller or the
particle size larger than described above, prepare the solid portion of
the sample for extraction by crushing, cutting, or grinding the waste to
a surface area or particle size as described above. If the solids are
prepared for organic volatiles extraction, special precautions must be
taken (see Step 7.3.6).
NOTE: Surface area criteria are meant for filamentous (e.g.,
paper, cloth, and similar) waste materials. Actual measurement of
surface area is not required, nor is it recommended. For materials
that do not obviously meet the criteria, sample-specific methods
would need to be developed and employed to measure the surface
area. Such methodology is currently not available.
7.1.4 Determination of appropriate extraction fluid:
7.1.4.1 For soils, if the sample is from a site that is
east of the Mississippi River, extraction fluid #1 should be used.
If the sample is from a site that is west of the Mississippi River,
extraction fluid #2 should be used.
7.1.4.2 For wastes and wastewater, extraction fluid #1
should be used.
7.1.4.3 For cyanide-containing wastes and/or soils,
extraction fluid #3 (reagent water) must be used because leaching
of cyanide-containing samples under acidic conditions may result
in the formation of hydrogen cyanide gas.
7.1.5 If the aliquot of the sample used for the preliminary
evaluation (Steps 7.1.1 - 7.1.4) was determined to be 100% solid at Step
7.1.1.1, then it can be used for the Step 7.2 extraction (assuming at
least 100 grams remain), and the Step 7.3 extraction (assuming at least 25
grams remain). If the aliquot was subjected to the procedure in Step
7.1.1.7, then another aliquot shall be used for the volatile extraction
procedure in Step 7.3. The aliquot of the waste subjected to the
procedure in Step 7.1.1.7 might be appropriate for use for the Step 7.2
extraction if an adequate amount of solid (as determined by Step 7.1.1.9)
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was obtained. The amount of solid necessary is dependent upon whether a
sufficient amount of extract will be produced to support the analyses. If
an adequate amount of solid remains, proceed to Step 7.2.10 of the
nonvolatile 1312 extraction.
7.2 Procedure When Volatiles Are Not Involved
A minimum sample size of 100 grams (solid and liquid phases) is
recommended. In some cases, a larger sample size may be appropriate, depending
on the solids content of the waste sample (percent solids, See Step 7.1.1),
whether the initial liquid phase of the waste will be miscible with the aqueous
extract of the solid, and whether inorganics, semivolatile organics, pesticides,
and herbicides are all analytes of concern. Enough solids should be generated
for extraction such that the volume of 1312 extract will be sufficient to support
all of the analyses required. If the amount of extract generated by a single
1312 extraction will not be sufficient to perform all of the analyses, more than
one extraction may be performed and the extracts from each combined and aliquoted
for analysis.
7.2.1 If the sample will obviously yield no liquid when subjected
to pressure filtration (i.e., is 100 % solid, see Step 7.1.1), weigh out
a subsample of the sample (100 gram minimum) and proceed to Step 7.2.9.
7.2.2 If the sample is liquid or multiphasic, liquid/solid
separation is required. This involves the filtration device described in
Step 4.3.2 and is outlined in Steps 7.2.3 to 7.2.8.
7.2.3 Pre-weigh the container that will receive the filtrate.
7.2.4 Assemble the filter holder and filter following the
manufacturer's instructions. Place the filter on the support screen and
secure. Acid wash the filter if evaluating the mobility of metals (see
Step 4.4).
NOTE: Acid washed filters may be used for all nonvolatile
extractions even when metals are not of concern.
7.2.5 Weigh out a subsample of the sample (100 gram minimum) and
record the weight. If the waste contains <0.5 % dry solids (Step 7.1.2),
the liquid portion of the waste, after filtration, is defined as the 1312
extract. Therefore, enough of the sample should be filtered so that the
amount of filtered liquid will support all of the analyses required of the
1312 extract. For wastes containing >0.5 % dry solids (Steps 7.1.1 or
7.1.2), use the percent solids information obtained in Step 7.1.1 to
determine the optimum sample size (100 gram minimum) for filtration.
Enough solids should be generated by filtration to support the analyses to
be performed on the 1312 extract.
7.2.6 Allow slurries to stand to permit the solid phase to settle.
Samples that settle slowly may be centrifuged prior to filtration. Use
centrifugation only as an aid to filtration. If the sample is
centrifuged, the liquid should be decanted and filtered followed by
filtration of the solid portion of the waste through the same filtration
system.
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7.2.7 Quantitatively transfer the sample (liquid and solid phases)
to the filter holder (see Step 4.3.2). Spread the waste sample evenly
over the surface of the filter. If filtration of the waste at 4°C reduces
the amount of expressed liquid over what would be expressed at room
temperature, then allow the sample to warm up to room temperature in the
device before filtering.
Gradually apply vacuum or gentle pressure of 1-10 psig, until air
or pressurizing gas moves through the filter. If this point if not
reached under 10 psig, and if no additional liquid has passed through the
filter in any 2-minute interval, slowly increase the pressure in 10-psig
increments to maximum of 50 psig. After each incremental increase of 10
psig, if the pressurizing gas has not moved through the filter, and if no
additional liquid has passed through the filter in any 2-minute interval,
proceed to the next 10-psig increment. When the pressurizing gas begins
to move through the filter, or when the liquid flow has ceased at 50 psig
(i.e., filtration does not result in any additional filtrate within a
2-minute period), stop the filtration.
NOTE: If waste material (>1 % of the original sample weight) has
obviously adhered to the container used to transfer the sample to
the filtration apparatus, determine the weight of this residue and
subtract it from the sample weight determined in Step 7.2.5, to
determine the weight of the waste sample that will be filtered.
NOTE:Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
7.2.8 The material in the filter holder is defined as the solid
phase of the sample, and the filtrate is defined as the liquid phase.
Weigh the filtrate. The liquid phase may now be either analyzed (see Step
7.2.12) or stored at 4°C until time of analysis.
NOTE; Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material which appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in Step
7.2.7, this material may not filter. If this is the case, the
material within the filtration device is defined as a solid, and
is carried through the extraction as a solid. Do not replace the
original filter with a fresh filter under any circumstances. Use
only one filter.
7.2.9 If the sample contains <0.5% dry solids (see Step 7.1.2),
proceed to Step 7.2.13. If the sample contains >0.5 % dry solids (see
Step 7.1.1 or 7.1.2), and if particle-size reduction of the solid was
needed in Step 7.1.3, proceed to Step 7.2,10. If the sample as received
passes a 9.5 mm sieve, quantitatively transfer the solid material into the
extractor bottle along with the filter used to separate the initial liquid
from the solid phase, and proceed to Step 7.2.11.
7.2.10 Prepare the solid portion of the sample for extraction by
crushing, cutting, or grinding the waste to a surface area or particle-
size as described in Step 7.1.3. When the surface area or particle-size
has been appropriately altered, quantitatively transfer the solid material
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into an extractor bottle. Include the filter used to separate the initial
liquid from the solid phase.
NOTE; Sieving of the waste is not normally required. Surface area
requirements are meant for filamentous (e.g., paper, cloth) and
similar waste materials. Actual measurement of surface area is not
recommended. If sieving is necessary, a Teflon-coated sieve should
be used to avoid contamination of the sample.
7.2.11 Determine the amount of extraction fluid to add to the
extractor vessel as follows:
20 x % solids (Step 7.1.1) x weight of waste
filtered (Step 7.2.5 or 7.2.7)
Weight of =
extraction fluid
100
Slowly add this amount of appropriate extraction fluid (see Step
7.1.4) to the extractor vessel. Close the extractor bottle tightly (it is
recommended that Teflon tape be used to ensure a tight seal), secure in
rotary extractor device, and rotate at' 30+2 rpm for 18+2 hours.
Ambient temperature (i.e., temperature of room in which extraction takes
place) shall be maintained at 23 + 2°C during the extraction period.
NOTE; As agitation continues, pressure may build -up within the
extractor bottle for some types of sample (e.g., limed or calcium
carbonate-containing sample may evolve gases such as carbon
dioxide). To relieve excess pressure, the extractor bottle may be
periodically opened (e.g., after 15 minutes, 30 minutes, and 1
hour) and vented into a hood.
7.2.12 Following the 18 + 2 hour extraction, separate the material
in the extractor vessel into its component liquid and solid phases by
filtering through a new glass fiber filter, as outlined in Step 7.2.7.
For final filtration of the 1312 extract, the glass fiber filter may be
changed, if necessary, to facilitate filtration. Filter(s) shall be
acid-washed (see Step 4.4) if evaluating the mobility of metals.
7.2.13 Prepare the 1312 extract as follows:
7.2.13.1 If the sample contained no initial liquid phase,
the filtered liquid material obtained from Step 7.2.12 is defined
as the 1312 extract. Proceed to Step 7.2.14.
7.2.13.2 If compatible (e.g., multiple phases will not
result on combination), combine the filtered liquid resulting from
Step 7.2.12 with the initial liquid phase of the sample obtained
in Step 7.2.7. This combined liquid is defined as the 1312
extract. Proceed to Step 7.2.14.
7.2.13.3 If the initial liquid phase of the waste, as
obtained from Step 7.2.7, is not or may not be compatible with the
filtered liquid resulting from Step 7.2.12, do not combine these
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liquids. Analyze these liquids, collectively defined as the 1312
extract, and combine the results mathematically, as described in
Step 7.2.14.
7.2.14 Following collection of the 1312 extract, the pH of the
extract should be recorded. Immediately aliquot and preserve the extract
for analysis. Metals aliquots must be acidified with nitric acid to pH <
2. If precipitation is observed upon addition of nitric acid to a small
aliquot of the extract, then the remaining portion of the extract for
metals analyses shall not be acidified and the extract shall be analyzed
as soon as possible. All other aliquots must be stored under
refrigeration (4°C) until analyzed. The 1312 extract shall be prepared
and analyzed according to appropriate analytical methods. 1312 extracts
to be analyzed for metals shall be acid digested except in those instances
where digestion causes loss of metallic analytes. If an analysis of the
undigested extract shows that the concentration of any regulated metallic
analyte exceeds the regulatory level, then the waste is hazardous and
digestion of the extract is not necessary. However, data on undigested
extracts alone cannot be used to demonstrate that the waste is not
hazardous. If the individual phases are to be analyzed separately,
determine the volume of the individual phases (to + 0.5 %), conduct the
appropriate analyses, and combine the results mathematically by using a
simple volume-weighted average:
(Vi) (C,) + (V2) (C2)
Final Analyte Concentration =
V + V
V1 + V2
where:
VT = The volume of the first phase (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.2.15 Compare the analyte concentrations in the 1312 extract with
the levels identified in the appropriate regulations. Refer to Section
8.0 for quality assurance requirements.
7.3 Procedure When Volatiles Are Involved
Use the ZHE device to obtain 1312 extract for analysis of volatile
compounds only. Extract resulting from the use of the ZHE shall not be used to
evaluate the mobility of non-volatile analytes (e.g., metals, pesticides, etc.).
The ZHE device has approximately a 500 ml internal capacity. The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional liquid may be forced out by an applied pressure
of 50 psig), due to the need to add an amount of extraction fluid equal to 20
times the weight of the solid phase.
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Charge the ZHE with sample only once and do not open the device until the
final extract (of the solid) has been collected. Repeated filling of the ZHE to
obtain 25 grams of solid is not permitted.
Do not allow the sample, the initial liquid phase, or the extract to be
exposed to the atmosphere for any more time than is absolutely necessary. Any
manipulation of these materials should be done when cold (4"C) to minimize loss
of volatiles.
7.3.1 Pre-weigh the (evacuated) filtrate collection container
(see Step 4.6) and set aside. If using a TEDLAR* bag, express all liquid
from the ZHE device into the bag, whether for the initial or final
liquid/solid separation, and take an aliquot from the liquid in the bag
for analysis. The containers listed in Step 4.6 are recommended for use
under the conditions stated in Steps 4.6.1-4.6.3.
7.3.2 Place the ZHE piston within the body of the ZHE (it may be
helpful first to moisten the piston 0-rings slightly with extraction
fluid). Adjust the piston within the ZHE body to a height that will
minimize the distance the piston will have to move once the ZHE is charged
with sample (based upon sample size requirements determined from Step 7.3,
Step 7.1.1 and/or 7.1.2). Secure the gas inlet/outlet flange (bottom
flange) onto the ZHE body in accordance with the manufacturer's
instructions. Secure the glass fiber filter between the support screens
and set aside. Set liquid inlet/outlet flange (top flange) aside..
7.3.3 If the sample is 100% solid (see Step 7.1.1), weigh out
a subsample (25 gram maximum) of the waste, record weight, and proceed to
Step 7.3.5.
7.3.4 If the sample contains <0.5% dry solids (Step 7.1.2), the
liquid portion of waste, after filtration, is defined as the 1312 extract.
Filter enough of the sample so that the amount of filtered liquid will
support all of the volatile analyses required. For samples containing
>0.5% dry solids (Steps 7.1.1 and/or 7.1.2), use the percent solids
information obtained in Step 7.1.1 to determine the optimum sample size to
charge into the ZHE. The recommended sample size is as follows:
7.3.4.1 For samples containing <5% solids (see Step
7.1.1), weigh out a 500 gram subsample of waste and record the
weight.
7.3.4.2 For wastes containing >5% solids (see Step
7.1.1), determine the amount of waste to charge into the ZHE as
follows:
25
Weight of waste to charge ZHE = x 100
percent solids (Step 7.1.1)
Weigh out a subsample of the waste of the appropriate size and
record the weight.
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7.3.5 If particle-size reduction of the solid portion of the
sample was required in Step 7.1.3, proceed to Step 7.3.6. If particle-
size reduction was not required in Step 7.1.3, proceed to Step 7.3.7.
7.3.6 Prepare the sample for extraction by crushing, cutting, or
grinding the solid portion of the waste to a surface area or particle size
as described in Step 7.1.3.1. Wastes and appropriate reduction equipment
should be refrigerated, if possible, to 4°C prior to particle-size
reduction. The means used to effect particle-size reduction must not
generate heat in and of itself. If reduction of the solid phase of the
waste is necessary, exposure of the waste to the atmosphere should be
avoided to the extent possible.
NOTE: Sieving of the waste is not recommended due to the
possibility that volatiles may be lost. The use of an
appropriately graduated ruler is recommended as an acceptable
alternative. Surface area requirements are meant for filamentous
(e.g., paper, cloth) and similar waste materials. Actual
measurement of surface area is not recommended.
When the surface area or particle-size has been appropriately
altered, proceed to Step 7.3.7.
7.3.7 Waste slurries need not be allowed to stand to permit the
solid phase to settle. Do not centrifuge samples prior to filtration.
7.3.8 Quantitatively transfer the entire sample (liquid and solid
phases) quickly to the ZHE. Secure the filter and support screens into
the top flange of the device and secure the top flange to the ZHE body in
accordance with the manufacturer's instructions. Tighten all ZHE fittings
and place the device in the vertical position (gas inlet/outlet flange on
the bottom). Do not attach the extraction collection device to the top
plate.
Note: If sample material (>1% of original sample weight) has
obviously adhered to the container used to transfer the sample to
the ZHE, determine the weight of this residue and subtract it from
the sample weight determined in Step 7.3.4 to determine the weight
of the waste sample that will be filtered.
Attach a gas line to the gas inlet/outlet valve (bottom flange)
and, with the liquid inlet/outlet valve (top flange) open, begin applying
gentle pressure of 1-10 psig (or more if necessary) to force all headspace
slowly out of the ZHE device into a hood. At the first appearance of
liquid from the liquid inlet/outlet valve, quickly close the valve and
discontinue pressure. If filtration of the waste at 4°C reduces the
amount of expressed liquid over what would be expressed at room
temperature, then allow the sample to warm up to room temperature in the
device before filtering. If the waste is 100 % solid (see Step 7.1.1),
slowly increase the pressure to a maximum of 50 psig to force most of the
headspace out of the device and proceed to Step 7.3.12.
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7.3.9 Attach the evacuated pre-weighed filtrate collection
container to the liquid inlet/outlet valve and open the valve. Begin
applying gentle pressure of 1-10 psig to force the liquid phase of the
sample into the filtrate collection container. If no additional liquid
has passed through the filter in any 2-minute interval, slowly increase
the pressure in 10-psig increments to a maximum of 50 psig. After each
incremental increase of 10 psig, if no additional liquid has passed
through the filter in any 2-minute interval, proceed to the next 10-psig
increment. When liquid flow has ceased such that continued pressure
filtration at 50 psig does not result in any additional filtrate within a
2-minute period, stop the filtration. Close the liquid inlet/outlet
valve, discontinue pressure to the piston, and disconnect and weigh the
filtrate collection container.
NOTE: Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
7.3.10 The material in the ZHE is defined as the solid phase of
the sample and the filtrate is defined as the liquid phase.
NOTE: Some samples, such as oily wastes and some paint wastes,
will obviously contain some material which appears to be a liquid.
Even after applying pressure filtration, this material will not
filter. If this is the case, the material within the filtration
device is defined as a solid, and is carried through the 1312
extraction as a solid.
If the original waste contained <0.5 % dry solids (see Step 7.1.2),
this filtrate is defined as the 1312 extract and is analyzed directly.
Proceed to Step 7.3.15.
7.3.11 The liquid phase may now be either analyzed immediately
(see Steps 7.3.13 through 7.3.15) or stored at 4"C under minimal headspace
conditions until time of analysis. Determine the weight of extraction
fluid #3 to add to the ZHE as follows:
20 x % solids (Step 7.1.1) x weight
of waste filtered (Step 7.3.4 or 7.3.8)
Weight of extraction fluid = —
100
7.3.12 The following steps detail how to add the appropriate
amount of extraction fluid to the solid material within the ZHE and
agitation of the ZHE vessel. Extraction fluid #3 is used in all cases
(see Step 5.4.3).
7.3.12.1 With the ZHE in the vertical position, attach a
line from the extraction fluid reservoir to the liquid inlet/outlet
valve. The line used shall contain fresh extraction fluid and
should be preflushed with fluid to eliminate any air pockets in the
line. Release gas pressure on the ZHE piston (from the gas
inlet/outlet valve), open the liquid inlet/outlet valve, and begin
transferring extraction fluid (by pumping or similar means) into
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the ZHE. Continue pumping extraction fluid into the ZHE until the
appropriate amount of fluid has been introduced into the device.
7.3.12.2 After the extraction fluid has been added,
immediately close the liquid inlet/outlet valve and disconnect the
extraction fluid line. Check the ZHE to ensure that all valves are
in their closed positions. Manually rotate the device in an
end-over-end fashion 2 or 3 times. Reposition the ZHE in the
vertical position with the liquid inlet/outlet valve on top.
Pressurize the ZHE to 5-10 psig (if necessary) and slowly open the
liquid inlet/outlet valve to bleed out any headspace (into a hood)
that may have been introduced due to the addition of extraction
fluid. This bleeding shall be done quickly and shall be stopped
at the first appearance of liquid from the valve. Re-pressurize
the ZHE with 5-10 psig and check all ZHE fittings to ensure that
they are closed.
7.3.12.3 Place the ZHE in the rotary extractor apparatus
(if it is not already there) and rotate at 30 + 2 rpm for 18+2
hours. Ambient temperature (i.e., temperature of room in which
extraction occurs) shall be maintained at 23 + 28C during
agitation.
7.3.13 Following the 18+2 hour agitation period, check the
pressure behind the ZHE piston by quickly opening and closing the gas
inlet/outlet valve and noting the escape of gas. If the pressure has not
been maintained (i.e., no gas release observed), the ZHE is leaking.
Check the ZHE for leaking as specified in Step 4.2.1, and perform the
extraction again with a new sample of waste. If the pressure within the
device has been maintained, the material in the extractor vessel is once
again separated into its component liquid and solid phases. If the waste
contained an initial liquid phase, the liquid may be filtered directly
into the same filtrate collection container (i .e. . TEDLAR* bag) holding the
initial liquid phase of the waste. A separate filtrate collection
container must be used if combining would create multiple phases, or there
is not enough volume left within the filtrate collection container.
Filter through the glass fiber filter, using the ZHE device as discussed
in Step 7.3.9. All extracts shall be filtered and collected if the TEDLAR
bag is used, if the extract is multiphasic, or if the waste contained an
initial liquid phase (see Steps 4.6 and 7.3.1).
NOTE: An in-line glass fiber filter may be used to filter the
material within the ZHE if it is suspected that the glass fiber
filter has been ruptured
7.3.14 If the original sample contained no initial liquid phase,
the filtered liquid material obtained from Step 7.3.13 is defined as the
1312 extract. If the sample contained an initial liquid phase, the
filtered liquid material obtained from Step 7.3.13 and the initial liquid
phase (Step 7.3.9) are collectively defined as the 1312 extract.
7.3.15 Following collection of the 1312 extract, immediately
prepare the extract for analysis and store with minimal headspace at 4°C
1312 - 17 Revision 0
September 1994
*
-------
until analyzed. Analyze the 1312 extract according to the appropriate
analytical methods. If the individual phases are to be analyzed
separately (i.e., are not miscible), determine the volume of the
individual phases (to 0.5%), conduct the appropriate analyses, and combine
the results mathematically by using a simple volume- weighted average:
(V,) (C,) + (V2) (C2)
Final Analyte
Concentration , V, + V2
where:
V, = The volume of the first phases (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.3.16 Compare the analyte concentrations in the 1312 extract with
the levels identified in the appropriate regulations. Refer to Step 8.0
for quality assurance requirements.
8.0 QUALITY CONTROL
8.1 A minimum of one blank (using the same extraction fluid as used for
the samples) for every 20 extractions that have been conducted in an extraction
vessel. Refer to Chapter One for additional quality control protocols.
8.2 A matrix spike shall be performed for each waste type (e.g.,
wastewater treatment sludge, contaminated soil, etc.) unless the result exceeds
the regulatory level and the data is being used solely to demonstrate that the
waste property exceeds the regulatory level. A minimum of one matrix spike must
be analyzed for each analytical batch. As a minimum, follow the matrix spike
addition guidance provided in each analytical method.
8.2.1 Matrix spikes are to be added after filtration of the 1312
extract and before preservation. Matrix spikes should not be added prior
to 1312 extraction of the sample.
8.2.2 In most cases, matrix spike levels should be added at a
concentration equivalent to the corresponding regulatory level. If the
analyte concentration is less than'one half the regulatory level, the
spike concentration may be as low as one half of the analyte
concentration, but may not be less than five times the method detection
limit. In order to avoid differences in matrix effects, the matrix spikes
must be added to the same nominal volume of 1312 extract as that which was
analyzed for the unspiked sample.
8.2.3 The purpose of the matrix spike is to monitor the
performance of the analytical methods used, and to determine whether
1312 - 18 Revision 0
September 1994
-------
matrix interferences exist. Use of other internal calibration methods,
modification of the analytical methods, or use of alternate analytical
methods may be needed to accurately measure the analyte concentration in
the 1312 extract when the recovery of the matrix spike is below the
expected analytical method performance.
8.2.4 Matrix spike recoveries are calculated by the following
formula:
%R (% Recovery) = 100 (X8 - XJ / K
where:
Xs = measured value for the spiked sample
Xu = measured value for the unspiked sample, and
K = known value of the spike in the sample.
8.3 All quality control measures described in the appropriate analytical
methods shall be followed.
8.4 The use of internal calibration quantitation methods shall be
employed for a metallic contaminant if: (1) Recovery of the contaminant from the
1312 extract is not at least 50% and the concentration does not exceed the
appropriate regulatory level, and (2) The concentration of the contaminant
measured in the extract is within 20% of the appropriate regulatory level.
8.4.1. The method of standard additions shall be employed as the
internal calibration quantitation method for each metallic contaminant.
8.4.2 The method of standard additions requires preparing
calibration standards in the sample matrix rather than reagent water or
blank solution. It requires taking four identical aliquots of the
solution and adding known amounts of standard to three of these aliquots.
The forth aliquot is the unknown. Preferably, the first addition should
be prepared so that the resulting concentration is approximately 50% of
the expected concentration of the sample. The second and third additions
should be prepared so that the concentrations are approximately 100% and
150% of the expected concentration of the sample. All four aliquots are
maintained at the same final volume by adding reagent water or a blank
solution, and may need dilution adjustment to maintain the signals in the
linear range of the instrument technique. All four aliquots are analyzed.
8.4.3 Prepare a plot, or subject data to linear regression, of
instrument signals or external-calibration-derived concentrations as the
dependant variable (y-axis) versus concentrations of the additions of
standards as the independent variable (x-axis). Solve for the intercept
of the abscissa (the independent variable, x-axis) which is the concentra-
tion in the unknown.
8.4.4 Alternately, subtract the instrumental signal or external-
calibration-derived concentration of the unknown (unspiked) sample from
the instrumental signals or external-calibration-derived concentrations of
the standard additions. Plot or subject to linear regression of the
corrected instrument signals or external-calibration-derived concentra-
1312 - 19 Revision 0
September 1994
-------
tions as the dependant variable versus the independent variable. Derive
concentrations for the unknowns using the internal calibration curve as if
it were an external calibration curve.
8.5 Samples must undergo 1312 extraction within the following time
periods:
SAMPLE MAXIMUM HOLDING TIMES (days)
Volatiles
Semi-
volatiles
Mercury
Metals,
except
mercury
From: Field
Collec-
tion
To: 1312
extrac-
tion
14
14
28
180
From: 1312
extrac-
tion
To: Prepara-
tive
extrac-
tion
NA
7
NA
NA
From: Prepara-
tive
extrac-
tion
To: Determi-
native
analysis
14
40
28
180
Total
Elapsed
Time
28
61
56
360
NA = Not Applicable
If sample holding times are exceeded, the values obtained will be considered
minimal concentrations. Exceeding the holding time is not acceptable in
establishing that a waste does not exceed the regulatory level. Exceeding the
holding time will not invalidate characterization if the waste exceeds the
regulatory level.
9.0 METHOD PERFORMANCE
9.1 Precision results for semi-volatiles and metals: An eastern soil
with high organic content and a western soil with low organic content were used
for the semi-volatile and metal leaching experiments. Both types of soil were
analyzed prior to contaminant spiking. The results are shown in Table 6. The
concentration of contaminants leached from the soils were reproducible, as shown
by the moderate relative standard deviations (RSDs) of the recoveries (averaging
29% for the compounds and elements analyzed).
9.2 Precision results for volatiles: Four different soils were spiked
and tested for the extraction of volatiles. Soils One and Two were from western
and eastern Superfund sites. Soils Three and Four were mixtures of a western
soil with low organic content and two different municipal sludges. The results
are shown in Table 7. Extract concentrations of volatile organics from the
eastern soil were lower than from the western soil. Replicate Teachings of Soils
1312 - 20
Revision 0
September 1994
-------
Three and Four showed lower precision than the leachates from the Superfund
soils.
10.0 REFERENCES
1. Environmental Monitoring Systems Laboratory, "Performance Testing of
Method 1312; QA Support for RCRA Testing: Project Report". EPA/600/4-
89/022. EPA Contract 68-03-3249 to Lockheed Engineering and Sciences
Company, June 1989.
2. Research Triangle Institute, "Interlaboratory Comparison of Methods 1310,
1311, and 1312 for Lead in Soil". U.S. EPA Contract 68-01-7075, November
1988.
1312 - 21 Revision 0
September 1994
-------
Table 1. Volatile Analytes1
Compound CAS No.
Acetone 67-64-1
Benzene 71-43-2
n-Butyl alcohol 71-36-3
Carbon disulfide 75-15-0
Carbon tetrachloride 56-23-5
Chlorobenzene 108-90-7
Chloroform 67-66-3
1,2-Dichloroethane 107-06-2
1,1-Dichloroethylene 75-35-4
Ethyl acetate 141-78-6
Ethyl benzene 100-41-4
Ethyl ether 60-29-7
Isobutanol 78-83-1
Methanol 67-56-1
Methylene chloride 75-09-2
Methyl ethyl ketone 78-93-3
Methyl isobutyl ketone 108-10-1
Tetrachloroethylene 127-18-4
Toluene 108-88-3
1,1,1,-Trichloroethane 71-55-6
Trichloroethylene 79-01-6
Trichlorofluoromethane 75-69-4
1,1,2-Tri chloro-1,2,2-tri f1uoroethane 76-13-1
Vinyl chloride 75-01-4
Xylene 1330-20-7
1 When testing for any or all of these analytes, the zero-headspace extractor
vessel shall be used instead of the bottle extractor.
1312 - 22 Revision 0
September 1994
-------
Table 2. Suitable Rotary Agitation Apparatus1
Company
Location
Model No.
Analytical Testing and
Consulting Services,
Inc.
Associated Design and
Manufacturing Company
Environmental Machine and
Design, Inc.
IRA Machine Shop and
Laboratory
Lars Lande Manufacturing
Millipore Corp.
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Lynchburg, VA
(804) 845-6424
Santurce, PR
(809) 752-4004
4-vessel extractor (DC20S);
8-vessel extractor (DC20);
12-vessel extractor (DC20B)
2-vessel
4-vessel
6-vessel
8-vessel
12-vessel
24-vessel
(3740-2);
(3740-4);
(3740-6);
(3740-8);
(3740-12);
(3740-24)
8-vessel (08-00-00)
4-vessel (04-00-00)
8-vessel (011001)
Whitmore Lake, MI 10-vessel (10VRE)
(313) 449-4116 5-vessel (5VRE)
Bedford, MA
(800) 225-3384
4-ZHE or
4 1-liter
bottle extractor
(YT300RAHW)
1 Any device that rotates the extraction vessel in an end-over-end fashion at 30
+2 rpm is acceptable.
1312 - 23
Revision 0
September 1994
-------
Table 3. Suitable Zero-Headspace Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
Consulting Services, Inc.
Associated Design and
Manufacturing Company
Lars Lande Manufacturing2
Millipore Corporation
Environmental Machine
and Design, Inc.
Harrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Whitmore Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
Lynchburg, VA
(804) 845-6424
C102, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
ZHE-11, Gas
Pressure Device
YT30090HW, Gas
Pressure Device
VOLA-TOX1, Gas
Pressure Device
1 Any device that, meets the specifications listed in Step 4.2.1 of the method is
suitable.
2 This device uses a 110 mm filter.
1312 - 24
Revision 0
September 1994
-------
Table 4. Suitable Filter Holders1
Company
Nucleopore Corporation
Micro Filtration
Systems
Millipore Corporation
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Bedford, MA
(800) 225-3384
Model/
Catalogue #
425910
410400
302400
311400
YT30142HW
XX1004700
Size
142 mm
47 mm
142 mm
47 mm
142 mm
47 mm
1 Any device capable of separating the liquid from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed. Plastic devices (not listed above) may be used when
only inorganic analytes are of concern. The 142 mm size filter holder is
recommended.
Table 5. Suitable Filter Media1
Company
Mi Hi pore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Location Model
Bedford, MA AP40
(800) 225-3384
Pleasanton, CA 211625
(415) 463-2530
Clifton, NJ GFF
(201) 773-5800
Dublin, CA GF75
(800) 334-7132
(415) 828-6010
Pore
Size
(Mm)
0.7
0.7
0.7
0.7
1 Any filter that meets the specifications in Step 4.4 of the Method is suitable.
1312 - 25 Revision 0
September 1994
-------
TABLE 6 - METHOD 1312 PRECISION RESULTS FOR SEMI-VOLATILES AND METALS
Eastern Soil (t>H 4.2)
FORTIFIED ANALYTES
bis(2-chloroethyl)-
ether
2-Chlorophenol
1 , 4-Dichlorobenzene
1 , 2-Dichlorobenzene
2-Methylphenol
Nitrobenzene
2 ,4-Dimethylphenol
Hexachlorobutadiene
Acenaphthene
2,4-Dinitrophenol
2,4-Dinitrotoluene
Hexachlorobenzene
famma BHC (Lindane)
eta BHC
METALS
Lead
Cadmium
Amount
Spiked
(Mg)
1040
1620
2000
8920
3940
1010
1460
6300
3640
1300
1900
1840
7440
640
5000
1000
Amount
Recovered*
(Mg)
834
1010
344
1010
1860
812
200
95
210
896**
1150
3.7
230
35
70
387
% RSD
12.5
6.8
12.3
8.0
7.7
10.0
18.4
12.9
8.1
6.1
5.4
12.0
16.3
13.3
4.3
2.3
Western Soil (oH 5.0)
Amount
Recovered*
(Mg)
616
525
272
1520
1130
457
18
280
310**
23**
585
10
1240
65.3
10
91
% RSD
14.2
54.9
34.6
28.4
32.6
21.3
87.6
22.8
7.7
15.7
54.4
173.2
55.2
51.7
51.7
71.3
* - Triplicate analyses.
** - Duplicate analyses; one value was rejected as an outlier at the 90%
confidence level using the Dixon Q test.
1312 - 26
Revision 0
September 1994
-------
TABLE 7 - METHOD 1312 PRECISION RESULTS FOR VOLATILES
Soil
No. 1
Soil
No. 2
Soil No
. 3
(Western and
(Western)
Compound Name
Acetone
Acrylonitrile
Benzene
n-Butyl Alcohol
(1-Butanol)
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1 , 2 -Dichloroe thane
1 , 1 -Dichloroe thane
Ethyl acetate
Ethylbenzene
Ethyl ether
Isobutanol (4 -Methyl
-1-propanol)
Methylene chloride
Methyl ethyl ketone
(2-Butanone)
Methyl isobutyl
ketone
1,1,1, 2 -Tetrachloro -
ethane
1,1,2, 2 -Tetrachloro -
ethane
Tetrachloroethene
Toluene
1,1,1-Trichloro-
e thane
1,1,2-Trichloro-
e thane
Trichloroethene
Trichloro-
fluorome thane
1,1,2-Trichloro-
trifluoroethane
Vinyl chloride
Avg.
%Rec.
44.0
52.5
47.8
55.5
21.4
40.6
64.4
61.3
73.4
31.4
76.4
56.2
48.0
0.0
47.5
56.7
81.1
69.0
85.3
45.1
59.2
47.2
76.2
54.5
20.7
18.1
10.2
* %RSD
12.4
68.4
8.29
2.91
16.4
18.6
6.76
8.04
4.59
14.5
9.65
9.22
16.4
ND
30.3
5.94
10.3
6.73
7.04
12.7
8.06
16.0
5.72
11.1
24.5
26.7
20.3
(Eastern)
Avg.
%Rec.
43.8
50.5
34.8
49.2
12.9
22.3
41.5
54.8
68.7
22.9
75.4
23.2
55.1
0.0
42.2
61.9
88.9
41.1
58.9
15.2
49.3
33.8
67.3
39.4
12.6
6.95
7.17
* %RSD
2.25
70.0
16.3
14.6
49.5
29.1
13.1
16.4
11.3
39.3
4.02
11.5
9.72
ND
42.9 ,
3.94
2.99
11.3
4.15
17.4
10.5
22.8
8.43
19.5
60.1
58.0
72.8
Sludge)
Avg.
%Rec.**
116.0
49.3
49.8
65.5
36.5
36.2
44.2
61.8
58.3 .
32.0
23.0
37.5
37.3
61.8
52.0
73.7
58.3
50.8
64.0
26.2
45.7
40.7
61.7
38.8
28.5
21.5
25.0
%RSD
11.5
44.9
36.7
37.2
51.5
41.4
32.0
29.1
33.3
54.4
119.8
36.1
31.2
37.7
37.4
31.3
32.6
31.5
25.7
44.0
35.2
40.6
28.0
40.9
,
34.0
67.8
61.0
Soil No. 4
(Western and
Sludge)
Avg.
%Rec.*** %RSD
21.3 71.4
51.8 4.6
33.4 41.1
73.0 13.9
21.3 31.5
24.0 34.0
33.0 24.9
45.8 38.6
41.2 37.8
16.8 26.4
11.0 115.5
27.2 28.6
42.0 17.6
76.0 12.2
37.3 16.6
40.6 39.0
39.8 40.3
36.8 23.8
53.6 15.8
18.6 24.2
31.4 37.2
26.2 38.8
46.4 25.4
25.6 34.1
19.8 33.9
15.3 24.8
11.8 25.4
* Triplicate analyses
** Six replicate analyses
*** Five replicate analyses
1312 - 27
Revision 0
September 1994
-------
Motor
(30±2rpm)
Extraction Vessel Holder
Figure 1. Rotary Agitation Apparatus
Uquid Met/Outlet Vifee
t
F»er
Support Sown'
VKon
Bottom Range—*{_.
Pressurized Qas
inlevOutM Valvt
Sample
* Piston
Gas
Pressure
QauQf
Figure 2. Zero-Headspace Extractor (ZHE)
1312 - 28
Revision 0
Septenter 1994
-------
METHOD 1312
SYNTHETIC PRECIPITATION LEACHING PROCEDURE
I
Start
I
Select
representative
sample.
Prepare filtrate
according to
appropriate
methods.
Analyze filtrate.
Separate liquids
from solids.
Is
particle
reduction
required?
f Stop J
Extract w/
appropriate fluid via
1. Bottle extraction
for non-volatiles,
2. ZHE for volatiles.
Reduce particle
size to <9.5 mm.
1312 - 29
Revision 0
September 1994
-------
METHOD 1312
SYNTHETIC PRECIPITATION LEACHING PROCEDURE (continued)
0
Discard
Solids
Solids
-rf
^
r
Separate liquids
from solids.
Extract
Is
extract
compatible
with initial
liquid
phase?
Prepare and analyze
each liquid
separately,
mathematically
combine results.
Combine extract
with liquid phase
of waste.
I
f Stop J
Prepare extract
according to
appropriate
methods.
T
Analyze extract.
>
r
( Stop J
1312 - 30
Revision 0
Septenter 1994
-------
1330A
-------
METHOD 1330A
EXTRACTION PROCEDURE FOR OILY WASTES
/
,1.0 SCOPE AND APPLICATION
' 1.1 Method 1330 is used to determine the mobile metal concentration
(MMC) in oily wastes.
1.2 Method 1330 is applicable to API separator sludges, rag oils, slop
oil emulsions, and other oil wastes derived from petroleum refining.
2.0 SUMMARY OF METHOD >
2.1 The sample is separated int;o solid and liquid components by
filtration.
2.2 The solid phase is placed in a Soxhlet extractor, charged with
tetrahydrofuran, and extracted. The THF is removed,' the extractor is then
charged with toluene, and the sample is reextracted.
2.3 The EP method (Method 1310) is run on the dry solid residue.
2.4 The original liquid, combined extracts, and EP leachate are
analyzed for the EP metals.
3.0 INTERFERENCES • •• ,
• . ^
3.1 Matrix interferences will be coextracted from the sample. - The
extent of these interferences will vary considerably from waste to waste,
depending on the nature and diversity of the particular refinery waste being
analyzed.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extraction apparatus.
4.2 Vacuum pump or other source of vacuum.
4.3 Buchner funnel 12. .
4.4 Electric heating mantle.
4.5 Paper extraction thimble.
4.6 Filter paper.
4.7 . Muslin cloth disks. .
4.8 .Evaporative flask - 250-mL'.
4.9 Balance - Analytical, capable of weighing to ±0.5 mg.
1330A - 1 , Revision 1
:i" ; July 1992
-------
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. All references to water;in this method refer to
.reagent water, as defined, in Chapter One. '
5.3 Tetrahydrofuran, C4H80.
- 5.4 Toluene, C6H5CH3.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Samples must be collected in glass containers having a total volume
of at least 150 mL. No solid material should interfere with sealing the sample
.container. .
6.2 Sampling devices should be wiped clean with paper towels or
absorbent cloth, rinsed with a small amount of hexane followed by acetone rinse,
and dried between samples. Alternatively, samples can be taken with disposable
sampling devices in beakers. . •
7.0 PROCEDURE .
7.1 Separate the sample (minimum 100 g) into its solid and liquid
components. The liquid component is defined as that portion of the sample which
passes through a 0.45 urn filter media under a pressure differential of 75 psi.
7.2 Determine the quantity of liquid (mL) and the concentration of the
toxicants of concern in the liquid phase (mg/L).
7.3 Place the solid phase into a Soxhlet extractor, charge the
concentration flask with 300 mL tetrahydrofuran, and extract for 3 hours.
/ '• '
7.4 Remove the flask containing tetrahydrofuran .and replace it with one
containing 300 mL toluene. .
7.5 Extract the solid a second time, for 3 hours, with the toluene.
7.6 Combine the tetrahydrofuran and toluene extracts.,
7.7 Analyze the combined extracts for the toxicants of concern.
7.8 Determine the quantity of liquid (mL) and the concentration of the
toxicants of concern in the combined extracts (mg/L).
7.9 Take the solid material remaining in the Soxhlet thimble and dry
it at 100°C for 30 minutes.
1330A - 2 Revision 1
> . .. • July 1992
-------
7.10 Run the EP (Method 1310) on the dried solid.
7.11 Calculate the mobile metal concentration (MMC) in mg/L using the
following formula:
MMC - 1,000
(Li + 1-2 + L3)
where: ,'..,-'
Q, = Mass of toxicant in initial liquid phase of sample (amount
of liquid x concentration of toxicant) (mg).
Q2 = Mass of toxicant in combined organic extracts of sample
(amount of liquid x concentration of toxicant) (mg).
Q3 = Mass of toxicant in EP extract of solid (amount of extract
x concentration of toxicant) (mg).
L, = Volume of initial liquid (ml).
L2 = Volume of liquid in THF and toluene extract (Step 7.8)
(ml).
, -N
L3 = Volume of liquid in EP (ml) = 20 x [weight of dried solid
from Step 7.9 (g)].
8.0 QUALITY CONTROL
8.1 Any reagent blanks or replicates 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.
9.0 METHOD PERFORMANCE . .' ' ' ,
i
9.1 No data provided. .
/
10.0 REFERENCES '
1. Rohrbough, VI. 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.
1330A - 3 Revision 1
July 1992
-------
Figure 1. Extractor
Non-Clogging Support Bushing
1-Inch Blade at 30* to Horizontal
1330A - 4
Revision 1
July 1992
-------
2-Liter Plastic or Glass Bottles
1/15-Horsepower Electric Motor
29RPM
t*>
o"
-J>
I
Ul
Screws for Holding Bottles
o>
•yo
Q
X
it-
O
~\
(D
«0
rv>
-------
Figures. EPRI Extractor
l-Galkm Plastk
or Glass Bottle
Totally Enclosed
Faa Cooled Motor
30 rpm, 1/8 HP
Hinged Cover
-. Foam Bonded to Cover
Box Assembly
Plywood Construction
1330A - 6
Revision 1
1992
-------
Figure 4. Compaction Tester
Combined Weight
0.33 kg (0.73 Ib)
i~
15.25 cm
6" .
3.15 cm
(1.25")
Sample
Elastomeric
Sample Holder
^ 1
**
3.3cm
(1.3")
9.4 cm
(3.7") .
7.1 cm
(2.8")
1
1330A - 7
Revision 1
July 1992
-------
METHOD 1330A
EXTRACTION PROCEDURE FOR OILY WASTE
f STURT J
7 . 1 S«p«rat« »ampl«
into liquid and
•olid phaa«*
1
7 .2 Determine
quantity of liquid
and concentration
of toxicant* in
liquid pHa*e
7 . 3 Place aolid
phase in •(tractor.
add THF to
concentration
f laak . ((tract for
3 houri
7 . 8 0«t«rain«
quantity of liquid
and concentration
of toxieanti in
combined ((tract*
'
7.9 R«nov« tolida.
from thimble and
dry
1
7.10 Run EP (1310)
on dried »olid»
.7,4 Replace THF
fla*k vith toluene
concentration flatk
711 Calculate
mobile metal
concentration'
7.S-7.7 Eitract for
3 hour*; combine
eiitractt; analyze
combined extract*
1330A - 8
Revision 1
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3005A
-------
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 me'tals 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-jum 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
July 1992
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Precipitation will cause a lowering of the silver concentration and therefore an
inaccurate analysis.
i
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 sh'all 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 ac.id (concentrated), HNO,. Acid should be analyzed ^to
determine level of impurities. If method blank 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-/Lim filter and then acidified-at the time of collection with HN03
(5 mL/L).
3005A - 2 Revision 1
. . July 1992
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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
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. 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
'•-,.- July 1992
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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.
3005A - 4 Revision 1
July 1992
. -- • • i
-------
METHOD 3005A
ACID DIGESTION OF WATERS FOR TOTAL RECOVERABLE OR
DISSOLVED METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
7.2 H.«t
• »pl« to
r«duc« voluM
7.3 Cool
b««k«r;
filUr if
7.4 Adju.t
final voluai
Stop
3005A - 5
Revision 1
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3010A
-------
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
July 1992
-------
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 HNO,. 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.. i
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
• ' ' July 1992
-------
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
July 1992
-------
METHOD 3010A
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
FOR TOTAL METALS ANALYSIS BY FLAA OR ICP SPECTROSCOPY
Start
7.1 Trantfar taapli
aliquot to beaker,
add concentrated
HHO. •
7.1 H.at to
evaporate to lov
volume, cool, and
add concentrated
HNO.
7.1 Rahaat,
increaie
temperature to
create gantla
raflux action
7.2 Haat to
complete digestion,
evaporate,add
HC1,war> beaker
7.3 Filter if
nace*»ary and
adjuit volume
3010A - 5
Revision 1
July 1992
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3015
-------
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
September 1994
-------
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
September 1994
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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
September 1994
-------
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
September 1994
-------
absorbs microwave energy and is hot 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 i 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) (•) (AT)
Eq. 1
t
Where: • >
P = the apparent power absorbed by the sample in watts (W).
(W=joule-seO
K = the conversion factor for thermochemical calories-sec"1 to watts
(=4.184)
C_ = the heat capacity, thermal capacity, or specific heat
(cal-g'f'°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:
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
hot 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
September 1994
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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 (PFAorTFM) 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 ± 48C 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
160eC + 4eC 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
-------
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
-------
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, 19.85.; Dl 193-77.
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)
Elea
Al
Al
Al
Al
Ba
Ba
Ba
Cd
Cd
Cd
Cd
Zn
Zn
Zn
Zn
As
As
Co
Co
1C
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
UP980-2
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
U.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. SOX
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 en
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
I
7.1 Calibrate
the microwave
equipment.
.
7.2 AeM wee
end MJO rlnae
all dlgeetion
veeaele end
gtoeewere.
-»
^
r
7.3.2 Meeeure
46 ml aliquot
Into the
i
V1MWI.
»-
7.3.3 Uae blank
umptoe ef
reagent t£D In
veeaeta.
7.3.4 Add
oono«ntrat*d
I
7.3.S PtoM
v«M«4« In MM
blank* If naewurv
to b«l«ne* pewvr.
I
7. 3. a Ptoe*
in «v«n. h««t
•eaordlng to
pawvr program.
I
7.3.7 Allow
•amplM IB
oool ae th*y
ara net hot
to touch.
7.3.1 PteM
aampla In
aoid-«l«an*d
bottla.
7.3.8 • 7.3.8.3
Cantrlfug*.
•attla, and
flrta* lampta.
7.3.9 Camel
valuaa for
tho dilution
factor.
Stop
3015 - 12
Revision 0
Septenter 1994
-------
3020A
-------
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 spectroscbpy (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 MATERIAL'S
4.1 Griffin beakers - 150-mL, or equivalent. '
4.2 Watch glasses - ribbed or equivalent.
1 , _ '
3020A - .1 Revision 1
July 1992
-------
, 4.3 .Qualitative filter paper or centrifugation equipment.
4.4 Funnel or equivalent.
4.5 Graduated Cylinder - 100ml. " ' .
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 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 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
-------
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 refluxingj. 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 sol utilization 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.
' • • - i ' •
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 Chemiral 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 «ample
•liquot in
beaker, add
concentrated
HNOi,evaporate to
low volume . .
.1 Cool beaker,add
concentrated
HNO,,heat until
gentle reflux
action occur*
•7.2 H.«t to
.complete digestion,
evaporate to low
voluB«,cool
7.2 Add r««g«nt
watar,warB Vo
dmolvo an;
precipitate or
raiidu*
7.3 Filter or
centrifuge if
nece'*»ary and
adjuat volume
3020A - 5
Revision 1
July 1992
-------
3050A
-------
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)
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. 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
-------
4.0 APPARATUS AND MATERIALS
- • -i
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 i 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
-------
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 AT-1 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 wi'th 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 wa'tch 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% H2Q2 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
-------
7.5.2 Centrifugation - Centrifugatipn at 2,000-3,000 rpm for
10 minutes is usually sufficient to clear the supernatant.
7.5,3 vThe diluted sample has an approximate acid concentration of
5.0% (v/v) HC'l 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.
i.
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. v
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 Jteplicate 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.
' i '
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. v
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
analytif
for A» , Be,
Cd, Co, Cr,
F., Mo, Pb,
S., Ti, V
7.6 Continue
heating; to
reduce volume
7.6 Dilut. with
reagent water
and filter
partieulate* in
.digaitate
7.1 Mix
•ample; take
1-2 9 portion
for each
digestion
7.2 Add HNO,,
r«flux;repeat
HNO, reflux
until aolution
i» S ml
7.3 Add r.ag.nt
water and H,0i;
heat b«ak«r to
•tart pvroxida
reaction
7.4 Continue
adding H,0.
with heating
ICP or Flame AA
analyii* for
A., Ag, Al, Ba,
Be, Ca, Cd, Co,
Cr, Cu, Fe, K,
Mg, Mn, Ho, Ha,
Ni, 0., Pb, Se,
Tl, V, 2n
7.5 Add
eoneentrated
HC1 and
reagent
water; reflux
7.7.1 Report
concentration*,
and % «olid* of
*anple for dry
weight analyaii
7.5 Cooljdilute
with reagent
water, filter
partculate* in
digeitate
7.7. 2 -If *
•olid*
required,u««
homogeneoui
sample aliquot
Stop
3050A - 6
Revision 1
July 1992
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3051
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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
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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.
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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
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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-°C1) 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
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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
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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: Centrifugati.on 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 SW-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 interlaboratory test results, is located in Tables 1
and 2.
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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 fjg/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 //g/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
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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
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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
0.082"
- 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.
bRepeatability 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
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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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METHOD 3051
(MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS, SLUDGES,
SOILS, AND OILS)
HM
weight
decreaiad >
10% from
original?
3051 - 14
Revision 0
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3500A
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METHOD 3500A
ORGANIC EXTRACTION AND SAMPLE PREPARATION
1.0 SCOPE AND APPLICATION
i ' ' .
1.1 The 3500 Methods are procedures for quantitatively extracting
nonvolatile and semivolatile organic compounds from various sample matrices.
Cleanup and/or analysis of the resultant extracts are described,in Chapter Two,
Sections 2.3.2 and. 2.3.}, respectively. '
1.2 Method 3580 describes a solvent dilution technique that may be used
on non-aqueous nonvolatile and semivolatile 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 (if necessary). 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 organfcs (particularly chlorofluoro-carbons
and methylene chloride) through the sample container septum during shipment and
storage. A field blank prepared from organic-free reagent water and carried
through sampling and subsequent storage and handling can serve as a check on such
contamination.
3.2 Solvents, reagents, glassware,, and other sample processing hardware
may yield artifacts and/or interferences to sample analysis. All these materials
must be demonstrated to be free from interferences under the conditions of the
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.
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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 organophosphorus pesticides will degrade in this
situation. This problem is especially pronounced with glassware that may be
difficult to rinse (e.g.,500 ml K-D flask). These items should be hand-rinsed
very carefully to avoid this problem.
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific method of interest for a description of the
apparatus and materials needed.
,' . . \ •
5.0 REAGENTS
5.1 . Refer to.the specific method of interest for a description of the
solvents needed.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water as defined in Chapter One.
5.3 Stock standards: Stock solutions may be prepared from pure standard
materials or purchased as certified solutions.
5.3.1 Purgeable stock standards: Prepare stock standards in
methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these
materials should be prepared in a hood.
5.3.1.1 Place about 9.8 ml of methanol in a 10-mL tared
ground-glass-stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 min or until all alcohol-wetted surfaces
have dried. Weigh the flask to the nearest 0.0001 g.
5.3.1.2 Using a 100-/LiL syringe, immediately add two or
more drops of assayed reference material to the flask, then reweigh.
The liquid must fall directly into the alcohol without, contacting
the neck of the flask.
5.3.1.3 Reweigh, dilute to volume, stopper, then mix by
inverting the flask several times. Calculate the concentration in
milligrams, per liter (mg/L) from the net gain in weight. When
compound purity is assayed to be 96% or greater, the weight, may be
used without correction to calculate the, concentration of the stock
standard. Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by an
independent source.
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5.3.1.4 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.
5.3.1.5 All standards must be replaced after 1 month, or
sooner if comparison with check standards indicates a problem.
5.3.2 Semivolatile stock standards: Base/neutral and acid stock
standards are prepared in methanol. Organochlorine pesticide standards
are prepared in acetone.
i
5.3.2.1 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 qual'ity control check
samples indicate a problem.
5.4 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.
5.4.1 Base/neutral and acid surrogate spiking solutions: The
following are recommended surrogate standards.
Base/neutral Acid
2-Fluorobiphenyl 2-Fluorophenol
Nitrobenzene-d5 2,4,6-Tribromophenol
Terphenyl-d14 Phenol-d6
5.4.1.1 Prepare a surrogate standard spiking solution in
methanol that contains the base/neutral compounds at a concentration
of 100 mg/L, and the acid compounds at 200 mg/L for water and
sediment/soil samples (low- and medium-level). For waste samples,
the concentration should be 500 mg/L for base/neutrals and 1000 mg/L
for acids.
5.4.2 Organochlorine pesticide/PCB surrogate spiking solution: The
'• following are recommended surrogate standards for -Organochlorine
pesticides/PCBs.
Orqanochlorine pesticides/PCBs
Dibutylchlorendate (DBC) (if available)
2,4,5,6-Tetrachloro-meta-xylene (TCMX)
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5.4.2.1 Prepare a surrogate standard spiking solution at
a concentration of 1 mg/L in acetone for water and sediment/soil
samples. For waste samples, the concentration should be 5 mg/L.
5.4.3 Purgeable surrogate spiking solution: The following are
recommended surrogate standards for volatile organics.
', Purqeable orqanics
p-Bromof 1 uorobenzene"
l,2-Dichloroethane-d4
Toluene-d8
5.4.3.1 Prepare a surrogate spiking solution (as described
in Section 5.3.1 or through secondary dilution of the stock
standard) in methanol containing the surrogate standards at a
concentration of 25 mg/L.
5.5 .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.
5.5.1 Base/neutral and acid matrix spiking solution: Prepare a
spiking solution in methanol that contains each of the following
base/neutral compounds at 100 mg/L and the acid compounds at 200 mg/L for
water and sediment/soil samples. The concentration of these compounds
should be five, times higher for waste samples.
Base/neutrals Acids
1,2,4-Trichlorobenzene Pentachlorophenol
Acenaphthene Phenol '
2,4-Dinitrotoluene , 2-Chlorophenol
Pyrene • „ . • 4-Chloro-3-methylphenol
N-Nitroso-di-n-propylamine 4-Nitrophenol
1,4-Dichlorobenzene , .
5.5.2 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 (mq/U
Lindane 0.2
Heptachlor . 0.2
Aldrin 0.2
Dieldrin 0.5
Endrin 0.5 ,
4,4'-DDT 0.5
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5.5.3 Purgeable matrix spiking solution: Prepare a spiking solution
in methanol that contains the following compounds at a concentration of 25
mg/L.,
Purgeable organics
1,1-Dichloroethene ,
Trichlbroethene . ' \
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 Semivolatile organic sample extraction: Water, soil/sediment,
sludge, and waste samples requiring analysis for 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, if necessary,
matrix spiking solutions are added to the sample prior to extraction for all four
methods. . .
' . ' i
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 is 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. .
7.1.3 Method 3540: This is a procedure for extracting nonvolatile
and semivolatile 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
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extract is dried, concentrated and,, if necessary, exchanged into a solvent
compatible with further analysis.
• X
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 ultrasonic extraction. Two
procedures are detailed depending upon .the expected concentration of
organics in the sample; a low concentration and a high concentration
method. In both, a known weight of sample is mixed.with anhydrous sodium
sulfate and solvent extracted using ultrasonic extraction. The extract is
dried, concentrated and, if necessary, exchanged into a solvent compatible
with further analysis.
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. When using this method, the analyst
must use caution in determining,the correct concentration of spike and
surrogate solution to avoid diluting out these compounds when diluting the
sample. The loss of surrogate and spike data should only occur in samples
containing a high concentration of analytes which is unknown at the time
of extraction .or where sample interferences could not be eliminated
following the best attempts at extract cleanup .by the laboratory.
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 methods described
above is followed directly by gas chromatographic analysis (Methods 8010, 8011,
8015, 8020, 8021, 8030, 8240 and 8260). Samples prepared for semivolatile
analysis may, if necessary, undergo cle'anup (See Method 3600) prior to
application of a specific determinative method.
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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 is 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 iig/L. The evaluation of system.performance is,discussed in detail
in Method 8000, beginning with Paragraph 8.6
8.5.2 Semi volatile 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 spvked 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 semivolatile 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
mg/L in 2-propanol.
8.5.2.2 Method 8060 - Phthalate esters: The QC check
sample concentrate should contain the following analytes at the
following concentrations in acetone: butyl benzyl phthalate, 10
mg/L; bis(2.-ethylhexyl) phthalate, 50 mg/L; di-n-octylphthalate, 50
mg/L; and any other.phthalate.at 25 mg/L.
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8.5.2.3 '" Method 8070 - Nitrosamines: The QC check sample
concentrate should contain each analyte at 20 mg/L in methanol or
some other water miscible solvent. •
8.5.2.4 'Method 8080 - Organochlorine pesticides and PCBs:
The QC check sample concentrate should contain each single-component
analyte at the following concentrations in acetone or some other
water miscible solvent: 4,4'-ODD, 10 mg/L; 4,4'-DDT, 10 mg/L;
endosulfan II, 10 mg/L; endosulfan sulfate, 10 mg/L; endrin, 10
mg/L; and any other single-component pesticide at 2 mg/L . 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
mg/L in acetone.
,8.5.2.5 Method 8090.- Nitroaromatics and Cyclic Ketones:
The QC check sample concentrate should contain each analyte at the
following concentrations in acetone: each dinitrotoluene at 20
mg/L; and isophorone and nitrobenzene at 100 mg/L.
8.5.2.6 Method 8100 - Polynuclear aromatic hydrocarbons;
The QC check.sample concentrate should contain each analyte at the
following concentrations in acetonitrile: naphthalene, 100 mg/L;
acenaphthylene, 100 mg/L; acenaphthene, 100 mg/L; fluorene, 100
mg/L; pherianthrene, 100 mg/L; anthracene, 100 mg/L;
benzo(k)fluoranthene, 5 mg/L; and any other PAH at 10 mg/L .
8.3.2.7 Method 8110 - Haloethers: The QC check sample
concentrate should contain each analyte at a concentration of
20 mg/L in methanol or some other water miscible solvent.
8.5.2.8 Method 8120 - Chlorinated hydrocarbons: The QC
check sample concentrate should contain each analyte at the
following concentrations in acetone: hexachloro-substituted
hydrocarbons, 10 mg/L; ^and any other chlorinated hydrocarbon, 100
mg/L. , .-•;.-; ,
8.3.;2.9 Method 8140/8141 - Organophosphorus compounds:
The QC check sample concentrate should contain each analyte in
acetone at a concentration 1,000 times more concentrated than the
selected spike concentration.
8.3..2.10 Method 8150 - Chlorinated herbicides; The'QC
check sample concentrate should contain each analyte in acetone at
a concentration 1,000 times more concentrated 'than the selected
spike concentration. .
8.3.2.11 , Method 8250/8270 - SemivoTatile organics: The QC
check sample concentrate should contain each analyte in acetone at
a concentration of 100 mg/L.
8.3.2.12 Method 8310 - Polynuclear aromatic hydrocarbons:
The QC check sample concentrate should contain each analyte at the
following concentrations in acetonitrile: naphthalene, 100 mg/L;
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acenaphthylene, 100 mg/L; acenaphthene, 100 mg/L; fluorene,
100 mg/L; phenanthrene, 100 mg/L; anthracene, 100' mg/L;
. benzo(k)fluoranthene, 5 mg/L; and any other PAH at 10 mg/L.
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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METHOD 3500A
ORGANIC EXTRACTION AND SAMPLE PREPARATION
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3500A -' 10
Revision 1
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3510A
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METHOD 3510A
S'EPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method .also describes concentration techniques
suitable for preparing the extract for the appropriate determinative methods
described in Section 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly water-soluble organics in preparation for a variety
of chromatographic procedures.
2.0 SUMMARY OF METHOD
\- "•
2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), is serially extracted with methylene chloride using a separatory
funnel. The extract is dried, concentrated (if necessary), and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative step to be
used.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS ,
4.1 Separatory funnel - 2-liter, with Teflon stopcock.
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 elutipn solvent prior to packing the
column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025 or
.equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs. ^
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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-caps or crimp
tops.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Erlenmeyer flask - 250-ml.
4.9. Syringe - 5-mL.
,- 4.10 Graduated cylinder - 1-liter. ,
5.0 REAGENTS
5.1 Reagent,grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is
first ascertained.that the.reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination. Reagents -should be
stored in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide soluti'on (ION), NaOH. Dissolve 40 g NaOH in water
and dilute to 100 ml. .
5.4 .Sodium sulfate (granular, anhydrous), Na2S04. Purify by. heating at-
400°C for 4 hours in a shallow tray, or.by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is, precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate. ' •
5.5 : Sulfuric acid solution (1:1), H2S04. Slowly .add. .50 ml of H2S04
(sp. gr. 1.84) to 50 ml of water.
5.6 Extraction/exchange solvents (See Table 1 for choice of
extraction/exchange solvents).
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
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5.6.2 Hexane, C6HU - Pesticide quality or equivalent.
5.6.3 2-Propanol, CH3CH(OH)CH3 - Pesticide quality or equivalent.
5.6.4 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH3CN - Pesticide quality or equivalent.
5.6.6 Methanol, CH3OH - Pesticide quality or equivalent.
i • . .•'.-•
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING l
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE ,
7.1 Using a 1-liter graduated cylinder, measure 1 liter (nominal) of
sample and transfer it to the separatory funnel. If high concentrations are
anticipated, a smaller volume may be used and then diluted with water to 1 liter.
Add 1.0 mL of the surrogate standards to all samples, spikes, and blanks (see
Method 3500 and the determinative method to be used for details on the .surrogate
standard solution and the matrix spike solution). 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/nl of each
base/neutral analyte and 200 ng/juL of each acid analyte in the extract to be
analyzed (assuming a 1 juL injection). . If Method 3640, Gel-Permeation Cleanup,
is to be used, add twice the volume of surrogates and matrix spiking compounds
since half the extract is lost due to loading of the GPC column.
7.2 Check the pH of the sample with wide-range pH paper and, if
necessary, adjust the pH to that indicated in Table 1 for the specific
determinative method that will be used to analyze the extract.
7.3 Add 60 mL-of methylene chloride to the separatory funnel.
7.4 Seal and shake the separatory funnel vigorously for 1-2 minutes with
periodic venting to release excess pressure.
\ t
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken'once. The separatory
funnel should be vented into a hood to prevent unnecessary exposure
of the analyst to the organic vapor.
7.5 Allow the organic layer to separate from the water phase for a
minimum of 10 minutes. . If the^emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends upon
the sample and may include stirring, filtration of the emulsion through glass
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wool, centrifugation, or other physical methods. Collect the solvent extract in
an Erlenmeyer flask. If the emulsion cannot be broken (recovery of < 80% of the
methylene chloride, corrected for the water solubility of methylene chloride),
transfer the sample, solvent, .and emulsion into the extraction chamber of a
continuous extractor and proceed as described in Method 3520.
7.6 Repeat the extraction two more times u(sing fresh portions of solvent
(Sections 7.3 through 7.5). Combine the three solvent extracts.
. x " -
7.7 If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1.. Serially extract
three times with 60 ml of methylene chloride, as outlined in Sections 7.3
through 7.5. Collect and combine the extracts and label the combined extract
appropriately.
7.8 If performing GC/MS analysis (Method 8250 or 8270), the acid and.
base/neutral extracts may be combined prior to concentration. However, in some
situations, separate concentration and analysis of the acid and base/neutral
extracts may be preferable (e.g. if for regulatory purposes the presence or
absence of specific acid or base/neutral compounds at low concentrations must be
determined, separate extract analyses may be warranted).
7.9 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10-mL concentrator tube to a 500-mL evaporation flask.
7.10 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. Ririse:the Erlenmeyer flask, which contained the solvent extract,
with 20-30 ml of methylene chloride and add it to the column to complete the
quantitative transfer..
7.11 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
(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 10-20 minutes.• At the proper rate of
distillation the balls of the'column.will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 1 mL, remove the K-D
apparatus from the water bath and allow it to drain and cool for at least 10
minutes. .
7.12 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent, a.new
boiling chip, and reattach the Snyder column. Concentrate -the extract, as
described in Section 7.11, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.13 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.
3510A - 4 Revision 1
July 1992
-------
If sulfur crystals are a problem, proceed to Method 3660 for cleanup. The
extract may be further concentrated by using the technique outlined in Section
7.14 or adjusted to 10.0 mL with the solvent last used.
7.14 If further concentration is indicated in Table 1, add another clean
boiling chip to the concentrator tube and attach a two ball micro-Snyder column.
Prewet the column by adding 0.5,ml .of methylene chloride or exchange solvent to
the top of the column. Place the K-D apparatus in a hot water bath so that the
concentrator tube is partially immersed in the hot water. Adjust the vertical
position of the apparatus and the water temperature, as required, to complete the
concentration in 5-10 minutes. At the proper rate of distillation the balls of
the column will actively chatter, but the chambers will not flood. When the
apparent volume of liquid reaches 0.5 ml, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes. Remove the Snyder
column and rinse the flask and its lower joints into the concentrator tube with
0.2 ml of extraction solvent. Adjust the final volume to 1.0-2.0 mL, as
indicated in Table 1, with solvent.
7.15 The extract obtained (from either Section 7.13 or 7.14) may now be
analyzed for analyte content using a variety of organic techniques. If analysis
of the extract will not be performed immediately, stopper the concentrator tube
and store refrigerated. If the extract will be stored longer than 2,days, it
should be transferred to a vial with a Teflon lined screw-cap, 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.
. .' • i
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. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, D.C.,
. 1986." , . :
3510A - 5 Revision 1
July 1992
-------
TABLE 1.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8070
8080
8090
8100
8110
8120
8140
8141
8250b
8270b
8310
Initial
extraction
pH
<2
as received
as received
5-9
5-9
as received
as received
as received
6-8,
as received
>11
>11
as received
Secondary
extraction
PH
none
none
hone
none
none
none
none
none
none
none
<2
<2
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
methanol
hexane
hexane
none
hexane
hexane
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
methyl ene chloride
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
•
~" - . '
—
Volume
of extract ,
required
for
cleanup (ml)
1.0
2.0
2.0
10.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
*••
F i nal
extract
vol ume
for
analysis (ml)
1.0, 10. Oa
10.0
10.0
10.0
1.0
1.0
10.0
1.0
10.0
10.0
1.0
1.0
1.0
a 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 mi hexane extract to be analyzed by GC/ECD.
b 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.
3510A - 6
Revision 1
July 1992
-------
METHOD 3510A
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
7.1 Add eurrogata
cm* to u Mfflpw
•pikee, and blanks
7.7 Collect and
combine •xLrvctB
and label
7.6 GO/MS
analytls (Method
8250,8270)
being performed?
73. Cheek and
adjuetpH
7.6 Combine
baae/neuttaJ
extract* prior to
ooncenfratlon
7.3 • 7.6
Extracts
ttmee
7.9-7.14
Concentrate
extract
7.15
Ready for
analysie
7.7 Further
extracuona
required?
3510A - 7
Revision 1
July 1992
-------
3510B
-------
METHOD 3510B
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative methods
described in Sec. 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly water-soluble organics in preparation for a variety
of chromatographic procedures.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), is serially extracted with methylene chloride using a separatory
funnel. The extract is dried, concentrated (if necessary), and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method to
be used (see Table 1 for appropriate exchange solvents).
3.0 INTERFERENCES ,
3.1 Refer to Method 3500.
3.2 Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated. Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates. These reactions increase with
increasing pH, and are decreased by the shorter reaction times available in
Method 3510. Methods 3520/8270, 3510/8270, and 3510/8250, respectively, are
preferred over Method 3520/8250 for the analysis of these classes of compounds.
4.0 APPARATUS AND MATERIALS
4.1 Separatory funnel - 2 liter, with Teflon stopcock.
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
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.
3510B - 1 Revision 2
September 1994
-------
4.3 Kuderna-Danish (K-D) apparatus.
4.3.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
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 - 2 ml, glass with Teflon lined screw-caps or crimp tops.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Erlenmeyer flask - 250 ml.
4.9 Syringe - 5 ml.
4.10 Graduated cylinder - 1 liter.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
3510B - 2 Revision 2
September 1994
-------
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H2S04. Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, CH3CH(OH)CH3 - Pesticide quality or equivalent.
5.6.4 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH3CN - Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Using a 1 liter graduated cylinder, measure 1 liter (nominal) of
sample .and transfer it quantitatively to the separatory funnel. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter. Add 1.0 mL of the surrogate
standards to all samples, spikes, and blanks (see Method 3500 and the
determinative method to be used, for details on the surrogate standard solution
and the matrix spike solution). 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/^L of each base/neutral analyte and
200 ng//zL of each acid analyte in the extract to be analyzed (assuming a 1 pL
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.
7.2 Check the pH of the sample with wide-range pH paper and, if
necessary, adjust the pH to that indicated in Table 1 for the specific
determinative method that will be used to analyze the extract.
7.3 Add 60 mL of methylene chloride to the separatory funnel.
7.4 Seal and shake the separatory funnel vigorously for 1-2 minutes with
periodic venting to release excess pressure.
3510B - 3 Revision 2
September 1994
-------
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once. Venting of the
separatory funnel should be into a hood to avoid needless exposure
of the analyst to solvent vapors.
7.5 Allow the organic layer to separate from the water phase for a
minimum of 10 minutes. If the emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends upon
the sample and may include stirring, filtration of the emulsion through glass
wool, centrifugation, or other physical methods. Collect the solvent extract in
an Erlenmeyer flask. If the emulsion cannot be broken (recovery of < 80% of the
methylene chloride, corrected for the water solubility of methylene chloride),
transfer the sample, solvent, and emulsion into the extraction chamber of a
continuous extractor and proceed as described in Method 3520, Continuous Liquid-
Liquid Extraction.
7.6 Repeat the extraction two more times using fresh portions of solvent
(Sees. 7.3 through 7.5). Combine the three solvent extracts.
7.7 If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1. Serially extract
three times with 60 mL of methylene chloride, as outlined in Sees. 7.3
through 7.5. Collect and combine the extracts and label the combined extract
appropriately.
7.8 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral or base compounds at low concentrations must be determined, separate
extract analyses may be warranted).
7.9 Perform the concentration (if necessary) using the Kuderna-Danish
(K-D) Technique (Sees. 7.10.1 through 7.10.4).
7.10 K-D Technique
7.10.1 Assemble a Kuderna-Danish (K-D) concentrator by
attaching a 10 mL concentrator tube to a 500 mL evaporation flask. Dry
the extract by passing it through a drying column containing about 10 cm
of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Rinse the Erlenmeyer flask, which contained the solvent
extract,'* with 20-30 mL of methylene chloride and add it to the column to
complete the quantitative transfer.
7.10.2 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
3510B - 4 Revision 2.
September 1994
-------
vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 10-20 minutes.
At the proper rate of distillation the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume of
liquid reaches 1 ml, remove the K-D apparatus from the water bath and
allow it to drain and cool for at least 10 minutes.
7.10.3 If a solvent exchange is required (as indicated in Table
1), momentarily remove the Snyder column, add 50 ml of the exchange
solvent, a new boiling chip, and reattach the Snyder co-lumn. Concentrate..
the extract, as described in Sec. 7.11, raising the temperature of the
water bath, if necessary, to maintain proper distillation.
7.10.4 Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 mL of methylene chloride
or exchange solvent. If sulfur crystals are a problem, proceed to
Method 3660 for cleanup. The extract may be further concentrated by using
the technique outlined in Sec. 7.11 or adjusted to 10.0 ml with the
solvent last used.
7.11 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.11.1) or nitrogen blowdown technique (7.11.2) is used
to adjust the extract to the final volume required.
7.11.1 Micro-Snyder Column Technique
7.11.1.1 If further concentration is indicated in Table 1,
add another clean boiling chip to the concentrator tube and attach
a two ball micro-Snyder column. Prewet the column by adding 0.5 ml
of methylene chloride or exchange solvent to the top of the column.
Place the K-D apparatus in a hot water bath so that the concentrator
tube is partially immersed in the hot water. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
0.5 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 minutes. Remove the Snyder column
and rinse the flask and its lower joints into the concentrator tube
with 0.2 ml of extraction solvent. Adjust the final volume to 1.0-
2.0 ml, as indicated in Table 1, with solvent.
/
7.11.2 Nitrogen Blowdown Technique
7.11.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the
carbon trap and the sample, since it may
introduce interferences.
3510B - 5 Revision 2
September 1994
-------
7.11.2.2 The internal wall of the tube must be rinsed down
several times with methylene chloride or appropriate solvent during
the operation. During evaporation, the tube solvent level must be
positioned to avoid water condensation. Under normal procedures,
the extract must not be allowed to become dry.
CAUTION; When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.12 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored longer
than 2 days it should be transferred to a vial with a Teflon lined screw-cap or
crimp top, 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.
3510B - 6 Revision 2
September 1994
-------
TAB
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250bc
8270bd
8310
8321
8410
Initial
extraction
PH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
<2
as received
as received
as received
Secondary
extraction
PH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
>11
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
-
-
-
-
methylene chloride
Vol ume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Oa
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
a 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.
b 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.
c Loss of phthalate esters, organochlorine pesticides and phenols can occur under these extraction conditions (see Sec. 3.2).
d Extraction pH sequence may be reversed to better separate acid and neutral waste components. Excessive pH adjustments may
result in the loss of some analytes (see Sec. 3.2).
3510B - 7
Revision 2
September 1994
-------
METHOD 3510B
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
| Start j
7.1 Add surrogate
standards to all
samples, spikes,
and blanks.
7.7 Collect
and combine
extracts and label
7.8
GC/MS
analysis (Metho
8270) being
performed?
7.2 Check
and adjust pH.
7.8 Combine
base/neutral
extracts prior
to concentration
7.3 - 7.6
Extract 3
times.
7.9 - 7.11
Concentrate
extract.
7.7
Further
extractions
required?
7.12
Ready.for
analysis.
3510B - 8
Revision 2
September 1994
-------
3520A
-------
METHOD 3520A
CONTINUOUS LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the -extract for the appropriate determinative steps
described in Sectton 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly soluble organics in preparation for a variety of
chromatographic procedures.
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate the
effectiveness of any such automatic extraction device before employing it in
sample, extraction. '
2.0 SUMMARY OF METHOD , ,
i p •
2.1 A measured volume of sample, usually 1 liter, is placed into a
continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH (see
Table 1), and extracted with organic solvent for 18-24 hours. The extract is
dried, concentrated (if. necessary), and,-as necessary, exchanged into a solvent
compatible with the determinative step being employed.
!•
3.0, INTERFERENCES
3.1 Refer to Method 3500. J
4.0 APPARATUS AND MATERIALS
\ • .
4.1 Continuous liquid-liquid extractor - Equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication (Hershberg-Wolf
Extractor -- Ace Glass Company, Vineland, New Jersey, P/N 6841-10, or
equivalent). .
4.2 Drying column - 20 mm i.d. Pyrex chromatographic column w.ith 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.
3520A - 1 Revision 1
July 1992
-------
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
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 - 2-mL, glass with Teflon lined screw-caps or crimp tops.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Heating mantle - Rheostat controlled.
/ .
4.9 Syringe - 5-mL.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such, specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to,permit its
use without lessening the accuracy of the determination. Reagents .should be
stored in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g .NaOH in .water
and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a'shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
3520A -.2 Revision 1
July 1992
-------
5.5 Sulfuric acid solution (1:1), H2S04. Slowly add 50 ml of H2SO;
(sp. gr. 1.84) to 50 ml of water.
5.6 Extraction/exchange solvents (See Table, 1 for choice of
extraction/exchange solvents).
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
<• ' i i
5.6.2 Hexane, C6HU - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.6.4 Cyclohexane, C6H12 - Pesticide quality or equivalent.
. 5.6.5 Acetoni'trile, CH3CN - 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.
i - i
7.0 PROCEDURE : «
7.1 Using a graduated cylinder, measure out 1 liter (nominal) of sample
and transfer it to the continuous extractor. If high concentrations are
anticipated, a smaller volume may be used and then diluted with water to 1 1 iter.
Check the pH of the sample with wide-range - pH .paper and adjust the pH, if
necessary, to the pH indicated in Table 1. Pipet 1.0 mL of the surrogate
standard' spiking solution into each sample into the extractor and mix well. (See
Method 3500 and the determinative method to be used for details on the surrogate
standard solution and the matrix spike solution.) For the sample in each
analytical batch selected for spiking, add 1.0 mL of the1 matrix spiking standard.
For base/neutral-acid analysis, the amount of the surrogates and matrix spiking
compounds added to the sample should result in a final concentration of 100
ng/jiL of each base/neutral analyte and 200 ng/juL of * each acid analyte in the
extract to be analyzed (assuming a 1 /iL 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.
' 7.2 Add 300-500 mL of methylene chloride.to. the distilling flask. Add
several boiling chips to the flask.
7.3 Add sufficient water to the extractor to ensure .proper operation and
extract for 18-24 hours..
7.4 Allow to cool; then detach the boiling flask. If extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
as described in Sections 7.7 through 7.11.
3520A - 3 Revision 1
. July 1992
-------
7.5 Carefully, while stirring, adjust the pH of the aqueous phase to <2
with sulfuric acid (1:1). Attach a clean distilling flask containing 500 ml of
methylene chloride to the continuous extractor. Extract for 18-24 hours, allow
to cool, and detach the distilling flask.
7.6 If performing GC/MS analysis (Method 8250 or 8270), the acid and
base/neutral extracts may be combined prior to concentration. However, in some
situations, separate concentration and analysis of the acid and base/neutral
extracts may be preferable (e.g. if for regulatory purposes the presence or
absence of specific acid or base/neutral compounds at low concentrations must be
determined,1separate extract analyses may be warranted).
7.7 ' Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
concentrator tube,to a 500-mL evaporation flask.
7.8 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Rinse the flask which contained the solvent extract with 20-30 ml
of methylene chloride and add it to the column to complete the quantitative
transfer.
7.9 Add one or two clean boiling chips to the flask and attach a three
ball Snyder column. Prewet'the Snyder column by adding about 1 mL of methylene
chloride to the top of the column. Place the K-D apparatus on a:hot water bath
(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 10-20 minutes. , At the proper rate of
distillation the balls of the column will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 1 ml, remove the K-D
apparatus from the water bath and allow it to drain and cool for at least 10
minutes. Remove the Snyder column and rinse the flask and its lower joints into
the concentrator tube with 1-2 ml of extraction solvent.
7.10 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 mL of the exchange solvent, a new
boiling chip, and reattactv the Snyder column. . Concentrate the extract, as
described in Section 7.9, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.11 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange solvent.
If sulfur crystals are a problem, proceed to Method 3660 for cleanup. The
extract may be further concentrated by using the technique outlined in Section
7.12 or adjusted to 10.0 ml with the solvent last used.
7.12 Add another one or two clean boiling chips to the concentrator tube
and attach a two bail micro-Snyder column. Prewet the column by adding 0.5 ml
of methylene chloride or exchange solvent to the top of the column. Place the
K-D apparatus in a hot water bath so that the concentrator tube is partially
immersed in the hot.water. Adjust the vertical position of the 'apparatus and the
water temperature, as required, to complete the concentration in 5-10 minutes.
At the proper rate of distillation the balls of the column will actively chatter,
3520A - 4 - Revision 1
July 1992
-------
but the chambers will not flood.- When the apparent volume of liquid reaches
0.5 ml, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 minutes. Remove the Snyder column, rinse the flask and its
lower joints into the concentrator tube with 0.2 ml of methylene chloride or
exchange solvent, and adjust the final volume to 1.0 to 2.0 ml, as indicated in
Table 1, with solvent.
7.13 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 vial with a Teflon lined screw-cap and labeled
appropriately.
8.0 QUALITY CONTROL
. 8.1 Any reagent blanks, matrix spike, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample^preparation procedures.
9.0 METHOD PERFORMANCE
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. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical ,Society: Washington, D.C., 1986
3520A - 5 , Revision 1
' . July 1992
-------
TABLE 1. .
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8070
8080
8090
8100
8110
8120
8140
8141
8250b
8270b
8310
Initial
extraction
pH
<2
as received
as received
5-9
5-9
as received
as received
as received
6-8
as received
>11
as received
'
Secondary
extraction
pH
none
none
none
none
none
none
none
none
none :
none
<2
<2
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
methanol
hexane
hexane
none
hexane
hexane
, hexane
hexane
none
. none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
methyl ene chloride
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
;
-
Vol ume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
10.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-—
Final
extract
volume x
for
analysis (mL)
1.0,10.0° ,
10.0
10.0
10.0
1.0
1.0
10.0
1.0
10.0 ,
10.0
1.0
1.0
1.0
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.
b The specificity of GC/MS may make cleanup of the extracts unnecessary.
procedures available if required.
Refer to Method 3600 for guidance on the cleanup
3520A - 6
Revision 1
July 1992
-------
METHOD 3520A
CONTINUOUS LIQUID-LIQUID EXTRACTION
Start
7.1 Add appropriate
surrogate and
mafta spiking
solutions
7 2 Add methytene
cMoridei to
7.3 Add regent
water to extractor:
extract for 18-24
hours
7.5 Adjust pH of
aqueous phatw:
extract for 18-24
hours wtth dean
flask
7.6 Combine add
and bBMmeutm
extracts prior to
7.7 Assemble K-D
7.80ryex«raot:co»ict
dh0d •xftnctln
K-Ooono*mior
7.0 Conoantrtli Ming
Snyder column tnd
K-Oappwitue
7.10 Add exchange
solvent
concentrate exfract
7.11-7.12
Further concentrate
extract If necessary;
adjust fnal volume
I
7.13 Analyze
using organic
techniques
8000
Series
ises/
3520A - 7
Revision 1
July 1992
-------
3520B
-------
METHOD 3520B
CONTINUOUS LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative steps
described in Sec. 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly soluble organics in preparation for a variety of
chromatographic procedures.
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate the
effectiveness of any such automatic extraction device before employing it in
sample extraction.
2.0 SUMMARY OF'METHOD
2.1 A measured volume of sample, usually 1 liter, is placed into a
continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH (see
Table 1), and extracted with organic solvent for 18-24 hours. The extract is
dried, concentrated (if necessary), and, as necessary, exchanged into a solvent
compatible with the cleanup or determinative method being employed (see Table 1
for appropriate exchange solvents).
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated. Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates. Th'ese reactions increase with
increasing pH, and are decreased by the shorter reaction times available in
Method 3510. Methods 3520/8270, 3510/8270, and 3510/8250, respectively, are
preferred over Method 3520/8250 for the analysis of these classes of compounds.
4.0 APPARATUS AND MATERIALS .
4.1 Continuous liquid-liquid extractor - Equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication (Kontes 584200-0000,
584500-0000, 583250-0000, or equivalent).
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
3520B - 1 Revision 2
September 1994
-------
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small, pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 mL of
acetone followed by 50 ml of elution solvent prior to packing the
column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
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 - 2 ml, glass with Teflon lined screw-caps or crimp tops.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Heating mantle - Rheostat controlled.
4.9 Syringe - 5 ml.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
3520B - 2 Revision 2
September 1994
-------
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H2S04. Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.6.4 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH3CN - Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Using a 1 liter graduated cylinder, measure out 1 liter (nominal) of
sample and transfer it quantitatively to the continuous extractor. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter. Check the pH of the sample with wide-
range pH paper and adjust the pH, if necessary, to the pH indicated in Table 1
using 1:1 (V/V). salfuric acid or 10 N sodium hydroxide. Pipet 1.0 mL of the
surrogate standard spiking solution into each sample into the extractor and mix
well. (See Method 3500 and the determinative method to be used, for details on
the surrogate standard solution and the matrix spike solution.) 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 of the surrogates and
matrix spiking compounds added to the sample should result in a final
concentration of 100 ng/juL of each base/neutral analyte and 200 ng//iL of each
acid analyte in the extract to be analyzed (assuming a 1 juL injection). If
Method 3640, Gel-Permeation Cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.2 Add 300-500 mL of methylene chloride to the distilling flask. Add
several boiling chips to the flask.
3520B - 3 Revision 2
September 1994
-------
7.3 Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.
7.4 Allow to cool; then detach the boiling flask. If extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
using one of the techniques referred to in Sec. 7.7.
7.5 Carefully, while stirring, adjust the pH of the aqueous phase to the
second pH indicated in Table 1. Attach a clean distilling flask containing
500 ml of methylene chloride to the continuous extractor. Extract for 18-24
hours, allow to cool, and detach the distilling flask.
7.6 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral and base compounds at low concentrations must be determined,
separate extract analyses may be warranted).
7.7 Perform concentration (if necessary) using the Kuderna-Danish (K-D)
Technique (Sees. 7.8.1 through 7.8.4).
7.8 K-D Technique
7.8.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10
ml concentrator tube to a 500 ml evaporation flask. Dry the extract by
passing it through a drying column containing .about 10 cm of anhydrous
sodium sulfate. Collect the dried extract in a K-D concentrator. Rinse
the flask which contained the solvent extract with 20-30 ml of methylene
chloride and add it to the column to.complete the quantitative transfer.
7.8.2 Add one or two clean boiling chips to the flask and attach a
three,ball Snyder column. Prewet the Snyder column by adding about 1 ml
of methylene chloride to the top of the column. Place the K-D apparatus
on a hot water bath (15-20°C above the boiling point of the solvent) so
that the concentrator tube is partially immersed in the hot water and the
entire lower rounded surface of the flask is bathed with hot vapor.
Adjust the vertical position of the apparatus and the water temperature,
as required, to complete the concentration in 10-20 minutes. At the
proper rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 minutes. Remove the Snyder column and
rinse the flask and its lower joints into the concentrator tube with 1-2
ml of extraction solvent.
7.8.3 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent,
a new boiling chip, and reattach the Snyder column. Concentrate the
extract, as described in Sec. 7.9, raising the temperature of the water
bath, if necessary, to maintain proper distillation.
3520B - 4 Revision 2
September 1994
-------
7.8,4 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1-2 ml of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method
3660 for cleanup. The extract may be further concentrated by using the
techniques outlined in Sec. 7.9 or adjusted to 10.0 ml with the solvent
last used.
7.9 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.9.1) or nitrogen blowdown technique (7.9.2) is used
to adjust the extract to the final volume required.
7.9.1 Micro-Snyder Column Technique
7.9.1.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball micro-Snyder column. _Prewet
the column by adding 0.5 ml of methylene chloride or exchange
solvent to the top of the column. Place the K-D apparatus in a hot
water bath so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete the concentration in
5-10 minutes. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 0.5 ml, remove the K-D
apparatus from the water bath and allow it to drain and cool for at
least 10 minutes. Remove the Snyder column, rinse the flask and its
lower joints into the concentrator tube with 0.2 ml of methylene
chloride or exchange solvent, and adjust the final volume to 1.0 to
2.0 ml, as indicated in Table 1, with solvent.
7.9.2 Nitrogen Blowdown Technique
7.9.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the
carbon trap and the sample, since it may
introduce interferences.
7.9.2.2 The internal wall of the tube must be rinsed down
several times with methylene chloride or appropriate solvent during
the operation. During evaporation, the tube solvent level must be
positioned to avoid water condensation. Under normal procedures,
the extract must not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.10 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored longer
3520B - 5 Revision 2
September 1994
-------
than 2 days it should be transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spike, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample-preparation procedures.
9.0 METHOD PERFORMANCE
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.
3520B - 6 Revision 2
September 1994
-------
TABLl
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Initial Secondary
Determinative extraction extraction
method pH pH
8040 <2 none
8060 as received none
8061 as received none
8070 as received none
8080 5-9 none
8081 5-9 none
8090 5-9 none
8100 as received none
8110 as received none
8120 as received none
8121 as received none
8140 6-8 none
8141 as received none
8250b-c >11 <2
8270b'd <2 >11
8310 as received none
8321 as received none
8410 as received none
a Phenols may be analyzed, by Method 8040,
derivatization procedure for phenols whi
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
.
-
-
-
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also contains
ch results in a 10 ml hexane extract to be analyzed by GC/ECD.
b The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method
procedures available if required.
c Loss of phthalate esters, organochlorine
3600 for guidance on
pesticides and phenols can occur under these extraction conditions (see
d If further separation of major acid and neutral components is
recommended. Reversal of the Method 8270
continuous extraction (see Sec. 3.2).
required, Method 3650,
Acid-Base Partition
Final
extract
volume
for
analysis (mL)
1.0,10.0a
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
an optional
the cleanup
Sec. 3.2).
Cleanup, is
pH sequence is not recommended as analyte losses are more severe under the base first
3520B - 7
Revision 2
September 1994
-------
METHOD 3520B
CONTINUOUS LIQUID-LIQUID EXTRACTION
7.1 Add appropriate
surrogate and
matrix spiking
solutions.
7.7 - 7.8
Concentrate extract
7.2 Add methylene
chloride to
distilling flask.
7.8.3 Is
solvent
exchange
required?
7.8.3 Add
exchange solvent;
concentration extract
7.3 Add reagent
water to extractor
extract for 18-24
hours.
7.9 Further
concentrate extract
if necessary;
adjust final volume.
7.5 Adjust pH of
aqueous phase;
extract for 18-24
hours with clean
flask.
7.10 Analyze using
organic techniques.
7.6
GC/MS
analysis
(Method 8270)
performed?
8000
Series
Methods
7.6 Combine acid
and base/neutral
extracts prior to
concentration.
3520B - 8
Revision 2
September 1994
-------
3540A
-------
METHOD 3540A
SQXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3540 I:; 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 s.ulfate, 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 (if necessary), 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). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500-mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
3540A - 1 Revision 1
. July 1992
-------
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-caps or crimp
tops.
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 grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents, of the American Chemical Society, where
such specifications are. available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic^free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04: Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
3540A - 2 Revision 1
i July 1992
-------
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there, is no interference from
the sodium sulfate. . •
5.4 Extraction solvents
5.4.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems':
5.4.1.1 Toluene/Methanol ((10:1) (v/v)), C
Pesticide quality or equivalent. . ' , •
5.4.1.2 . Acetone/Hexane ((1:1) (v/v)), CH3COCH3/CH3(CH2)4CH3.
Pesticide quality or equivalent.,
5.4.2 Other samples shall be extracted using the following:
5.4.2.1 Methylene chloride, CH2C12. Pesticide quality or
equivalent. '
5.5. Exchange solvents
5.5..1 Hexane, C6H14. Pesticide quality or equivalent.
5.5.2 2-Propanol, (CH3).2CHOH. Pesticide quality or equivalent.
5.5.3 Cyclohexane, C6H12. Pesticide quality^or equivalent.
5.5.4 Acetpnitrile, CH3CN. 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 wa:ter 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 multiphase*-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.
3540A - 3 Revision 1
July 1992
-------
7.2 Determination of percent moisture - In certain cases, sample results
are desired based on 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:
% moisture = g of sample - q of drv sample x 100
g of sample
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble. The extraction thimble must drain freely for
the duration of the extraction period. A glass wool plug above and 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 and the determinative method to be used 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//iL of each
base/neutral analyte and 200 ng/juL of each acid analyte in the extract to be
analyzed (assuming a 1 jiL 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 approximately 300 mL of the extraction solvent (Section 5.3)
i.nto a 500-mL round-bottom flask containing one or two clean boiling chips.
Attach the flask to the extractor and extract the, sample for 16-24 hours at 4-6
cycles/hr. v . . , . •'
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 col.umn containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a-K-D
concentrator. Wash the extractor flask and sodium sulfate column with 100 to 125
mL of extraction solvent to complete the quantitative transfer.
7.8 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 minutes. At the proper rate of distillation the balls of the column
3540A - 4 Revision 1
. July 1992
-------
will actively chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 1 ml, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.
7.9 If a solvent ' exchange js required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 mi of the exchange solvent and a new
boiling chip, and reattach the Snyder column. Concentrate the extract as
described in Section 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 Section
7.9 or adjusted to 10.0 ml with the solvent last used!
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 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 0.5 ml, remove the K-D
apparatus from the water bath and allow it to drain and cool for at least 10
minutes. Remove the Snyder column and rinse the flask and its lower joints into
the concentrator tube with 0.2 ml of solvent. Adjust the final volume to 1.0-2.0
ml, as indicated in-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 vial with a Teflon lined screw-cap and labeled
appropriately.
; \ . l • . •'
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.
3540A - 5 " Revision 1
July 1992
-------
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. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; -American Chemical Society: Washington, D.C.,
1986. .
3540A - 6 Revision 1
•July 1992
-------
TABLE 1.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040a
8060
8070
8080
8090
8100
8110
8120
8140
8141
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
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
methanol
hexane
hexane
none
hexane
hexane
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane .
hexane
methylene chloride
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
--
•_'
Vol ume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
10.0
2.0
2.0
2.0
2.0
10.0
10.0
--
--
Final
extract
vol ume
for
analysis
1.0, 10.
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1-0.0
10.0
1.0
1.0
1.0
(ml)
Ob
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10..0 ml. '
b Phenols may be analyzed by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also
contains an optical derivatization procedure for phenols which results in a 10 ml hexane extract to be
analyzed by GC/ECD,
c 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.
3540A - 7
Revision 1
July 1992
-------
METHOD 3540A
SOXHLET EXTRACTION
Start
7.1 Use appropriate
sample handling
technique
I
7.2 Determine
sample percent
moisture
7.3 Add appropriate
surrogate and
matrix spiking •
standards
I
7.4 Add extraction
solvent to flask;
extract for 16-24
hours
7.5 Cool extract
7.6 Assemble K-0
concentrator
7.7 Dry and collect
' extract in K-D
concentrator
1
7.8 Concentrate
jslng Snyder column
and K-0 appartus
7.11 Reooncentrate
using Snyder
'column and K-0
appartus
Yes
7.12 Analyze using
organic technique
Proceed
to Method
3660 tor.
cleanup
7.91s
solvent
exchange
required?
8000
Series
Methods
7.9 Add exchange
solvent)
reconcentrate
extract
3540A - 8
Revision 1
July 1992
-------
3540B
-------
METHOD 35408
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 (if necessary), 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 ID, with 500 mL round bottom flask.
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 mL of
acetone followed by 50 mL of elution solvent prior to packing the
column with adsorbent.
4.3 Kuderna-Danish.(K-D) apparatus
4.3.1 Concentrator tube - 10 mL, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
3540B - 1 Revision 2
September 1994
-------
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
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 or crimp top.
4.7 Glass or paper thimble or glass wool - Contaminant free.
4.8 Heating mantle - Rheostat controlled.
4.9 Disposable glass pasteur pipet and bulb.
4.10 Apparatus for determining percent dry weight.
4.10.1 Oven - Drying.
4.10.2 Desiccator.
4.10.3 Crucibles - Porcelain or disposable aluminum.
4.11 Apparatus for grinding
4.12 Analytical balance - 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
3540B - 2 Revision 2
September 1994
-------
5.4 Extraction solvents
5.4.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems:
5.4.1.1 Acetone/Hexane (1:1) (v/v), CH3COCH3/C6HU.
Pesticide quality or equivalent.
NOTE: This solvent system has lower disposal cost and lower
toxicity.
5.4.1.2 Methylene chloride/Acetone (1:1 v/v),
CH2C12/CH3COCH3. Pesticide quality or equivalent.
5.4.2 Other samples shall be extracted using the following:
5.4.2.1 Methylene chloride, CH2C12. Pesticide quality or
equivalent.
5.4.2.2 Toluene/Methanol (10:1) (v/v), C6H5CH3/CH3OH.
Pesticide quality or equivalent.
5.5 Exchange solvents
5.5.1 Hexane, C6H14. Pesticide quality or equivalent.
5.5.2 2-Propanol, (CH3)2CHOH. Pesticide quality or equivalent.
5.5.3 Cyclohexane, C6H12. Pesticide quality or equivalent.
5.5.4 Acetonitrile, CH3CN. Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analysis, Sec.
4.1.
7.0 PROCEDURE
7.1 Sample Handling
7.1.1 Sediment/soil samples - Decant and discard any water layer on
a sediment sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7.1.2 Waste samples - Samples consisting of 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
3540B - 3 Revision 2
September 1994
-------
be extruded through a 1 mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.1.4 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. The professional
judgment of the analyst is required for handling these difficult matrices.
7.2 Determination of sample % dry weight - In certain cases, sample
results are desired based on dry weight basis. When such data are desired, a
portion of sample for this determination should be weighed out at the same time
as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be oven dried because
of concerns for personal safety. Laboratory discretion is advised. It may be
prudent to delay oven drying of the weighed-out portion until other analytical
results are available.
7.2.1 Immediately after weighing the sample for extraction, weigh 5-
,10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
% dry weight = q of dry sample x 100
g of sample
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble. The extraction thimble must drain freely for
the duration of the extraction period. A glass wool plug above-and 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//iL of each base/neutral analyte and 200 ng//iL of each acid analyte in
the extract to be analyzed (assuming a 1 /LiL injection). If Method 3640, Gel
Permeation Chromatography Cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.4 Place approximately 300 ml of the extraction solvent (Sec. 5.4) into
a 500 ml round bottom flask containing one or two clean boiling chips. Attach
the flask to the extractor and extract the sample for 16-24 hours at 4-6
cycles/hr.
7.5 Allow the extract to cool after the extraction is complete.
3540B - 4 Revision 2
September 1994
-------
7.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) 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 to 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 minutes. At the proper rate of distillation the balls of the column
will actively chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 1-2 ml, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.
7.9 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add approximately 50 ml of the exchange
solvent and a new boiling chip, and reattach the Snyder column. Concentrate the
extract as described in Sec. 7.8, raising the temperature of the water bath, if
necessary, to maintain proper distillation. When the apparent volume again
reaches 1-2 ml, remove the K-D apparatus from the water batch and allow it to
drain and cool for at least 10 minutes.
7.10 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 techniques described in Sec.
7.11 or adjusted to 10.0 ml with the solvent last used.
7.11 If further concentration is indicated in Table 1, either micro Snyder
column technique (Sec. 7.11.1) or nitrogen blowdown technique (Sec. 7.11.2) is
used to adjust the extract to the final volume required.
7.11.1 Micro Snyder Column Technique
7.11.1.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0.5 ml of methylene chloride or exchange
solvent to the top of the column. Place the K-D apparatus in a hot
water bath so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete the concentration in
5-10 minutes. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 0.5 ml, remove the K-D
apparatus from the water bath and allow it to drain and cool for at
least 10 minutes. Remove the Snyder column and rinse the flask and
its lower joints with about 0.2 ml of solvent and add to the
3540B - 5 Revision 2
September 1994
-------
concentrator tube. Adjust the final volume to 1.0-2.0 ml, as
indicated in Table 1, with solvent.
7.11.2 Nitrogen Slowdown Technique
7.11.2.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION; Do not use plasticized tubing between the carbon
trap and the sample.
7.11.2.2 The internal wall of the tube must be rinsed down
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.12 The extracts obtained may now be analyzed for the target analytes
using the appropriate organic technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store in a refrigerator. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon lined screw
cap or crimp top, 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.
3540B - 6 Revision 2
September 1994
-------
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040"
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250a'c
8270a'c
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
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
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methyl ene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
--
methylene chloride
Vol ume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
--
--
--
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10.0 ml.
b Phenols may be analyzed by Method 8040 using a 1.0 ml 2-propanol extract and analysis by GC/FID. Method 8040
also contains an optical 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.
on the cleanup procedures available if required.
Refer to Method 3600 for guidance
3540B - 7
Revision 2
September 1994
-------
METHOD 3540B
SOXHLET EXTRACTION
7.1
Use appropriate
sample handling
technique
1
7.2
Determine sample %
dry weight
i
, 7-3 '
Add appropriate
surrogate and matrix
spiking standards
7.4
Add extraction
solvent to flask:
extract for 16-24
hours
1 r
7.5
Cool extract
-.
7.6
Assemble K-D
concentrator
7.7
Dry and collect
extract in K-D
concentrator
7.8
Concentrate using .
Snyder column
and K-D apparatus
7.9
Is solvent
exchange required?
7.12
Analyze using
organic techniques
Proceed
to Method
3660 for
cleanup
8000
Series
Methods
Yes
7.9
Add exchange
solvent,
reconcentrate extract
3540B - 8
Revision 2
September 1994
-------
3541
-------
METHOD 3541
AUTOMATED SOXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3541 describes the extraction of organic analytes from soil,
sediment, sludges, and waste solids. The method uses a commercially available,
unique, three stage extraction system to achieve analyte recovery comparable to
Method 3540, but in a much, shorter time. There are two differences between this
extraction method and Method 3540. In the initial extraction stage of Method
3541, the sample-loaded extraction thimble is immersed into the boiling solvent.
This ensures very rapid intimate contact between the specimen and solvent and
rapid extraction of the organic analytes. In the second stage the thimble is
elevated above the solvent, and is rinse-extracted as in Method 3540. In the
third stage, the solvent is .evaporated, as would occur in the Kuderna-Danish
(K-D) concentration step in Method 3540. The concentrated extract is then ready
for cleanup (Method 3600) followed by measurement of the organic analytes.
1.2 The method is applicable to the extraction and concentration of water
insoluble or slightly water soluble polychlorinated biphenyls (PCBs) in
preparation for gas chromatographic determination using either Method 8080 or
8081. This method is applicable, to soils, clays, solid wastes and sediments
containing from 1 to 50 /jg of PCBs (measured, as Arochlors) per gram of sample.
.It has been statistically evaluated at 5 and 50 /ng/g of Arochlors 1254 and 1260,
and found to be equivalent to Method 3540 (Soxhlet Extraction). Higher
concentrations of PCBs are measured following volumetric dilution with hexane.
1.3 The method is also applicable the extraction and concentration of
seiiiivolatile organics in preparation for GC/MS analysis by Method 8270 or by
analysis using specific GC or HPLC methods.
2.0 SUMMARY OF METHOD
2.1 PCBs: Moist solid samples (e.g., soil/sediment samples) may be air-
dried and ground prior to extraction or chemically dried with anhydrous sodium
sulfate. The prepared sample is extracted using 1:1 (v/v) acetone:hexane in the
automated Soxhlet following the same procedure as outlined for semi volatile
organics in Sec. 2.1. The extract is then concentrated and exchanged into pure
hexane prior to final gas chromatographic PCB measurement.
2.2 Other semivolatile organics: A 10-g solid sample (the sample is pre-
mixed with anhydrous sodium sulfate for certain matrices) is placed in an
extraction thimble and usually extracted with 50 ml of 1:1 (v/v) acetone/hexane
for 60 minutes in the boiling extraction solvent. The thimble with sample is
then raised into the rinse position and extracted for an additional 60 minutes.
Following the extraction steps, the extraction solvent is concentrated to 1 to
2 ml.
3541 - 1 Revision 0
September 1994
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3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 The extraction thimble and the o-rings used to seal the extraction
cup are both a source of interference. Both should be checked by including a
method blank and following the extraction procedure as written. Solvent rinsing
or extraction, prior to use, may be necessary to eliminate or reduce
interferences. Viton seals contributed least to the interference problem,
however, even they contributed some interference peaks when the extraction
solvent was analyzed by the electron capture detector. Use of butyl or EPDM
rings are not recommended since they were found to contribute significant
background when the extraction solvent was 1:1 v/v hexane/acetone or 1:1 v/v
methylene chloride/acetone.
4.0 APPARATUS AND MATERIALS
4.1 Automated Soxhlet Extraction System - with temperature-controlled oil
bath (Soxtec, or equivalent). Tecator bath oil (catalog number 1000-1886) should
be used with the Soxtec. Silicone oil must not be used because it destroys the
rubber parts. See Figure 1. The apparatus is used in a hood.
4.2 Accessories and consumables for the automated Soxhlet system. (The
catalog numbers are Fisher Scientific based on the use of the Soxtec HT-6,
however, other sources that are equivalent are acceptable.)
4.2.1 Cellulose extraction thimbles - 26 mm ID x 60 mm
contamination free, catalog number 1522-0034, or equivalent.
4.2.2 Glass extraction cups (80 ml) - (set of six required for the
HT-6), catalog number 1000-1820.
4.2.3 Thimble adapters - (set of six required for the HT-6),
catalog number 1000-1466.
4.2.4 Viton seals - catalog number 1000-2516.
4.3 Syringes - 100 and 1000 juL and 5 ml.
4.4 Apparatus for Determining Percent Dry Weight
4.4.1 Drying Oven.
4.4.2 Desiccator.
4.4.3 Crucibles, porcelain.
4.4.4 Balance, analytical.
4.5 Apparatus for grinding - Fisher Cyclotec, Fisher Scientific catalog
number 1093, or equivalent.
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4.6 Spatula
4.7 Graduated cylinder - 100 ml.
4.8 Aluminum weighing dish - VWR Scientific catalog number 25433-008 or
equivalent.
4.9 Graduated, conical-bottom glass tubes - 15 ml, Kimble catalog number
45166 or equivalent, or 10 ml KD concentrator tube.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. A method blank must be analyzed, demonstrating that there
is no interference from the sodium sulfate.
5.4 Extraction solvents:
5.4.1 Organochlorine pesticides/PCB extraction:
5.4.1.1 Acetone/hexane (1:1 v/v), CH3COCH3/C6H14.
Pesticide quality or equivalent.
5.4.2 Semivolatile organics extraction:
5.4.2.1 Acetone/hexane (1:1 v/v), CH3COCH3/C6H14.
Pesticide quality or equivalent.
5.4.2.2 Acetone/methylene chloride (1:1 v/v),
CH3COCH3/CH2C12. Pesticide quality or equivalent.
5.5 Hexane, C6H14. Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
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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.
7.1.1.1 PCBs or high-boiling organochlorine pesticides -
Air-dry the sample at room temperature for 48 hours in a glass tray
or on hexane-cleaned aluminum foil, or dry the sample by mixing with
anhydrous sodium sulfate until a free-flowing powder is obtained
(see Sec. 7.2).
NOTE: Dry, finely ground soil/sediment allows the best
extraction efficiency for non-volatile, non-polar
organics, e.g., PCBs, 4,4'-DDT, etc. Air-drying
is not appropriate for the analysis of the more
volatile organochlorine pesticides (e.g. the
BHCs) or the more volatile of the semivolatile
organics because of losses during the drying
process.
7.1.2 Dried sediment/soil and 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 20 g after
grinding. Disassemble grinder between samples, according to
manufacturer's instructions, and clean with soap and water, followed by
acetone and hexane rinses.
NOTE: The same warning on loss of volatile analytes applies to the
grinding process. Grinding should only be performed when
analyzing for non-volatile organics.
7.1.3 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. If grinding of
these materials is preferred, the addition and mixing of anhydrous sodium
sulfate with the sample (1:1) may improve grinding efficiency. The
professional judgment of the analyst is required for handling such
difficult matrices.
7.1.4 Multiple phase waste samples - Samples consisting of multiple
phases must be prepared by the phase separation method in Chapter Two
before extraction. This procedure is for solids only.
7.2 For sediment/soil (especially gummy clay) that is moist and cannot
be air-dried because of loss of volatile analytes - Mix 5 g of sample with 5 g
of anhydrous sodium sulfate in a small beaker using a spatula. Use this approach
for any solid sample that requires dispersion of the sample particles to ensure
greater solvent contact throughout the sample mass.
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7.3 Determination of sample percent dry weight - In certain cases, sample
results are desired based on dry weight basis. When such data are desired, a
portion of sample for this determination should be weighed out at the same time
as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from the
drying of a heavily contaminated hazardous waste sample.
7.3.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
% dry weight = q of dry sample x 100 ,':'::
g of sample
7.4 Check the heating oil level in the automated Soxhlet unit and add oil
if needed. See service manual for details. Set the temperature on the service
unit at 140°C when using hexane-acetone (1:1, v/v) as the extraction solvent.
7.5 Press the "MAINS" button; observe that the switch lamp is now "ON".
7.6 Open the cold water tap for the reflux condensers. Adjust the flow
to 2 L/min to prevent solvent loss through the condensers.
7.7 Weigh 10 g of sample into extraction thimbles. For samples mixed
with anhydrous sodium sulfate, transfer the entire contents of the beaker (Sec.
7.2) to the thimble. Add surrogate spikes to each sample and the matrix
spike/matrix spike duplicate to the selected sample.
NOTE: When surrogate spikes and/or matrix spikes contain relatively
volatile compounds (e.g., trichlorobenzenes, BHCs, etc.), steps 7.8,
7.9, and 7.10 must be performed quickly to avoid evaporation losses
of these compounds. As the spike is added to the sample in each
thimble, the thimble should immediately be transferred to the
condenser and lowered into the extraction solvent.
7.8 Immediately transfer the thimbles containing the weighed samples into
the condensers. Raise the knob to the "BOILING" position. The magnet will now
fasten to the thimble. Lower the knob to the "RINSING" position. The thimble
will now hang just below the condenser valve.
7.9 Insert the extraction cups containing boiling chips, and load each
with 50 mL of extraction solvent (normally 1:1 (v/v) hexane:acetone, see Sec.
5.4). Using the cup holder, lower the locking handle, ensuring that the safety
catch engages. The cups are now clamped into position. (The seals must be pre-
rinsed or pre-extracted with extraction solvent prior to initial use.)
7.10 Move the extraction knobs to the "BOILING" position. The thimbles
are now immersed in solvent. Set the timer for 60 minutes. The condenser valves
must be in the "OPEN" position. Extract for the preset time.
3541 - 5 Revision 0
September 1994
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7.11 Move the extraction knobs to the "RINSING" position. The thimbles
will now hang above the solvent surface. Set timer for 60 minutes. Condenser
valves are still open. Extract for the preset time.
7.12 After rinse time has elapsed, close the condenser valves by turning
each a quarter-turn, clockwise.
7.13 When all but 2 to 5 ml of solvent have been collected, open the
system and remove the cups.
7.14 Transfer the contents of the cups to 15 ml graduated, conical-bottom
glass tubes. Rinse the cups using hexane (methylene chloride if 1:1 methylene
chloride-acetone was used for extraction and analysis is by GC/MS) and add the
rinsates to the glass tubes. Concentrate the extracts to 1 to 10 mL. The final
volume is dependent on the determinative method and the quantitation limit
required. Transfer a portion to a GC vial and store at 4°C until analyses are
performed.
NOTE: The recovery solvent volume can be adjusted by adding
solvent at the top of the condensers. For more details
concerning use of the extractor, see the operating manual
for the automated extraction system.
7.15 Shutdown
7.15.1 Turn "OFF" main switch.
7.15.2 Turn "OFF" cold water tap.
7.15.3 Ensure that all condensers are free of solvent. Empty
the solvent that is recovered in the evaporation step into an appropriate
storage container.
7.16 The extract is now ready for cleanup or analysis, depending on the
extent of interfering co-extractives. See Method 3600 for guidance on cleanup
methods and Method 8000 for guidance on determinative methods. Certain cleanup
and/or determinative methods may require a solvent exchange prior to cleanup
and/or determination.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for general quality control procedures and to
Method 3500 for specific extraction and sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free solid matrix (e.g., reagent sand) method blank
that all glassware and reagents are interference-free. Each time a set of
samples is extracted, or when there is a change in reagents, a method blank
should be processed as a safeguard against chronic laboratory contamination. The
blank samples should be carried through all stages of the sample preparation and
measurement. This is especially important because of the possibility of
interferences being extracted from the extraction cup seal.
3541 - 6 Revision 0
September 1994
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8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Each analysis batch of 20 or less samples must contain: a method
blank, either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis, and a laboratory control sample, unless the
determinative method provides other guidance. Also; routinely check the
integrity of the instrument seals.
8.4 Surrogate standards must be added to all samples when specified in
the appropriate determinative method.
9.0 METHOD PERFORMANCE
9.1 Multi-laboratory accuracy and precision data were obtained for PCBs
in soil. Eight laboratories spiked Arochlors 1254 and 1260 into three portions
of 10 g of Fuller's Earth on three non-consecutive days followed by immediate
extraction using Method 3541. Six of the laboratories spiked each Arochlor at
5 and 50 mg/kg and two laboratories spiked each Arochlor at 50 and 500 mg/kg.
All extracts were analyzed by Oak Ridge National Laboratory, Oak Ridge, TN, using
Method 8081. These data are listed in a table found in Method 8081, and were
taken from Reference 1.
9.2 Single-laboratory accuracy data were obtained for chlorinated
hydrocarbons, nitroaromatics, haloethers, and organochlorine pesticides in a clay
soil. The spiking concentrations ranged from 500 to 5000 Mg/kg, depending on
the sensitivity of the analyte to the electron capture detector. The spiking
solution was mixed into the soil during addition and then immediately transferred
to the extraction device and immersed in the extraction solvent. The data
represents a single determination. Analysis was by capillary column gas
chromatography/electron capture detector following Methods 8081 for the
organochlorine pesticides, 8091 for the nitroaromatics, 8111 for the
hydrocarbons, and 8121 for the chlorinated hydrocarbons. These data are listed
in a table located in their respective methods and were taken from Reference 2.
9.3 Single-laboratory accuracy and precision data were obtained for
semi volatile organics in soil by spiking at a concentration of 6 mg/kg for each
compound. The spiking solution was mixed into the soil during addition and then
allowed to equilibrate for approximately 1 hr prior to extraction. Three
determinations were performed and each extract was analyzed by gas
chromatography/mass spectrometry following Method 8270. The low recovery of the
more volatile compounds is probably due to volatilization losses during
equilibration. These data are listed in a Table located in Method 8270 and were
taken from Reference 2.
10.0 REFERENCES
1. Stewart, J. "Intra-Laboratory Recovery Data for the PCB Extraction
Procedure"; Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6138;
October 1989.
3541 - 7 Revision 0
September 1994
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2. Lopez-Avila, V. (Beckert, W., Project Officer), "Development of a Soxtec
Extraction Procedure for Extracting Organic Compounds from Soils and
Sediments", EPA 600/X-91/140, US EPA, Environmental Monitoring Systems
Laboratory-Las Vegas, October 1991.
3541 - 8 Revision 0
September 1994
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Figure 1
Automated Soxhlet Extraction System
Condenser
Thimble
Glass Wool Plug
Sample
Aluminum beaker (cup)
Hot plate
3541 - 9
Revision 0
September 1994
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METHOD 3541
AUTOMATED SOXHLET EXTRACTION
7.1
Use appropriate
sample handling
technique.
i
7.2
Add anhydrous
Na2SO4if
necessary
7.3
Determine percent
dry weight.
7.4
Check oil
level in
Soxhlet unit.
7.5
Press "Mains"
button.
7.6
Open Cold water
tap. Adjust flow.
7.7
Weigh sample into
extraction thimbles.
Add surrogate
spike.
7.8
Transfer samples
into condensers.
Adjust position of
magnet and thimble.
I
7.9
Insert extraction
cups and load
with solvent.
I
7.10
Move extraction
knobs to
"Boiling" for
60 mins.
©
3541 - 10
©
7.11
Move extraction
knobs to
"Rinsing" for
60 mins.
I
7.12
Close
condenser valves.
7.13
Remove cups.
I
7.14
Transfer contents
to collection
vials, dilute or
concentrate to
volume.
I
7.15
Shutdown
Revision 0
September 1994
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3550
-------
METHOD 3550 '.
SONICATION EXTRACTION
1.0 SCOPE AND APPLICATION
.1.1 Method 3550 1s a procedure for extracting nonvolatile and seml-
volatlle organic compounds from sol Ids such as soils, sludges, and wastes.
The sonlcation process ensures Intimate contact of the sample matrix with the
extraction solvent.
1.2 The method 1s divided Into two sections, based on the expected
concentration of organlcs 1n 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) 1s much simpler and therefore faster.
1.3 It 1s 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 1s solvent extracted three
times using sonlcatlon. The extract 1s separated from the sample by vacuum
filtration or centrlfugatlon. The extract 1s 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 1s solvent extracted once
using sonlcatlon. A portion of the extract 1s 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 beextruded through a 1-mm opening, 1t 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, 1s recommended for sample processing. This
grinder should handle most solid samples, except gummy, fibrous, or oily
materials.
3550 - 1
Revision
Date September 1986
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4.2 Sonication; A horn-type sonlcator 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:
i
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). x
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 (+5*C). The bath should be used in a hood.
3550 -' 2- • . ' v
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 eiution solvent prior to packing the column with adsorbent.
. - j •
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 1n 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
Revision
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-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 portjon
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 1n a.desiccator
before weighing:
: . q of sample^- q^dry sample x 100 = % .moisture
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 ahalyte 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 Pl'ace the bottom surface of the tip of the 1207 3/4 in.
1 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
Revision
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
ID-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) s,o 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
-------
TABLE 1. SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE MtTHUDS
Determinative
method
8040* .
8060
8380
8390
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
-
™
Volume
of extract
required
for
cleanup (roL)
1.0
2.0
10.0
2.0
2.0
2.0
.10.0.
.
**
Final
extract
volume
for
analysis (mL)
uo, io.ob
10.0
10.0
1.0
1.0
'1.0 .
10.0
1.0
. 1.0
' 1.0
o obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 mL.
\
I
Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by OC/FID. Method 8040
also contains an optional derivatization procedure for phenols which results in a 10 mL hexane
extract to be analyzed by OC/ECD. x
ihe specificity of OC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for
guidance on the cleanup procedures available if required. ,
3550 - 6
Revision, 0
Date September 1986
-------
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 m1n.
Remove the mlcro-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-Hned 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 1n each analytical batch
i 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 ahalyte 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 l/8-1n.
> tapered microtip ultrasonic probe for 2 m1n 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.
t • •
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
35,50- 7
Revision
Date September 1986
-------
5.0 mL 1n av concentrator tube 1f further concentration 1s required.
Follow Paragraphs 7.4.6 through 7.4.12 for details on concentration.
, Normally, the 5.0 ml extract 1s concentrated to 1.0 ml.
7.5.6 The extract 1s ready for cleanup or analysis, depending on
the extent of Interfering co-extractives.
i . •
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
Revision
Date September 1986
-------
METHOD 3550
SONICATION EXTRACTION
C
7.1
Prepare
samples using
appropriate
method for the
•aste matrix
7 . 5. Z
Add anhydrous
codlum sulfate
to sample
Determine
the percent
e' «Ol«ture in
the sample
7.3
7.5.3
7 .4. 1
Add
surrogate
standards to
all samples.
spikes, and
blanks
Add
surrogate
standards
to all samples.
spikes, and
Dlanks
Determine pH
e' sample
Sonicate sample
at least 3
times
7.5.4 Adjust
volume:
xltri tapered
mlcrotlp ultra
sonic prooe
o
s
7.S.5
Filter tnrougn
glass wool '
7.4.e|
Conce
extra
collect
concen
;t and
In K-O
7.4.9
Is a solvent
exchange
reoulred7
Add exchange
solvent:
concentrate
extract
3550 - 9
Revision 0
Date September 1986
-------
• METHOD 3350
SONICATION EXTRACTION
.(Continued)
o
Oo sulfur
cryitcll fern?
U«e Matted 3660
for cleanup
concentrate
•nd/or adjust
velum*
Cleanup
• or
analyze
3550 - 10
Revision 0
Date September 1986
-------
3550A
-------
METHOD 3550A
ULTRASONIC EXTRACTION
See DISCLAIMER-1. See manufacturer's specifications for operational settings.
1.0 SCOPE AND APPLICATION
1.1 Method 3550 is a procedure for extracting nonvolatile and semi-
volatile organic compounds from solids such as soils, sludges, and wastes. The
ultrasonic process ensures intimate contact of the sample matrix with the
extraction solvent.
1.2 The method is divided into two sections, based on the expected
concentration of organics in the sample. The low concentration method
(individual organic components of < 20 mg/kg) uses a larger sample size and a
more rigorous extraction procedure (lower concentrations are more difficult to
extract). The medium/high concentration method (individual organic components
of > 20 mg/kg) is much simpler and therefore faster.
1.3 It is highly recommended that the extracts be cleaned up prior to
analysis. See Chapter Four (Cleanup), Sec. 4.2.2, for applicable methods.
2.0 SUMMARY OF METHOD
2.1 Low concentration method - A 30 g sample is mixed with anhydrous
sodium sulfate to form a free-flowing powder. This is solvent extracted three
times using ultrasonic extraction. The extract is separated from the sample by
vacuum filtration or centrifugation. The extract is ready for cleanup and/or
analysis following concentration.
2.2 Medium/high concentration method - A 2 g sample is mixed with
anhydrous sodium sulfate to form a free-flowing powder. This is solvent
extracted once using ultrasonic extraction. A portion of the extract is removed
for cleanup and/or analysis.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Apparatus for grinding dry waste samples.
4.2 Ultrasonic preparation - A horn type device equipped with a titanium
tip, or a device that will give equivalent performance, shall be used.
3550A - 1 Revision 1
September 1994
-------
4.2.1 Ultrasonic Disrupter - The disrupter must have a minimum power
wattage of 300 watts, with pulsing capability. . A device designed to
reduce the cavitation sound is recommended. Follow the manufacturers
instructions for preparing the disrupter for extraction of samples with
low and medium/high concentration.
Use a 3/4" horn for the low concentration method and a 1/8" tapered
microtip attached to a 1/2" horn for the medium/high concentration method.
4.3 Sonabox - Recommended with above disrupters for decreasing cavitation
sound (Heat Systems - Ultrasonics, Inc., Model 432B or equivalent).
4.4 Apparatus for determining percent dry weight.
4.4.1 Oven - Drying.
4.4.2 Desiccator.
4.4.3 Crucibles - Porcelain or disposable aluminum.
4.5 Pasteur glass pipets - 1 ml, disposable.
4.6 Beakers - 400 ml.
4.7 Vacuum or pressure filtration apparatus.
4.7.1 Buchner funnel.
4.7.2 Filter paper - Whatman No. 41 or equivalent.
4.8 Kuderna-Danish (K-D) apparatus.
4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.8.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.8.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.8.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.8.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.9 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
3550A - 2 Revision 1
September 1994
-------
4.10 Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C). The batch should be used in a hood.
4.11 Balance - Top loading, capable of accurately weighing to the nearest
0.01 g.
4.12 Vials - 2 ml, for GC autosampler, with Teflon lined screw caps or
crimp tops.
4.13 Glass scintillation vials - 20 ml, with Teflon lined screw caps.
4.14 Spatula - Stainless steel or Teflon.
4.15 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after
highly contaminated extracts have been passed through.
Columns without frits may be purchased. Use a small pad of
Pyrex glass wool to retain the adsorbent. Prewash the glass
wool pad with 50 ml of acetone followed by 50 ml of elution
solvent prior to packing the column with adsorbent.
4.16 Syringe - 5 ml.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise specified, it is intended that all inorganic reagents shall conform to
the specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.4 Extraction solvents.
5.4.1 Low concentration soil/sediment and aqueous sludge samples
shall be extracted using a solvent system that gives optimum, reproducible
recovery for the matrix/analyte combination to be measured. Suitable
solvent choices are given in Table 1.
3550A - 3 Revision 1
September 1994
-------
5.4.2 Methylene chloride:Acetone, CH2C12:CH3COCH3 (1:1, v:v).
Pesticide quality or equivalent.
5.4.3 Methylene chloride, CH2C12. Pesticide quality or equivalent.
5.4.4 Hexane, C6H14. Pesticide quality or equivalent.
5.5 Exchange solvents.
5.5.1 Hexane, C6H14. Pesticide quality or equivalent.
5.5.2 2-Propanol, (CH3)2CHOH. Pesticide quality or equivalent.
5.5.3 Cyclohexane, C6H12. Pesticide quality or equivalent.
5.5.4 Acetonitrile, CH3CN. Pesticide quality or equivalent.
5.5.5 Methanol, CH3OH. Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes, Sec.
4.1.
7.0 PROCEDURE
7.1 Sample handling
7.1.1 Sediment/soil samples - Decant and discard any water layer on
a sediment sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7.1.1.2 Determine the dry weight of the sample (Sec. 7.2)
remaining after decanting. Measurement of soil pH may be required.
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
grinder to yield at least 100 g after grinding.
7.1.4 Gummy, fibrous or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. The professional
judgment of the analyst is required for handling of these difficult
matrices.
3550A - 4 Revision 1
September 1994
-------
7.2 Determination of percent dry weight - In certain cases, sample
results are desired based on a dry weight basis. When such data are desired, or
required, a portion of sample for this determination should be weighed out at the
same time as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from drying a
heavily contaminated hazardous waste sample.
However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be overdried because
of concerns for personal safety. Laboratory discretion is advised. It may be
prudent to delay overdrying of the weighed-out portion until other analytical
results are available.
7.2.1 Immediately after weighing the sample for extraction, weigh 5-
10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
% dry weight = q of dry sample x 100
g of sample
7.3 Extraction method for samples expected to contain low concentrations
of organics and pesticides (< 20 mg/kg):
7.3.1 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 weigh to the nearest 0.1 g. Nonporous
or wet samples (gummy or clay type) that do not have a free-flowing sandy
texture must be mixed with 60 g of anhydrous sodium sulfate, using a
spatula. If required, more sodium sulfate may be added. After addition
of sodium sulfate, the sample should be free flowing. Add 1 ml of
surrogate standards to all samples, spikes, standards, and blanks (see
Method 3500 for details on the surrogate standard solution and the matrix
spike solution). 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/juL of each base/neutral
analyte and 200 ng/juL of each acid analyte in the extract to be analyzed
(assuming a 1 /xL injection). If Method 3640, Gel-Permeation Cleanup, is
.to be used, add twice the volume of surrogates and matrix spiking
compounds since half of the extract is lost due to loading of the GPC
column. Immediately add 100 ml of 1:1 methylene chloride:acetone.
7.3.2 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.
7.3.3 Extract ultrasonically for 3 minutes, with output control knob
set at 10 (full power) and with mode switch on Pulse (pulsing energy
3550A - 5 Revision 1
September 1994
-------
rather than continuous energy) and percent-duty cycle knob set at 50%
(energy on 50% of time and off 50% of time). Do not use microtip probe.
7.3.4 Decant the extract and filter it through Whatman No. 41 filter
paper (or equivalent) in a Buchner funnel that is attached to a clean 500
ml filtration flask. Alternatively, decant the extract into a centrifuge
bottle and centrifuge at low speed to remove particles.
7.3.5 Repeat the extraction two or more times.with two additional
100 ml portions of solvent. Decant off the solvent after each ultrasonic
extraction. On the final ultrasonic extraction, pour the entire sample
into the Buchner funnel and rinse with extraction solvent. Apply a vacuum
to the filtration flask, and collect the solvent extract. Continue
filtration until all visible solvent is removed from the funnel, but do
not attempt to completely dry the sample, as the continued application of
a vacuum may result in the loss of some analytes. Alternatively, if
centrifugation is used in Sec. 7.3.4, transfer the entire sample to the
centrifuge bottle. Centrifuge at low speed, and then decant the solvent
from the bottle.
7.3.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10 ml concentrator tube to a 500 ml evaporator flask.
Transfer filtered extract to a 500 ml evaporator flask and proceed to the
next section.
7.3.7 Add one to two clean boiling chips to the evaporation flask,
and attach a three ball Snyder column. Prewet the Snyder column by adding
about 1 mL methylene chloride to the top. Place the K-D apparatus on a
hot water bath (80-90 °C) so that the concentrator tube is partially
immersed in the\hot water and the entire lower rounded surface of the
flask is. bathed, with hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the
concentration in 10-15 min. At the proper rate of distillation the balls
of the column will actively chatter, but the chambers will not flood with
condensed solvent. When the apparent volume of liquid reaches 1 mL,
remove the K-D apparatus and allow it to drain and cool for at least 10
min." •
7.3.8 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent
and a new boiling chip, and re-attach the Snyder column. Concentrate the
extract as described in Sec. 7.3.10, raising the temperature of the water
bath, if necessary, to maintain proper distillation. When the apparent
volume again reaches 1-2 ml, remove the K-D apparatus and allow it to
drain and cool for at least 10 minutes.
7.3.9 Remove the Snyder column and rinse the flask and its lower
joints into the"concentrator tube with 1-2 mL of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method
3660 for.cleanup. The extract may be further concentrated by using the
technique outlined in Sec. 7.3.10 or adjusted to 10.0 mL with the solvent
last used. .
3550A - 6 Revision 1
September 1994
-------
7.3.10 If further concentration is indicated in Table 1, either
micro Snyder column technique (Sec. 7.3.10.1) or nitrogen blow down
technique (Sec. 7.3.10.2) is used to adjust the extract to the final
volume required.
7.3.10.1 Micro Snyder Column Technique
7.3.10.1.1 Add a clean boiling chip and attach a
two ball micro Snyder column to the concentrator tube. Prewet
the column by adding approximately 0.5 ml of methylene
chloride or exchange solvent through the top. Place the
apparatus in the hot water bath. Adjust the vertical position
and the water temperature, as required, to complete the
concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively chatter,
but the chambers will not flood. When the liquid reaches an
apparent volume of approximately 0.5 mL, remove the apparatus
from the water bath and allow to drain and cool for at least
10 minutes. Remove the micro Snyder column and rinse its
lower joint with approximately 0.2 ml of appropriate solvent
and add to the concentrator tube. Adjust the final volume to
the volume required for cleanup or for the determinative
method (see Table 1).
7.3.10.2 Nitrogen Slowdown Technique
7.3.10.2.1 Place the concentrator tube in a warm
water bath (approximately 35 °C) and evaporate the solvent
volume to the required level using a gentle stream of clean,
dry nitrogen (filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the
carbon trap and the sample.
7.3.10.2.2 The internal wall of the tube must be
rinsed down several times with the appropriate solvent during
the operation. During evaporation, the solvent level in the
.tube must be positioned to prevent water from condensing into
the sample (i.e., the solvent level should be below the level
of the water bath). Under normal operating conditions, the
extract should not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below
1 ml, semivolatile analytes may be lost.
7.4 If analysis of the extract will not be performed immediately, stopper
the concentrator tube and store refrigerated. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon lined cap
and labeled appropriately.
3550A - 7 Revision 1
September 1994
-------
7.5 Extraction method for samples expected to contain high concentrations
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 1.0 ml of surrogate spiking solution
to sample mixture. 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//LtL of each acid analyte in the extract to be analyzed
(assuming a 1 juL injection). If Method 3640, Gel-Permeation Cleanup, is
to be used, add twice the volume of surrogates and matrix spiking
compounds since half the extract is lost due to loading of the .GPC column.
7.5.4 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 minutes at output control setting 5 and
with mode switch on pulse and percent duty cycle at 50%. Extraction
solvents are:
1. For nonpolar compounds (i.e., organochlorine pesticides and
PCBs), use hexane or appropriate solvent.
2. For extractable priority pollutants, use 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
5.0 ml in a concentrator tube if further concentration is required.
Follow Sec. 7.3.10 for details on concentration. Normally, the 5.0 ml
extract is concentrated to approximately 1.0 ml or less.
7.5.6 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 subjected to
exactly the same analytical procedures as those used on actual samples.
3550A - 8 Revision 1
September 1994
-------
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 method 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.
3. Christopher S. Hein, Paul J. Marsden, Arthur S. Shurtleff, "Evaluation of
Methods 3540 (Soxhlet) and 3550 (Sonication) for Evaluation of Appendix IX
Analytes form Solid Samples", S-CUBED, Report for EPA Contract 68-03-33-
75, Work. Assignment No. 03, Document No. SSS-R-88-9436, October 1988.
3550A - 9 Revision 1
September 1994
-------
TABLE 1.
EFFICIENCY OF EXTRACTION SOLVENT SYSTEMS8
Solvent System*
D
Compound
4-Bromophenyl phenyl ether
4-Chloro-3 -methyl phenol
bis(2-Chloroethoxy)methane
bis(2-Chloroethyl) ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
Diethyl phthalate
4,6-Dinitro-o-cresol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Heptachlor epoxide
Hexachl orobenzene
Hexachlorobutadiene
Hexachl orocyclopent ad iene
Hexachl oroethane
5-Nitro-o-toluidine
Nitrobenzene
Phenol
1, 2, 4-Tri chl orobenzene
CAS No.b
101-55-3
59-50-7
111-91-1
111-44-4
91-58-7
7005-72-3
95-50-1
541-73-1
84-66-2
534-52-1
121-14-2
606-20-2
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
99-55-8
98-95-3
108-95-2
120-82-1
ABNC
N
A
N
N
N
N
N
N
N
A
N
N
N
N
N
N
N
B
N
A
N
%R
64.2
66.7
71.2
42.0
86.4
68.2
33.3
29.3
24.8
66.1
68.9
70.0
65.5
62.1
55.8
26.8
28.4
52.6
59.8
51.6
66.7
SD
6.5
6.4
4.5
4.8
8.8
8.1
4.5
4.8
1.6
8.0
1.6
7.6
7.8
8.8
8.3
3.3
3.8
26.7
7.0
2.4
5.5
%R
56.4
74.3
58.3
17.2
78.9
63.0
15.8
12.7
23.3
63.8
65.6
68.3
58.7
56.5
41.0
19.3
15.5
64.6
38.7
52.0
49.9
SD
0.5
2.8
5.4
3.1
3.2
2.5
2.0
1.7
0.3
2.5
4.9
0.7
1.0
1.2
2.7
1.8
1.6
4.7
5.5
3.3
4.0
%R
86.7
97.4
69.3
41.2
100.8
96.6
27.8
20.5
121.1
74.2
85.6
88.3
86.7
95.8
63.4
35.5
31.1
74.7
46.9
65.6
73.4
SD
1.9
3.4
2.4
8.4
3.2
2.5
6.5
6.2
3.3
3.5
1.7
4.0
1.0
2.5
4.1
6.5
7.4
4.7
6.3
3.4
3.6
%R
84.5
89.4
74.8
61.3
83.0
80.7
53.2
46.8
99.0
55.2
68.4
65.2
84.8
89.3
76.9
46.6
57.9
27.9
60.6
65.5
84.0
SD
0.4
3.8
4.3
11.7
4.6
1.0
10.1
10.5
4.5
5.6
3.0
2.0
2.5
1.2
8.4
4.7
10.4
4.0
6.3
2.1
7.0
%R
73.4
84.1
37.5
4.8
57.0
67.8
2.0
0.6
94.8
63.4
64.9
59.8
77.0
78.1
12.5
9.2
1.4
34.0
13.6
50.0
20.0
SD
1.0
1.6
5.8
1.0
2.2
1.0
1.2
0.6
2.9
2.0
2.3
0.8
0.7
4.4
4.6
1.7
1.2
4.0
3.2
8.1
3.2
Percent recovery of analytes spiked at 200 mg/kg into NIST sediment SRM 1645
Chemical Abstracts Service Registry Number"
Compound Type: A = Acid, B = Base, N = neutral
A = Methylene chloride
B = Methylene chloride/Acetone (1/1)
C = Hexane/Acetone (1/1)
D = Methyl t-butyl ether
E = Methyl t-butyl ether/Methanol (2/1)
3550A - 10
Revision 1
September 1994
-------
TABLE 2.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040°
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8250a'c
8270°
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
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
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
--
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
--
--
--
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
1.0
1.0
1.0
1.0
0.0 (dry)
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10.0 ml.
b Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also
contains an optical 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.
on the cleanup procedures available if required.
Refer to Method 3600 for guidance
3550A - 11
Revision 1
September 1994
-------
METHOD 3550A
ULTRASONIC EXTRACTION
J Start J
I
r
7.1 Prepare sample*
using appropriate method
for the waste matrix
x
r
7.2 Determine the
percent dry weight
of the
sample
7.5.2 Add anhydrous
sodium sulfata to
sample
I
7.5.2
Is organic
concentration
expected to be
< 20 mg/kg?
7.3.1 Add surrogate
standards to all
samples, spikes,
and blanks
7.S.3 Add surrogate
standards to all
samples, spikes,
and blanks
I
7.3.2 - 7.3.5
Sonicate sample at
least 3 timee
7.5.4 Adjust
volume; disrupt
sample with taperad
microtip ultrasonic
probe
7.3.7 Dry and
collect extract in
K-D concentrator
7.5.5 Is
further
concentration
required?
7.5.5 Filter
through glass wool
7.3.8 Concentrate
sxtract and collect
in K-D concentrator
3550A - 12
Revision 1
September 1994
-------
METHOD 3550A
continued
7.3.9 Add exchange
solvent;
concentrate extract
Yes
7.3.10 Use Method
3660 for cleanup
Yes
7.3.9 Is
a solvent
exchange
required?
7.3.10 Do
sulfur crystals
form?
7.3.11 Further
concentrate and/or
adjust volume
(Cleanup or \
analyze j
3550A - 13
Revision 1
September 1994
-------
METHOD 3580A
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 concentration greater than 20,000 mg/kg and that
are soluble in the dilution solvent. • .
i
1.2 It is recommended that an aliquot of the diluted sample be cleaned
up. See this chapter, Organic Analytes, Section 4.2.2 (Cleanup).
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
i '
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, or equivalent.
4.2 Spatula: Stainless steel or Teflon.
,4.3 Balance: Capable of weighing 100 g to the nearest 0.01 g.
/
4.4 Vials and caps: 2 mL for GC autosampler.
4.5 Disposable pi pets: Pasteur.
4.6 Test tube rack.
4.7 Pyrex glass wool.
4.8 Volumetric flasks, Class A: 10 mL (optional).
5.0 REAGENTS , i
5.1 'Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
1 • /
3580A - 1 Revision 1
- . July 1992
-------
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate. . .' ,
5.2 Methylene chloride, CH2C12 - Pesticide quality or, equivalent.
5.3 Hexane, C6HU - 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. ,
j ,
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. Pipet 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 of the sample to separate
20 mL vials or 10 mL volumetric flasks (record weight to the nearest 0.1 g).
Wipe the mouth of the vial with a tissue to remove any sample material. Cap the
vial before proceeding with the next sample to avoid any cross-contamination.
7.4 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/jiL of each base/neutral analyte and 400 ng/^L of each acid analyte in
the extract to be analyzed (assuming a 1 /iL 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 and the determinative method to be used 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 the dilution is to be cleaned
up by gel permeation chrqmatography (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.
3580A - 2 ' Revision 1
July 1992
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7.8 Loosely pack disposable Pasteur plpets 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.
7.9 The extract is ready for cleanup or analysis, depending on the extent
of interfering co-extractives. '
1 l • \
B.O 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. ' , <
3580A - 3 Revision 1
July 1992
-------
METHOD 3580A
WASTE DILUTION
7 1 Does
sample
contain more
than 1
phase7
7 3 Transfer 1 g of
each phase to-
.separate vials or
Masks
7 4 Add surrogate
spiking solution to
.all samp 1es and
blanki
7 4 Add matrix
spiking standard to
sample selected for
spiking
7- 5 Dilute «ilh .
•appropriate solvent
7.1 Us. phase
separation method
(Chapter 2)
.'7 6 Add anhydrous
ammonium tulfate
7 7 Cap and shake
7 8 filter through
glass »ool
Cleanup or analyze
3580A - 4
Revision 1
July 1992
-------
3600A
-------
METHOD 3600A
CLEANUP
1.0 SCOPE AND APPLICATION
1.1 General "
1.1.1 Injection of sample extracts, without further cleanup or
isolation of analytes, into a gas or liquid chromatograph can cause
extraneous peaks, deterioration of peak resolution and column efficiency,
and loss of detector sensitivity and can greatly shorten the lifetime of
expensive columns. The following techniques have been applied to extract
purification: partitioning between immiscible solvents; adsorption
chromatography; gel permeation chromatography; chemical destruction of
interfering substances with acid, alkali, or oxidizing agents; and
distillation. These techniques may be used individually or in various
combinations, depending on the-extent and nature of the co-extractives.
1.1.2 It is an unusual situation (e.g. with some water samples) when
extracts can be directly determined without further treatment. Soil and
waste extracts often require a combination of. cleanup methods. For
example, when analyzing for organochlorine pesticides and PCBs, it may be
necessary to use gel permeation chromatography (GPC), to eliminate the
high boiling material and a micro alumina or Florisil column to eliminate
interferences with the analyte peaks on the GC/ECD.
1.2 Specific
1.2.1 Adsorption column chromatography - Alumina (Methods 3610 and
3611), Florisil (Method 3620), and silica gel (Method 3630) are useful for
separating analytes of a relatively narrow polarity range away from
extraneous, interfering peaks of a different polarity.
1.2.2 Acid-base partitioning (Method 3650) - Useful for separating
acidic or basic organics from neutral organics. It has been applied to
analytes such as the chlorophenoxy herbicides and phenols.
1.2.3 Gel permeation chromatography (GPC) (Method 3640) - The most
universal cleanup technique for a broad range, of semivolatile organics and
pesticides. It is capable of separating high molecular-weight material
from the sample analytes. It has been used successfully for all the
semivolatile base, neutral, and acid compounds associated with the EPA
Priority Pollutant and the Superfund Target Compound list for GC/MS
analysis for semivolatiles and pesticides. GPC is usually not applicable
for eliminating extraneous peaks on a chromatograro which interfere with
the analytes of interest.
1.2.4 Sulfur cleanup'(Method 3660) -.Useful in eliminating sulfur
from sample extracts, which may cause chromatographic interference with
analytes of interest.
3600A - 1 . Revision 1
. July 1992
-------
1.2.5 Table 1 indicates the recommended cleanup techniques for the
indicated groups of compounds. This information can also be used as
guidance for compounds that are not listed. Compounds that are chemically
similar to these groups of compounds should follow a similar elution
pattern.
2.0 SUMMARY OF METHOD
2.1 Refer to the specific cleanup method for a summary of the procedure.
3.0 INTERFERENCES ,
3.1 Analytical interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free of interferences, under the
conditions of the analysis, by running laboratory reagent blanks.
3.2 More extensive procedures than those outlined in the methods may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific cleanup method for apparatus and materials
needed.
» " *' ' .
5.0 REAGENTS -
5.1 Refer to the specific cleanup method for the reagents needed.
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 Prior to using the cleanup procedures, samples should undergo solvent
extraction. Chapter Two, Section 2.3.3, may be used as a guide for choosing the
appropriate extraction procedure based on the physical composition of the waste
and on the analytes of interest in the matrix (see also Method 3500 for a general
description of the extraction technique). For some organic liquids, extraction
prior to cleanup may not be necessary.
7.2 In most cases, the extracted sample is then analyzed by one of the
determinative'methods available in Section 4.3 of this chapter. If the analytes
of interest are not able to be determined due.to interferences, cleanup is
performed. . .
3600A - 2 Revision 1
July 1992
-------
7.3 Many of the determinative methods specify cleanup methods that should
be used when determining particular analytes (e.g. Method 8060, gas
chrpmatography of phthalate esters, recommends using either Method 3610 (Alumina
column cleanup) or Method 3620 (Florisil column cleanup) if interferences prevent
analysis). However, the experience of the analyst may -prove invaluable in
determining which cleanup methods are needed. As indicated in Section 1:0 of
this method, many matrices may require a combination of cleanup procedures in
order to ensure proper analytical determinations.
7.4 Guidance for cleanup is specified in each of the methods that follow.
The amount of extract cleanup required prior to the final determination depends
on the selectivity of both the extraction procedure and the determinative method
and the required detection limit.
7.5 Following cleanup, the sample is concentrated to whatever volume is
required in the determinative method. Analysis follows as specified in the
determinative procedure (Section 4.3 of this Chapter).
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 The analyst must demonstrate that the compounds of interest are being
quantitatively recovered by the cleanup technique before the cleanup is applied
to actual samples.
8.3 For sample extracts that are cleaned up, the associated quality
control samples (e.g. spikes, blanks, replicates, and duplicates) must also be
processed' through the same cleanup procedure.
8.4 The analysis using each determinative method (GC, GC/MS, HPLC)
specifies instrument calibration procedures using stock standards. It is
recommended that cleanup also be performed on a series of the same type of
standards to validate chromatographic elution patterns for the compounds of
interest and to verify the absence of interferences from reagents.
• ' • x
9.0 METHOD PERFORMANCE
,9.1 Refer to the specific cleanup method for performance data.
10.0 REFERENCES .
10.1 Refer to the specific cleanup method. ,
3600A - 3 Revision 1
July 1992
-------
TABLE 1. :
RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Determinative8 Cleanup
Analyte Group Method Method Option
Phenols . 8040 3630b, 3640, 3650, 8040C
Phthalate esters 8060 3610, 3620, 3640
Nitrosamines 8070 3610, 3620, 3640
Organochlorine pesticides & PCBs 8080 3620, 3640, 3660
Nitroaromatics and cyclic ketones 8090 3620, 3640
Polynuclear aromatic hydrocarbons 8100 3611, 3630, 3640
Chlorinated hydrocarbons 8120 3620, 3640
Organophosphorus pesticides 8140 3620
Chlorinated herbicides 8150 8150
Priority pollutant semivolatiles 8250, 8270 3640, 3650, 3660
Petroleum waste 8250,8270 : 3611,3650
1
8 The GC/MS Methods, 8250 and 8270, are also appropriate determinative methods
for all analyte groups, unless lower detection limits are required.
b Cleanup applicable to derivatized phenols.
c Method 8040 includes a derivatization technique followed by GC/ECD analysis,
if interferences are encountered using GC/FID.
d Method 8150 incorporates an acid-base cleanup step as an integral part of the
method. ,
3600A - 4 - Revision 1
.July 1992
-------
METHOD 3600A
CLEANUP
START
7 1 Do
solvent
••traction
? 2 Analyze
analyte by a
determinative
method from
S.c 4 3
7 2 Are
analytei
undeterminable
due to
inter ference?
7 3 Use cleanup
method
specified for
the determina-
tive method
7 5
Concent rate
sample to
required
volume
3600A - 5
Revision 1
July 1992
-------
3600B
-------
METHOD 3600B
CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Method 3600 provides general guidance on selection of cleanup methods
that are appropriate for the target analytes of interest. Cleanup methods are
applied to the extracts prepared by one of the extraction methods, to eliminate
sample interferences. The following table lists the cleanup methods and provides
a brief description of the type of cleanup.
SW-846 CLEANUP METHODS
Method # Method Name . Cleanup Type
3610 Alumina Cleanup Adsorption
3611 Alumina Cleanup & Separation Adsorption
for Petroleum Waste
3620 Florisil Cleanup Adsorption
3630 Silica Gel Cleanup Adsorption
3640 Gel-Permeation Cleanup Size-Separation
3650 Acid-Base Partition Cleanup Acid-Base Partitioning
3660 Sulfur Cleanup Oxidation/Reduction
3665 Sulfuric Acid/Permanganate Oxidation/Reduction
Cleanup
1.2 The purpose of applying a cleanup method to an extract is to remove
interferences and high boiling material that may result in: (1) errors in
quantitation (data may be biased low because of analyte adsorption in the
injection port or front of the GC column or biased high because of overlap with
an interference peak); (2) false positives because of interference peaks falling
within the analyte retention time window; (3) false negatives caused by shifting
the analyte outside the retention time window; (4) rapid deterioration of
expensive capillary columns; and, (5) instrument downtime caused by cleaning and
rebuilding of detectors and ion sources. Most extracts of soil and waste require
some degree of cleanup, whereas, cleanup for water extracts may be unnecessary.
Highly contaminated extracts (e.g. sample extracts of oily waste or soil
containing oily residue) often require a combination of cleanup methods. For
example, when analyzing for organochlorine pesticides and PCBs, it may be
necessary to use gel permeation chromatography (GPC), to eliminate the high
boiling material and a micro alumina or Florisil column to eliminate
interferences with the analyte peaks on the GC/ECD.
3600B - 1 Revision 2
September 1994
-------
1.3 The following techniques have been applied to extract purification:
adsorption chromatography; partitioning between immiscible solvents; gel
permeation chromatography; oxidation of interfering substances with acid, alkali,
or oxidizing agents. These techniques may be used individually or in various
combinations, depending on the extent and nature of the. co-extractives.
1.3.1 Adsorption column chromatography - Alumina (Methods 3610
and 3611), Florisil (Method 3620), and silica gel (Method 3630) are useful
for separating analytes of a relatively narrow polarity range away from
extraneous, interfering peaks of a different polarity. These are
primarily used for cleanup of a specific chemical group of relatively
non-polar analytes, i.e., organochlorine pesticides, polynuclear aromatic
hydrocarbons (PAHs), nitrosamines, etc.. Solid phase extraction
cartridges have been added as an option.
1.3.2 Acid-base partitioning (Method 3650) - Useful for
separating acidic or basic organics from neutral organics. It has been
applied to analytes such as the chlorophenoxy herbicides and phenols. It
is very useful for separating the neutral PAHs from the acidic phenols
when analyzing a site contaminated with creosote and pentachlorophenol.
1.3.3 Gel permeation chromatography (GPC) (Method 3640) - The
most universal cleanup technique for a broad range of semivolatile
organics and pesticides. It is capable of separating high
molecular-weight, high boiling material from the sample analytes. It has
been used successfully for all the semivolatile base, neutral, and acid
compounds associated with the EPA Priority Pollutant and the Superfund
Target Compound list prior to GC/MS analysis for semivdlatiles and
pesticides. GPC may not be applicable to elimination of extraneous peaks
on a chromatogram which interfere with the analytes of interest. It is,
however, useful for the removal of high boiling materials which would
contaminate injection ports and column heads, prolonging column life,
stabilizing the instrument, and reducing column reactivity.
1.3.4 Sulfur cleanup (Method 3660) - Useful in eliminating
sulfur from sample extracts, which may cause chromatographic interference
with analytes of interest.
1.4 Several of the methods are also useful for fractionation of complex
mixtures of analytes. Use the solid phase extraction cartridges in Method 3630
(Silica Gel) for separating the PCBs away from most organochlorine pesticides.
Method 3611 (Alumina) is for the fractionation of aliphatic, aromatic and polar
analytes. Method 3620 (Florisil) provides fractionation of the organochlorine
pesticides.
1.5 Cleanup capacity is another factor that must be considered in
choosing a cleanup technique. The adsorption methods (3610, 3620, and 3630)
provide the option of using standard column chromatography techniques or solid
phase extraction cartridges. The decision process in selecting between the
different options available generally depends on the amount of interferences/high
boiling material in the sample extract and the degree of cleanup required by the
determinative method. The solid phase extraction cartridges require less elution
solvent and less time, however, their cleanup capacity is drastically reduced
when comparing a 0.5 g or 1.0 g Florisil cartridge to a 20 g standard Florisil
3600B - 2 Revision 2
September 1994
-------
column. The same factor enters into the choice of the 70 g gel permeation column
specified in Method 3640 versus a high efficiency column.
1.6 Table 1 indicates the recommended cleanup techniques for the
indicated groups of compounds. This information can also be used as guidance for
compounds that are not listed. Compounds that are chemically similar to these
groups of compounds should behave similarly when taken through the cleanup
procedure,however, this must be demonstrated by determining recovery of standards
taken through the method.
2.0 SUMMARY OF METHOD
2.1 Refer to the specific cleanup method for a summary of the procedure.
3.0 INTERFERENCES
3.1 Analytical interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free of interferences, under the
conditions of the analysis, by running laboratory reagent blanks.
3.2 More extensive procedures than those outlined in the methods may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific cleanup method for apparatus and materials
needed.
5.0 REAGENTS
5.1 Refer to the specific cleanup method for the reagents needed.
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 Prior to using the cleanup procedures, samples normally undergo
solvent extraction. Chapter Two, Section 2.0, may be used as a guide for
choosing the appropriate extraction procedure based on the physical composition
of the waste and on the analytes of interest in the matrix (see also Method 3500
for a general description of the extraction technique). For some organic
liquids, extraction prior to cleanup may not be necessary.
3600B - 3 Revision 2
September 1994
-------
7.2 Most soil/sediment and waste sample extracts will require some degree
of cleanup. The extract is then analyzed by one of the determinative methods.
If interferences still preclude analysis for the analytes of interest, additional
cleanup may be required.
7.3 Many of the determinative methods specify cleanup methods that should
be used when determining particular analytes (e.g. Method 8061, gas
chromatography of phthalate esters, recommends using either Method 3610 (-Alumina
column cleanup) or Method 3620 (Florisil column cleanup) if interferences prevent
analysis. However, the experience of the analyst may prove invaluable in
determining which cleanup methods are needed. As indicated in Section 1.0 of
this method, many matrices may require a combination of cleanup procedures in
order to ensure proper analytical determinations.
7.4 Guidance for cleanup is specified in each of the methods that follow.
The amount of extract cleanup required prior to the final determination depends
on the concentration of interferences in the sample, the selectivity of both the
extraction procedure and the determinative method and the required detection
limit.
7.5 Following cleanup, the sample is concentrated to whatever volume is
required in the determinative method. Analysis follows as specified in the
determinative procedure.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered by the cleanup technique before the cleanup is
applied to actual samples. For sample extracts that are cleaned up, the
associated quality control samples (e.g. spikes, blanks, replicates, and
duplicates) must also be processed through the same cleanup procedure.
8.3 The analysis using each determinative method (GC, GC/MS, HPLC)
specifies instrument calibration procedures using stock standards. It is
recommended that cleanup also be performed on a series of the same type of
standards to validate chromatographic elution patterns for the compounds of
interest and to verify the absence of interferences from reagents.
9.0 METHOD PERFORMANCE
9.1 Refer to the specific cleanup method for performance data.
10.0 REFERENCES
10.1 Refer to the specific cleanup method.
3600B - 4 Revision 2
September 1994
-------
TABLE 1.
RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Analyte Group
Determinative8
Method
Cleanup
Method Options
Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Chlorinated hydrocarbons
Organophosphorus pesticides
Chlorinated herbicides
Semivolatile organics
Petroleum waste
PCDDs and PCDFs by LR/MS
PCDDs and PCDFs by HR/MS
N-methyl carbamate pesticides
8040
8060/8061
8070
8080/8081
8080/8081
8090
8100/8310
8120/8121
8140/8141
8150/8151
8250/8270
8250/8270
8280
8290
8318
3630b, 3640, 3650, 8040C
3610, 3620, 3640
3610, 3620, 3640
3620, 3640, 3660
3665
3620, 3640
3611, 3630, 3640
3620, 3640
3620
8150d, 8151d, 3620
3640, 3650, 3660
3611, 3650
8280
8290
8318
a The GC/MS Methods, 8250 and 8270, are also appropriate determinative methods
for all analyte groups, unless lower detection limits are required.
b Cleanup applicable to derivatized phenols.
c Method 8040 includes a derivatization technique followed by GC/ECD analysis,
if interferences are encountered using GC/FID.
d Methods 8150 and 8151 incorporate an acid-base cleanup step as an integral
part of the methods.
3600B - 5
Revision 2
September 1994
-------
METHOD 3600B
CLEANUP
7.1
Do solvent
extraction
I
7.2
Analyze analyte
by a determinative
method from Sec. 4.3
7.2 Are
analytes
undeterminable
due to
nterference?
7.3
Use cleanup method
specified for the
determinative method
7.5
Concentrate sample
to required volume
3600B - 6
Revision 2
September 1994
-------
3610 A
-------
METHOD 361OA
\
ALUMINA COLUMN CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Scope: Alumina is a highly porous and granular form of aluminum
oxide. It is available in three pH ranges (basic, neutral, and acidic) for use
in column chromatography. It is used to separate analytes from interfering
compounds of a different chemical polarity.
1.2 General Applications (Gordon and Ford):
1.2.1 Basic (B) pH (9-10): USES: Basic and neutral compounds stable
to alkali, alcohols, hydrocarbons, steroids, alkaloids, natural pigments.
DISADVANTAGES: Can cause polymerization, condensation, and dehydration
reactions; cannot use acetone or ethyl acetate as eluants.
1.2.2 Neutral (N): USES: Aldehydes, ketones, quinones, esters,
lactones, glycoside. DISADVANTAGES: Considerably less active than the
basic form. < .
1.2.3 Acidic (A) pH (4-5): USES: Acidic pigments (natural and
synthetic), strong acids (that otherwise chemisorb to neutral and basic
alumina).
1.2.4 Activity grades: Acidic, basic, or neutral alumina can be
prepared in various activity grades (I to V), according to the Brockmann
, scale, by addition of water to Grade 1 (prepared.by heating at 400-450°C
until no more water is lost). The Brockmann scale (Gordon and Ford, p.
374) is reproduced below:
Water added (wt. %): 0 3 6 10 15
Activity grade: I II III IV V
RF (p-aminoazobenzene): 0.0 0.13 0.25 0.45 0.55
1.3 Specific applications: This method includes guidance for cleanup of
sample extracts containing phthalate esters and nitrosamines. For alumina column
cleanup of petroleum wastes, see Method 3611, Alumina Column Cleanup of Petroleum
Wastes.
2.0 SUMMARY OF METHOD " .
2.1 The column is packed with the required amount of adsorbent, topped
with a water adsorbent, and then loaded with the sample to be analyzed. Elution
of the analytes is effected with a suitable solvent(s)., leaving the interfering
compounds on the column. The eluate is then concentrated (if necessary).
3610A - 1 ., Revision 1
July 1992
-------
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compounds of interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Chromatography column: 300 mm x 10 mm ID, 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.
4.2 . Beakers: 500 ml.
4.3 Reagent bottle: 500 ml.
4.4^ Muffle furnace.
4.5 Kuderna-Danish (K-D) apparatus:
4.5.1 Concentrator tube: 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.5.2 Evaporation flask: 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent. .
4.5.3 Snyder column: Three ball macro (Kontes K-503000-0121 or
equivalent). ,
4.5.4 Snyder column: Two ball micro (Kontes K-569001-0219 or
equivalent). •' - • .
4.5.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.6 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.7 Water bath: Heated, With concentric ring cover, capable of
temperature control (±5°C). The bath should be used in a hood.
4.8 Vials: Glass, 2 ml capacity, with Teflon lined screw caps or crimp
tops. '
3610A - 2 Revision 1
. ; July 1992
-------
4.9 Erlenmeyer flasks: 50 and 250 ml
5.0 REAGENTS
5.1 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Sodium sulfate: Sodium sulfate (granular, anhydrous), Na2S04.
Purify by heating at 400°C for 4 hours in a shallow tray, or by precleaning the
sodium sulfate with methylene chloride. If the sodium sulfate is precleaned with
methylene chloride, a method blank must be analyzed, demonstrating that there is
no interference from the sodium sulfate.
5.3 Eluting solvents:
5.3.1 Oiethyl Ether, C2H5OC2H5. Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided, with the
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.3.2 Methanol, CH3OH - Pesticide quality or equivalent.
\ •> \ • • .
5.3.3 Pentane, CH3(CH2)3CH3 - Pesticide quality or equivalent.
5.3.4 Hexane, C6HU - Pesticide quality or equivalent.
5.3.5 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5,.4 Alumina:
5.4.1 For cleanup of phthalate extracts: Alumina-Neutral,, activity
Super I, W200 series (ICN Life Sciences Group, No. 404583, or equivalent).
To prepare for use, place 100 g of alumina into a 500 ml beaker and heat
for approximately 16 hr at 400°C. After heating, transfer to a 500 ml
reagent bottle. Tightly seal and cool to room temperature. When cool,
add 3 ml of organic-free reagent water. Mix thoroughly by shaking or
rolling for 10 min and let it stand for at least 2 hr. Keep the bottle
sealed tightly.
5.4.2 For cleanup of nitrosamine extracts: Alumina-Basic, activity
Super I, W200 series (ICN Life Sciences Group, No. 404571, or equivalent).
To prepare for use, place 100 g of alumina into a 500 mL reagent bottle
and add 2 mL of organic-free reagent water. Mix the alumina preparation
thoroughly by shaking or rolling for 10 min and let it stand for at least
2 hr. The preparation should be .homogeneous, before use. Keep the bottle
sealed, tightly to ensure proper activity. ,
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3610A - 3 Revision 1
July 1992
-------
7.0 PROCEDURE
7.1 Phthalate esters: <
7.1.1 Reduce the sample extract volume to 2 mL prior to cleanup.
The extract solvent must be hexane.
7.1.2 Place approximately 10 g * of alumina into a 10, mm ID
chromatographic column. Tap the column to settle the alumina and add 1-2
cm of anhydrous sodium sulfate to the top.
7.1.3 Pre-elute the column with 40 ml of hexane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and, just prior to
exposure of the sodium sulfate layer to the air, quantitatively transfer
the 2 mL sample extract onto the column using an additional 2 ml of hexane
to complete the transfer. Just prior to exposure of the sodium sulfate
layer to the air, add 35 ml of hexane and continue the elution of the
column. Discard this hexane eluate.
7.1.4 Next, elute the column with 140 ml of 20% ethyl ether in
hexane (v/v) into a 500 ml K-D flask equipped with a 10 ml concentrator
tube. Concentrate the collected fraction using the Kuderna-Danish
technique. No solvent exchange is necessary. Adjust the volume of the
cleaned up extract to whatever volume is required (10.0 ml for Method
8060) and analyze. Compounds that elute in this fraction are as follows:
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate • . (.
Di-n-octyl phthalate.
7.2 Nitrosamines:
•7.2.1 Reduce the sample extract to 2 ml prior to cleanup.
7.2.2 Diphenylamine, if present in the original sample extract, must
be separated from the nitrosamines if N-nitrosodiphenylamine is to be'
determined by this method.
7.2.3. Place approximately 12 g of the alumina preparation into a 10
mm ID chromatographic column. Tap the column to settle the alumina and
add 1-2 cm of anhydrous sodium sulfate to the top.
7.2.4 Pre-elute the1 column with 10 mL of ethyl ether/pentane
(3:7)(v/v). Discard the eluate (about 2 mL) and, just prior to exposure
of the sodium sulfate layer to the air, quantitatively transfer the 2 mL
sample extract onto the column using an additional 2 mL of pehtane to
complete the transfer.
7.2.5 Just prior to exposure of the sodium sulfate layer to the air,
add 70 mL of ethyl ether/pentane (3:7)(v/v). Discard the first 10 mL of
eluate. Collect the remainder of the eluate in a 500 mL K-D flask
3610A - 4 , Revision 1
- July 1992
-------
equipped with a 10 mL concentrator tube. This fraction contains N-
nitroso-di-n-propylamine.
7.2.6 Next, elute .the column with 60 ml of eithyl ether/pentane
(l:l)(v/v), collecting the eluate in a second 500 mL K-D flask equipped
with a 10 ml concentrator tube. Add 15 ml of methanol to the K-D flask.
This fraction will contain N-nitrosodimethylamine, most of the N-nitroso-
di-n-propylamine, and any diphenylamine that is present.
7.2.7 Concentrate both fractions using the Kuderna-Danish Technique
(if necessary), using pentane to prewet the Snyder column. When the
apparatuses cool, remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube With 1-2 ml of pentane. Adjust the
final volume ta whatever is required in the appropriate determinative
method (Section 4.3 of this chapter). Analyze the fractions.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of^interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Performance data are not available.
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.
3610A - 5 Revision 1
July 19.92
-------
METHOD 3610A
ALUMINA COLUMN CLEANUP
7 1.1 Reduce
volume of
sample
••tract.
7.1.7 Put
alumina in
column, add
anhydrous
•odium sulfate.
7.1.3
Preelute
column with
heiane.
7.1.3 Transfer
sample eitraet
to column,
alute column
•ith heiane.
7.1.4 Elute column
•ith «thyl
ether/heiane
Collect «luat« in
flaik.
. 7.1.4
Cone«ntrat«
collected
fraction.
adjuat volume.
Analyz* by
appropriate
determinativ
method
7 2.1 Reduce
volume of
tample
extract.
.. '7.2.3 Put
alumina in
column, add
' anhydrou*
•odium tulfate.
7.2.4 Preelute
column nith ethyl
ether/pentane.
Tranifer sample
•itract to column,
add pentane.
7.2.S Clute column
•ith ethyl
ether/pentane
Collect eluate in
fla»k.
7 2.-6 Elute column
• ith -ethyl
•ther/pentane
Collect eluate in
•acond flask, add
methano1
..
Concentrate
both fractions ;
adjust volume.
3610A - 6
Revision 1
July 1992
-------
3611A
-------
METHOD 3611A
ALUMINA COLUMN CLEANUP AND SEPARATION OF PETROLEUM WASTES
1.0 SCOPE AND APPLICATION
1.1 Method 3611 was formerly Method 3570 in the Second Edition of this
manual.
1.2 Specific application: This method includes guidance for separation
of petroleum wastes into aliphatic, aromatic, and polar fractions.
2.0 SUMMARY OF METHOD . /
2.1 The column is packed with the required amount of adsorbent, topped
with a water adsorbent, and then loaded with the sample to be analyzed. Elution
of the analytes is effected with a suitable solvent(s), leaving the interfering
compounds on the column. The eluate is then concentrated (if necessary).
3.0 INTERFERENCES
t»
3.1 A reagent blank should be performed for the compounds of interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
3.3 Caution must be taken to prevent overloading of the chromatographic
column. As the column loading for any of these types of wastes approaches
0.300 g of extractable organics, separation recoveries will suffer. If
overloading is suspected, an aliquot of, the base-neutral extract prior to cleanup
may be weighed and then evaporated to dryness. A gravimetric determination on
the aliquot will .indicate the weight of extractable organics in the sample.
3.4 Mixtures of petroleum wastes containing predominantly polar solvents,
i.e., chlorinated solvents or oxygenated solvents, are not appropriate for this
method. . . -v
'I
4.0 'APPARATUS AND MATERIALS
4.1 Chromatography column: 300 mm x 10 mm ID, 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.
3611A - 1 Revision ,1
July 1992
-------
4.2 Beakers: 500 ml.
4.3 Reagent bottle: 500 ml. x.
4.4 Muffle furnace.
4.5 Kuderna-Danish (K-D) apparatus:
4.5.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent); A ground-glass stopper is used to prevent evaporation of
extracts.
4.5.2 Evaporation flask - 500 * ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent. •
4.5.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.5.4 Snyder column - Two ball micro (Kontes, K-569001-0219 or
equivalent).
4.5.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.6 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.7 Water bath: Heated with concentric ring cover, capable of
temperature control (+5°C). The bath should be used in a hood.
4.8 • Erlenmeyer flasks: 50 and 250 ml.
5.0 REAGENTS
5.1 Sodium sulfate: (granular, anhydrous), Na2SO,. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.2 Eluting solvents:
5.2.1 Methanol, CH3OH - Pesticide quality or equivalent.
5.2.2 Hexane, C6HU - Pesticide quality or equivalent.
5.2.3 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.3 . Alumina: Neutral 80-325 MCB chromatographic grade or equivalent.
Dry alumina overnight at 130°C prior to use. v
3611A - 2 Revision 1
July 1992
-------
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 It is suggested that Method 3650, Acid-Base Partition Cleanup, be
performed on the sample extract prior to alumina cleanup.
7.2 Place approximately 10 g of alumina into a chromatographic column,
tap to settle the alumina, and add 1 cm of anhydrous sodium sulfate to the top.
7.3 Pre-elute the column with 50 mL of hexane. Discard the eluate and,
just prior to exposure of the sodium sulfate layer to the air, quantitatively
transfer the 1 mL sample extract onto the column using an additional 1 ml of
hexane to completeVthe transfer. To avoid overloading the column, it is
suggested that no more than 0.300 g of extractable organics be placed on the
.column (see Section 3.3).
. / * ' •!
7.4 Just prior to exposure of the sodium sulfate to the air, elute the
column with a total of 15 mL of hexane. If the extract is in 1 mL of hexane, and
if 1 mL of hexane was used as a rinse, then 13 mL of additional hexane should be
used. Collect the effluent in a 50 mL flask and label this fraction
"base/neutral aliphatics." Adjust the flow rate to 2 mL/min.
">-.',
7.5 Elute the column with 100 mL of methylene chloride and collect the
effluent in a 250 mL flask. Label this fraction "base/neutral aromatics."
7.6 Elute the column with 100 mL of methanol and collect the effluent in
a 250 mL flask. Label this fraction "base/neutral polars."
7.7 Concentrate the extracts (if necessary) by the standard K-D technique
to the volume (1-10 mL) required in the appropriate determinative method (Chapter
Four). Analyze the fractions containing the analytes of interest.
8.0 QUALITY CONTROL ' ' " ' . J ••
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For \sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method. ,
3611A - 3 Revision 1
July 1992
-------
9.0 METHOD PERFORMANCE
9.1 The precision and accuracy of the method will depend upon the overall
performance of the sample preparation and analysis.
9.2 Rag oil is an, emulsion consisting of crude oil, water, and soil
particles.. It has a density greater than crude oil and less than water. This
material forms a layer between the crude oil and water when the crude oil is
allowed to gravity separate at the refinery. A rag oil sample was analyzed by
a number of laboratories according to the procedure outlined in this method. The
results of these analyses by GC/MS for selected components in the rag oil are
presented in Table 1. Reconstructed ion chromatograms from the GC/MS analyses
are included as Figures 1 and 2.
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.
3611A - 4 . Revision 1
July 1992
-------
Table 1.
RESULTS OF ANALYSIS FOR SELECTED COMPONENTS IN RAG OIL
.Analyte
Naphthalene
Fluorene
Phenanthrene
2-Methyl naphthalene
Dibenzothiophene
Methyl phenanthrene
Methyl dibenzothtophene
•
Nitrobenzene-d5
Terphenyl-d14
Phenol -d6
Naphthalene-d8
i . .
Mean
Cone. (mg/kg)a
216
140
614
673
1084
2908
2200
Average Surrogate
58.6
83.0
80.5
64.5
Standard
Deviation
42
66
296
120
286 ~
2014
1017
Recovery
11
2.6
27.6
5.0
%RSDb
19
47
18
18
26
69
46
8 Based on five determinations from three laboratories.
& ~ -
b Percent Relative Standard Deviation.
3611A - 5 Revision 1
July 1992
-------
me
•1/77/tt
« WC OIL FV-I.
c i. in*
-1M.t
CO
CTk
TO
C_i'
C <
UD
VO
OAT* mow it .
CM.li 2/CM.I II
lilt OIL •.IOMH SMfU ftCO MM. FMC IMC SS
H •. <.» ouwh A •. i.t MSCI u ?*. 3
I
on or
TO znt
10
74671.
IO
Figure 1. Reconstructed 1on chromatogram from GC/MS analysis of the aromatic
fraction from Rag Oil
-------
MC on. ro-a.sa.» es O.MMM
C I.I7W UKU N •. «.•
•ML tl
CM.li 2ICM.I •!
0 M. 3
CO
c_, ro
C <
«< M
•— o
IO 3
10
2IM
Figure 2.
Reconstructed Ion chromatogram from GC/MS analysis of the aliphatic
fraction from Rag 011
-------
METHOD 3611A
ALUMINA COLUMN CLEANUP AND SEPARATION OF PETROLEUM WASTES
Start
7 1 Cleanup
using Method
3650
7 2 Add alumina
to
chromatographic
column.
7 2 Add
anhydroua
•odium julfata
to top of
column
7 3 Preelute
column with
7
3
Quantitatively
add extract to
eel
jmn
7.4 Elute
"base-neutral
aliphatic**
henane.
7' S Elut*
" baa«*naut ral
aromatica"
fraction >ith
CH2C12: '
• 7 6 Eluta
"ba»«-nautral
polara"
fraction «ith
mat Hanoi
7 7
Conc*n t ra t*
•Ktract*
X^ ^"
f Analyze using
/ appropriate
mat hod
3611A - 8
Revision 1
July 1992
-------
3620 A
-------
METHOD 3620A
FLORISIL COLUMN CLEANUP
1.0 SCOPE AND APPLICATION,
1.1 Florisil, a registered trade name of the Floridin Co., is a magnesium
silicate with acidic properties. It is used for general column chromatography
as a cleanup procedure prior to sample analysis by gas chromatography.
1.2 General applications: Cleanup of pesticide residues and other
chlorinated hydrocarbons; the separation of nitrogen compounds from hydrocarbons;
the separation of aromatic compounds from aliphatic-aromatic mixtures; and
similar^, applications for use with fats, oils, and waxes (Floridin).
Additionally, Florisil is considered good for separations with steroids, esters,
ketones, glycerides, alkaloids, .and some carbohydrates (Gordon and Ford).
1.3 Specific applications: This method includes guidance for cleanup of
sample extracts containing the following analyte groups: phthalate esters;
nitrosamines; organochlorine pesticides; nitroaromatics; halqethers; chlorinated
hydrocarbons; and organophosphorus pesticides.
2.0. SUMMARY OF METHOD
2.1 The column is packed with the required adsorbent, topped with a water
adsorbent, and then loaded with the, sample to be analyzed. Elution is effected
with a suitable solvent(s) leaving the interfering compounds on the column. The
eluate is then concentrated (if necessary).
3.0 INTERFERENCES • ...
3.l' A reagent blank should be performed for the compounds of interest
prior to the use'of this method. The .level of interferences must be below the.
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification. ,
4.0 APPARATUS AND MATERIALS
4.1 Beaker - 500 mL. ' - .
.4.2 Chromatographic column - 300 mm long x 10 mm ID or 400 mm long x
20 mm ID, as specified in Section 7.0; 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
3620A - 1 - Revision 1
July 1992
-------
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-570001-0500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent). >
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent). '•
4.3.5 Springs - 1/2 inch (Kontes K-662750 or'equivalent).
4.4 Muffle furnace. -
4.5 Reagent bottle - 500 ml.
4.6 Water bath - Heated, with concentric ring cover, capable of
temperature control (±5°C). The bath should be used in a hood.
4.7 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.8 Erlenmeyer flasks - 50 and 250 ml.
4.9 Top-loading balance - 0.01 g.
5.0 REAGENTS
5.1 Organic-free reagent water - All references to waterjn this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Florisil - Pesticide residue (PR) grade (60/100 mesh); purchase
activated at 1250°F (677°C), stored in glass containers with ground-glass
stoppers,or foil-lined screw caps.
5.2.1 Deactivation of Florisil - for cleanup of phthalate esters.
To prepare for use, place 100 g of Florisilinto a 500 ml beaker and heat
for approximately 16 hr at 40°C. After heating, transfer to a 500 ml
reagent bottle. Tightly seal and cool to room temperature; When cool add
3 mL of organic-free reagent, water. Mix thoroughly by shaking or rolling
for 10 min and let stand for at least 2 hr/ Keep the bottle sealed
tightly.
5.2.2 Activation of Florisil - for cleanup ,of nitrosamines,
3620A - 2 Revision 1
. July 1992
-------
organochlorine pesticides and PCBs, nitroaromatics, haloethers,
chlorinated hydrocarbons, and brganophosphorus pesticides. Just before
use, activate each batch at least 16 hr at 130°C in a glass container
loosely covered with aluminum foil. Alternatively, store the Florisil in
an oven at 130°C. Cool the Florisil before use in a desiccator. (Florisil
from different batches or sources may vary in adsorptive capacity. To
standardize the amount of Florisil which is used, the use of lauric acid
value is suggested. The referenced procedure determines the adsorption
from hexane solution of lauric acid (mg) per g of Florisil. The amount of
Florisil to be used for each column is calculated by dividing 110 by this.
ratio and multiplying by 20 g (Mills).
5.3 Sodium sulfate (granular, anhydrous), Na2S04 - Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.4 Eluting solvents
5.4.1 Diethyl ether, C^OCJL - Pesticide quality or equivalent.
Must be free of peroxides, as indicated by test strips (EM Quant or
equivalent). Procedures recommended for removal of peroxides are provided
with the test strips. After cleanup, 20 ml ethyl alcohol preservative
must be added to each liter of ether.
5.4.2 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.4.3 Hexane, C6HK - Pesticide quality or equivalent.
5.4.4 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.4.5 Pentane, CH3(CH2)3CH3 - Pesticide quality or equivalent.
5.4.6 Petroleum ether (boiling range 30-60°C) - 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 Phthalate esters
. 7.1.1 Reduce the sample extract volume to 2 mL prior to cleanup.
The extract solvent must be hexane.
7.T.2 Place approximately 10 g of deactivated Florisil (Section
5.1.1) into a 10 mm ID chromatographic column. Tap the column to settle
the Florisil and add approximately 1 cm of anhydrous sodium sulfate to the
3620A - 3 , Revision 1
- , July 1992
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top. , . . ' ,
7.1.3 Preelute the column with 40 ml of hexane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and, just prior to
exposure of the sodium sulfate layer to the air, quantitatively transfer
the 2 ml sample extract onto the column using an additional 2 mL of hexane
to complete the transfer. Just prior to exposure of the sodium sulfate
layer to the air; add 40 ml of hexane and continue the elution of the
column. Discard this hexane eluate.
7.1.4 Next, elute the column with 100 ml of 20% ethyl ether in
hexane (v/v) into a 500 ml K-D flask equipped with a 10,mL concentrator
tube. Concentrate the collected fraction as needed. No solvent exchange
is necessary. Adjust the volume of the cleaned-up extract to whatever
volume is required (10 mL for Method 8060) and analyze by gas
chromatography. Compounds that elute in this fraction are: .
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
' DUn-butyl phthalate
Diethyl phthalate
Dimethyl phthalate. -
Di-n-octyl phthalate
7.2 Nitrosamines
7.2.1 Reduce the sample extract volume to 2 mL prior to cleanup.
7.2.2 Add a weight of activated Florisil (nominally 22 g)
predetermined by calibration (Section 5.1.2) into a 20 mm ID
chromatographic column. Tap the column to settle the Florisil and add
about 5 mm of anhydrous sodium sulfate to the top.
7.2.3 Pre-elute the column with 40 mL of ethyl ether/pentane (15:85)
(v/v). Discard the eluate and, just prior to exposure of the sodium
sulfate layer to the air, quantitatively transfer the 2 mL sample extract
onto the column using an additional 2 mL of pentane to complete the
transfer. • .
7.2.4 Elute the column with 90 mL ,of ethyl ether/pentane (15:85)
(v/v) and discard the eluate. This fraction will contain the
diphenylamine, if it is present in the extract..
7.2.5 Next, elute the column with 100.mL of acetone/ethyl ether
(5:95) (v/v) into a 500 mL K-D flask equipped with a 10 mL concentrator
tube. This fraction will contain all of the nitrosamines listed in the
scope of the method. ,
7.2.6 Add 15 mL of methanol to the collected fraction, concentrate
as needed using pentane to prewet the K-D column and set the water bath at
70 to 75°C. When the apparatuses cool, remove the Snyder column and rinse
the flask and its lower joint into the concentrator tube with 1 to 2 mL of
pentane.
' 3620A - 4 • Revision 1
, . July 1992
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7.3 Organochlorine pesticides, haloethers, and organophosphorus
pesticides (see Tables 1 and 2 for fractionation patterns of compounds tested)
7.3.1 Reduce the sample extract volume to 10 ml prior to cleanup.
The extract solvent must be hexane.
7.3.2 Add a weight of activated Florisil (nominally 20 g),
predetermined by calibration (Section 5.1.2), to a 20 mm ID
chromatographic column. Settle the Florisil by tapping the column. Add
anhydrous sodium sulfate to the top of the Florisil to form a layer 1 to
2 cm deep. Add 60 ml of hexane to wet and rinse the sodium sulfate and
Florisil. Just prior to exposure of the sodium sulfate to air, stop the
elution of the hexane by closing the stopcock on the chromatographic
column. Discard the eluate.
7.3.3 Adjust the sample extract volume to 10 ml with hexane and
transfer it from the K-D concentrator tube to the Florisil column. Rinse
the tube twice with 1-2 ml hexane, adding each rinse to the column.
7.3.4 Place a 500 ml K-D flask and clean concentrator tube under the
chromatographic column. 'Drain the column into the flask until the sodium
sulfate layer is nearly exposed.' Elute the column with 200 ml of 6% ethyl
ether in hexane (v/v) (Fraction 1) using a drip rate of about 5 mL/min.
All of the haloethers are in this fraction. Remove the K-D flask and set
aside for later concentration. Elute the column again, using 200 ml of
15% ethyl ether in hexane (v/v) (Fraction 2)', into a second K-D flask.
Perform a third elution using 200 ml of 50% ethyl ether in hexane (v/v)
(Fraction 3), and a final elution with 200 ml of 100% ethyl ether
(Fraction 4),, into separate K-D flasks. .
' '
7.3.5 If necessary; concentrate the eluates by standard K-D
techniques using the water bath at about 85°C (75°C for Fraction 4).
Adjust the final volume to whatever volume is required (1-10 mL).
7.4 Nitroaromatics and isophorone
- , 7.4.1 Reduce the sample extract volume to 2. ml prior to cleanup.
7.4.2 Add a weight of .activated Florisil (nominally 10 r}-
predetermined by calibration (Section. 5.1.2) into a 10 mm ID
chromatographic column. Tap the column to settle the Florisil and add
about 1 cm of anhydrous sodium sulfate to the top.
7.4.3 Pre-elute the column with methylene chloride/hexane (1:9)
(v/v) at about 2 mL/min. Discard the eluate and, just prior to exposure
of the sodium sulfate layer to the air, quantitatively transfer the sample
extract onto the column using an additional 2 mL of hexane to complete the
transfer. Just prior to exposure of the sodium sulfate layer to the air,
add 30 mL of methylene chloride/hexane (1:9) (v/v) and continue the
elution of the column. Discard the eluate.
7.4.4 Elute the column with 90 mL of ethyl ether/pentane (15:8.5)
(v/v) and discard the eluate. This fraction will contain the
diphenylamine, if it is present in the.extract.
• 36,20A - 5 Revision 1
-. ' July 1992
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7.4.5 Next, elute the column with 100 ml of acetone/ethyl ether
(5:95) (v/y) into a 500 ml K-D flask equipped with a 10 ml concentrator
tube. This fraction will contain all of the nitrosamines listed in the
scope of the method.
i
7.4.6 Add 15 ml of methanol to the collected fraction, concentrate
using pentane to.prewet the K-D column, and set the water bath at 70 to
75°C. When the apparatus is cool, remove the Snyder column and rinse the1
flask, and its lower joint into the concentrator tube with"1 to 2 ml of
pentane. ,
7.4.7 Next, elute the column with 30 ml of acetone/methylene
chloride (1:9) (v/v) into a 500 ml K-D flask equipped with a 10 ml
concentrator tube. Concentrate the collected fraction, while exchanging
the solvent to hexane. To exchange the solvent, reduce the elution
solvent to about 10 ml. Add 50 ml of hexane, a fresh boiling chip, and
return the reassembled K-D apparatus to the hot water bath. Adjust the
final volume of the cleaned-up extract to whatever volume is required (1-
10 ml). Compounds that elute in this fraction are:
2,4-Dinitrotoluene
2,6-Dinitrotoluene r
Isophorone
Nitrobenzene. '
7.5 Chlorinated hydrocarbons
, 7.5.1 Reduce the sample extract volume to 2 ml prior to cleanup.
The extract solvent must be hexane.
7.5.2 Add a weight of activated Florisil (nominally 12 g)
predetermined by calibration (Section 5.1.2) into a 10 mm ID
chromatographic column. Tap the column to settle the FlorisiV and add
about 1 to 2 cm of anhydrous sodium sulfate to the top.
7.5,3 Preelute the column with 100 ml of petroleum ether; Discard
the eluate and,'just prior to exposure of the sodium sulfate layer to the
air, quantitatively transfer the sample extract to the column by
decantation and subsequent petroleum ether washings. Discard the eluate.
Just prior to exposure of the sodium sulfate layer to the air, begin
eluting the column with 200 ml of petroleum ether and collect the eluate
in a 500 ml K-D flask equipped with a 10 ml concentrator tube. This
fraction should contain all of the chlorinated hydrocarbons:
2-Chloronaphthalene :
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene '
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane ' : '
1,2,4-Trichlorobenzene. , •
3620A - 6 Revision 1
- . -. • ' July 1992
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7.5.4 Concentrate the fraction, using hexane to prewet the. column.
, When the apparatus' is cool, remove the Snyder column and rinse the flask
and its lower joint into the concentrator tube with hexane. Adjust the
final volume of the cleaned-up extract to whatever volume is required
(1-10 ml).
8.0 QUALITY CONTROL ,
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
' »
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the.
associated quality control samples should also be processed through this cleanup
method. ,
9.0 METHOD PERFORMANCE
9.1 Table 1 indicates the distribution of chlorinated pesticides, PCB's,
and haloethers in various F.lorisil column fractions.
9.2 Table 2 indicates the distribution of organophosphorus pesticides in
various Florisil column fractions. .
10.0 REFERENCES
1. Gordon, A.J. and R.A. Ford, The Chemist's Companion: A Handbook of
Practical Data. Techniques, and References (New York: John Wiley & Sons,
Inc.), pp. 372, 374, and 375, 1972.
2. Floridin of ITT System, Florisil: Properties, Application, Bibliography,
, Pittsburgh, Pennsylvania, 5M381DW. .
v .
3. Mills, P.A., "Variation of Florisil Activity; Simple Method for Measuring
Absorbent Capacity and its use in Standardizing Florisil Columns," Journal
.of the Association of Official Analytical Chemists, 5_1, 29, 1968.
4. U.S. Food and Drug Association, Pesticides Analytical Manual (Volume 1),
July 1985.
5. 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.
3620A - 7 Revision 1
. July 1992
-------
TABLE 1
DISTRIBUTION,OF CHLORINATED PESTICIDES. PCBs.
AND HALOETHERS INTO FLORISIL COLUMN FRACTIONS
Parameter
Percent Recovery by Fraction8
1
Aldrin
a-BHC ,
B-BHC
Y-BHC
5-BHC
Chlordane
4,4'-DDD
4, 4' -DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin. aldehyde
Haloethers
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
100
100
97
. 98
100
100
99
98
100
0
37
0
0
4
0
R
100
100 •
96
97
97
95
97
103
^ 90
95
.
100
64
7 91
0 106
96
.•=68, 26
,
j
4
•'
•• .• '
Eluant composition:
Fraction 1 - 6% ethyl ether in hexane
Fraction 2 - 15% ethyl ether in hexane
Fraction 3 - 50% ethyl ether in hexane
R = Recovered (no percent recovery data presented).
SOURCE: U.S. EPA and FDA data.
'3620A - 8
Revision 1
July 1992
-------
TABLE 2
DISTRIBUTION OF ORGANOPHOSPHORUS PESTICIDES
R
NR
V
ND
INTO
FLORISIL COLUMN FRACTIONS
Percent Recovery by
Parameter
Azinphos methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Oemeton
Diazinon
Dichlorvos
Dlmethoate
Disulfotori
EPN
Ethoprop
.Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Mohochrotophos
Naled
Parathion
Parathion methyl
Phorate
Ronnel
1
ND
>80
NR
100
NR
ND
25-40
-V
ND
R
V
ND>
ND
NR '.
0-62
>80
Stirophos (Tetrachlorvinphos) ND
Sulfotepp
TEPP
Tokuthion (Prothiofos)
Trichloronate
Eluant composition:
i(
V
ND
>80
>80
Fraction 1 -
Fraction 2 -
Fraction 3 -
Fraction 4 -
2
ND
NR
100
NR
ND
>80
V
ND .
R
5
V
ND
ND
NR
100
100
ND
V
ND
200 mL of 6%
200 mL of 15%
200 mL of 50%
•
Fraction8
3 4
20 80
ND ND
NR
NR
ND ND
V
ND ND
95
V
ND ND
ND ND
NR
ND ND
ND ND
ethyl ether in
ethyl ether in
ethyl ether in
hexane
hexane
hexane
200 mL of 100% ethyl ether
Recovered (no percent recovery information presented) (U.S. FDA).
Not recovered (U.S. FDA),
Variable recovery (U.S. FDA). ,
Not determined.
SOURCE: U.S. EPA and,FDA data.
3620A - 9
Revision 1
July 1992
-------
METHOD 3620A
FLORISIL COLUMN CLEANUP
START
7 1-1 Reduce volume
of sample extract
to 2 ml
Phthalate Esters
7. 1 2 Place
Flo'risil into
chr omatographic
column; add
anhydrous sodium
sulfate
Nitrosamines
I
7 1 3 Preelute
column «ith hexane,
transfer sample
extract, add heKane
7 1 4 E1 u t e column
M^th ethyl ether in
hexane
714 Concentrate
fraction, adjust
vo1ume. ana 1y ze
721 Reduce volume
of sample extract
to 2 ml
7 2 2 Put Florisil
into
chromito9raphic
column; add
anhydrous sodium
tulfate
7 2 3 Preelute .
column with ethyl
elher/pentane.
transfer extract.
add pentane
7 2 4 £lute column
•• -i'.h ethyl
ether/pentane
7 2 5 Clute column
.i'.h acetone/ethyl
etherinto flask
3620A - 10
Revision 1
July 1992
-------
METHOD 3620A
continued
Organochl onn«
paaticidat. haloalhari
and org»nophoiohorou«
'31 Raduca voluna
of tanpla ••tract
to 1 aL
timaa into
vol
Chi or ma lad
hyarocarbona
741 Raduca voluma
of lanpla a»traet
to 2 mL
flonail
lographic
n: add
a aodiun
• than
diacard
ata
uat lampla
vol una .
to column
th haiana
I' '
in col umn .
olumn 4
o veparate
• ki
ncenl ra la
ad jua t
~^v
'
7 S 1 Reduce vo lume
of sample *Rtract
to 2 ml
7 5 2 Place
f 1 o r 1 1 1 I in
chromatograohic
coluffl, add
anhyoroui 1001 urn
• .
7 S 3 Preelute
co lumn •i.ih
pel r o 1 eum ether .
• -t ran»f er sampl e
duca ro e i .a le
754' Concent, rale
f rac Lion, aa j u* I
f ina i vo i ume
,
7 4 2^ Put
• 1 ur i
chroma te
columr
anhydroui
• ul:
,
7 4 3 Tt
tamp i e eit i
co 1 umr
meth>
chloride/
• auca ra
7 4 4 -EUt
- -it
ace lone/t
.> o 1 ven l '
7 4 4 Con
fraction.
final v
'26 Add nathanal
lo fraction:
concanlrala
iluala
nga
3620A - 11
Revision 1
July 1992
-------
3630A
-------
METHOD.3630A
SILICA GEL CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Sil-ica gel is a regenerative adsorbent of amorphous silica with
weakly acidic properties. It is produced from sodium silicate and sulfuric aci.d.
Silica gel can be used for column chromatography and is for separating the
analytes from interfering compounds of a different chemical polarity.
1.2 General, applications (Gordon and Ford):
1.2.1 Activated: Heated at 150-160°C for several hours. USES:
Separation of hydrocarbons. ; .
1.2.2 Deactivated: Containing 10-20% water. USES: An adsorbent
for most functionalities with ionic or nonionic characteristics, including
alkaloids, sugar esters, glycosides, dyes, alkali metal cations, lipids,
glycerides, steroids, terpenoids and plasticizers. The disadvantages of
deactivated silica gel are that the solvents methanol, and ethanol decrease
adsorbent activity.
1.3 Specific applications: This method includes guidance for cleanup of
sample extracts containing polynuclear aromatic hydrocarbons, derivatized
phenolic compounds. ' '• ' ;
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required amount of adsorbent, topped
with a water adsorbent, and then loaded with the sample to be analyzed. Elution
of the analytes is effected with a suitable solvent(s) leaving the interfering
compounds on the column. The eluate is then concentrated (if necessary).
3.0 INTERFERENCES .
\
3.1 A reagent blank should be analyzed for the compounds of interest
prior to the use of this method. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS'
4,1 Chromatographic column - 250 mm long x 10 mm ID; 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
3630A - 1 Revision 1
- . ' July 1992
-------
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. '
4.2 Beakers - 500 ml.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts. ,
4.3.2 Evaporation flask - 500 ml (Kontes K-570001-0500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent). , , ,
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent). ,
4.3.5 Springs - 1/2 inch (Kontes K-662750 or'equivalent).
4.4 Vials - 10, 25 ml, glass with Teflon lined screw-caps or crimp tops.
4.5 Muffle furnace.
4.6 Reagent bottle - 500 ml.
4.7 Water bath - Heated, with concentric ring cover, capable of
temperature control (±5°C). The bath should be used in a hood.
4.8 Boiling chips - Solvent extracted, approximately 10/40 mesh (.silicon
carbide or equivalent).
.4.9 Erlenmeyer.fiasks - 50. and 250 ml.
5.0< REAGENTS . .
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Silica gel. 100/200 mesh desicc.ant (Davison Chemical grade 923 or
equivalent). Before use, activate for at least 16 hr. at 130°C in a shallow
3630A - 2 Revision 1
; . • July 1992
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glass tray, loosely covered with foil.
5.4 Sodium sulfate (granular, anhydrous), Na2SO,. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Eluting solvents
5.5.1 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5,5.2 Hexane, C6HU - Pesticide quality or equivalent.
5.5.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.5.4 Toluene, C6H5CH3 - Pesticide quality or equivalent,
5.5.5 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.5.6 Pentahe, C5H12 - 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
i
7.1 Polynuclear aromatic hydrocarbons
7.1.1 Before the silica gel cleanup technique can be utilized, the
extract solvent must be exchanged to cyclohexane. The exchange is
performed as follows: .
' \ . '
7.1.1.1 Following.K-D concentration of the extract to 1-
2 mL using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 minutes. Add one or two clean, boiling chips
to the K-D flask. Add 4 mL of exchange sol vent •• and attach a two
' ball micro-Snyder column. Prewet the Snyder column by adding about
0.5 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 5-1.0 minutes. At the proper rate of distillation
the balls of the column will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 0.5-1 mL,
remove the K-D apparatus from the water bath and allow it to drain
and cool for at least 10 minutes.
3630A - 3 Revision 1
July 1992
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CAUTION: When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.1.1.2 Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with a minimum amount of exchange
solvent. Adjust the extract volume to about 2 ml.
' 7.1.2 Prepare a slurry of 10 g of activated silica gel in methylene
chloride and place this into a 10 mm ID chromatpgraphic column. Tap the
column to settle the silica gel and elute the methylene chloride. Add 1
to 2 cm of anhydrous sodium sulfate to the top of the silica gel.
7.1.3 Preelute the column with 40 ml of pentane. The rate for all
elutions should be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, transfer the 2 ml
cyclohexane sample extract onto the column using an additional 2 ml
cyclohexane to complete the transfer. Just prior to exposure of the
sodium sulfate layer to the air, add 25 ml of pentane and continue the
elutipn of the column. Discard this pentane eluate.
7.1.4 Next, elute the column with 25 ml of methylene chloride/
pentane (2:3)(v/v) into a 500 mL K-D flask equipped with a 10 ml
concentrator tube. Concentrate the collected fraction to whatever volume
is required (1-10 ml). Proceed with HPLC or GC analysis. Components that
elute in this fraction, are:
Acenaphthene .
Acenaphthylene .
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene -
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene . ,
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
7.2 Derivatized phenols
7.2.1 This silica gel cleanup procedure is performed on sample
extracts that- have undergone pentafluorobenzyl bromide derivatization as
described in Method 8040. , ,
7.2.2 Place 4.0 g of activated silica gel. into a 10 mm ID
chromatographic column. Tap the column to settle the silica gel and add
about 2 g of anhydrous sodium sulfate to the top of the silica gel.
7.2.3 Preelute the column with-6 ml of hexane. The rate for all
3630A - 4 Revision 1
July 1992
-------
elutions should be about 2 mL/min. Discard the eluate and just prior to
exposure of the sodium sulfate layer to the air, pipet onto the column
2 ml of the hexane solution that. contains the derivatized sample or
standard. Elute the column with 10.0 ml of hexane and discard the eluate.
7.2.4 Elute the column, in order, with. 10.0 ml of 15% toluene in
hexane (Fraction 1); 10.0 ml of 40% toluene in hexane (Fraction 2);
10.0 ml of 75% toluene in hexane (Fraction 3); and 10.0 mL of 15% 2-
' propanol in toluene (Fraction 4). All elution mixtures are prepared on a
volume:volume basis. Elution patterns for the phenolic derivatives are
shown in Table 1. Fractions may be combined, as desired, depending upon
the specific phenols of interest or level of interferences. Proceed with
GC analysis (Method 8040).
') ' • .
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Table 1 provides performance information on the fractionation of
phenolic derivatives using this method.
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.
3630A - 5 Revision 1
July 1992
-------
TABLE 1
SILICA GEL FRACTIONATION OF PFBB DERIVATIVES
Percent Recovery by Fraction"
Parameter 1 ~ 23
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4-Dimethyl phenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-3-methyl phenol
Pentachlorophenol
4-Nitrophenol
90
"-
90
95
95
50 50
84
75 20
1
9
10
7
1
14
1
90
90
Eluant composition:
Fraction 1 - 15% toluene in hexane.
Fraction 2 - 40% toluene in hexane.
Fraction 3 - 75% toluene in hexane.
Fraction 4 - 15% 2-propanol in toluene.
3630A - 6 Revision 1
July 1992
-------
METHOD 3630A
SILICA GEL CLEANUP
C
Start
7 1 Exchange
• •traction .solvent
to eyclohesane,
adjust extract
• volume
Polynuclcar
aromatic
hydrocarbons
Denvatiied phenols
7 1 2 Put methylene
chloride slurry of
silica g«l in
column Elute
solvent. add
anhydrous lodiua
• • sulfate
T 1 3 Pr.«lut«
column »ith
p«ntan«; transfer
••tract to column.
• lut* >ith p«ntan« '
714 Clut* column
•ith m«thyl«n»
chlor id«/p«ntan«.
Conontrat*
fractionand adjust
volum*
Analyze by CC
(Method 8040)
721 Oarivatna
(PFBB) .a.pl.
••tract (Method
8040).
722 Put activated
silica g«l in
column, add
anhydrous sodium
sulfate
72.3 Preelute
column «ith heiian*.
add aiitract to
coluan. «luta ,
724 Elut« four.
fracIions fron
column, analyi*
using Mathod 8040
3630A - 7
Revision 1
July 1992
-------
3630B
-------
METHOD 3630B
SILICA GEL CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Silica gel is a regenerative adsorbent of amorphous silica with
weakly acidic properties. It is produced from sodium silicate and sulfuric acid.
Silica gel can be used in column chromatography for the separation of analytes
from interfering compounds of a different chemical polarity. It may be used
activated, after heating to 150 - 160°C, or deactivated with up to 10% water.
1.2 This method includes guidance for standard column cleanup of sample
extracts containing polynuclear aromatic hydrocarbons, derivatized phenolic
compounds, organochlorine pesticides, and PCBs as Aroclors.
1.3 This method also provides cleanup procedures using solid-phase
extraction cartridges for pentafluorobenzyl bromide-derivatized phenols,
organochlorine pesticides, and PCBs as Aroclors. This technique also provides
the best separation of PCBs from most single component organochlorine pesticides.
When only PCBs are to be measured, this method can be used in conjunction with
sul'furic acid/permanganate cleanup (Method 3665).
1.4 Other analytes may be cleaned up using this method if the analyte
recovery meets the criteria specified in Sec. 8.0.
2.0 SUMMARY OF METHOD
2.1 This method provides the option of using either standard column
chromatography techniques or solid-phase extraction cartridges. Generally, the
standard column chromatography techniques use larger amounts of adsorbent and,
therefore, have a greater cleanup capacity.
2.2 In the standard column cleanup protocol, the column is packed with
the required amount of adsorbent, topped with a water adsorbent, and then loaded
with the sample to be analyzed. Elution of the analytes is accomplished with a
suitable solvent(s) that leaves the interfering compounds on the column. The
eluate is then concentrated (if necessary).
2.3 The cartridge cleanup protocol uses silica solid-phase extraction
cartridges packed with 1 g or 2 g of adsorbent. Each cartridge is solvent washed
immediately prior to use. Aliquots of sample extracts are loaded onto the
cartridges, which are then eluted with suitable solvent(s). A vacuum manifold
is required to obtain reproducible results. The collected fractions may be
further concentrated prior to gas chromatographic analysis.
2.4 The appropriate gas chromatographic method is listed at the end of
each technique. Analysis may also be performed by gas chromatography/mass
spectrometry (Method 8270).
3630B - 1 Revision 2
September 1994
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3-.-0 INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All these materials must be demonstrated to be free from
interferences under the conditions of the analysis, by analyzing reagent blanks.
See Sec. 8 for guidance on a reagent blank check.
3.2 Phthalate ester contamination may be a problem with certain
cartridges The more inert the column and/or cartridge material (i.e., glass or
Teflon), the less problem with phthalates. Phthalates create interference
problems for all method analytes, not just the phthalate esters themselves.
3.3 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Chromatographic column - 250 mm long x 10 mm ID; 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.
4.2 Beakers - 500 ml.
4.3 Vials - 2, 10, 25 ml, glass with Teflon lined screw-caps or crimp
tops.
4.4 Muffle furnace.
4.5 Reagent bottle - 500 ml.
4.6 Erlenmeyer flasks - 50 and 250 mL.
4.7 Vacuum manifold: VacElute Manifold SPS-24 (Analytichem
International), Visiprep (Supelco, Inc.) or equivalent, consisting of glass
vacuum basin, collection rack and funnel, collection vials, replaceable stainless
steel delivery tips, built-in vacuum bleed valve and gauge. The system is
connected to a vacuum pump or water aspirator through a vacuum trap made from a
500 ml sidearm flask fitted with a one-hole stopper and glass tubing.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
3630B - 2 Revision 2
September 1994
-------
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Silica gel for chromatography columns.
5.3.1 Silica Gel for Phenols and Polynuclear Aromatic Hydrocarbons:
100/200 mesh desiccant (Davison Chemical grade 923 or equivalent). Before
use, activate for at least 16 hr. at 130°C in a shallow glass tray, loosely
covered with foil.
5.3.2 Silica Gel for Organochlorine pesticides/PCBs: 100/200 mesh
desiccant (Davison Chemical grade 923 or equivalent). Before use,
activate for at least 16 hr. at 130°C in a shallow glass tray, loosely
covered with foil. Deactivate it to 3.3% with reagent water in a 500 ml
glass jar. Mix the contents thoroughly and allow to equilibrate for 6
hours. Store the deactivated silica gel in a sealed glass jar inside a
desiccator.
5.4 Silica cartridges: 40 /im particles, 60 A pores. The cartridges with
which this method was developed consist of 6 mi serological-grade polypropylene
tubes, with the 1 g of silica held between two polyethylene or stainless steel
frits with 20 ^m pores. 2 g silica cartridges are also used in this method, and
0.5 g cartridges are available. The compound elution patterns must be verified
when cartridges other than the specified size are used.
5.5 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. A method blank must be analyzed in order to demonstrate that
there is no interference from the sodium sulfate.
5.6 Eluting solvents
5.6.1 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.6.4 Toluene, C6H5CH3 - Pesticide quality or equivalent.
5.6.5 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.6 Pentane, C5H12 - Pesticide quality or equivalent.
5.6.7 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.6.8 Diethyl Ether, C2H5OC2H5. Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
3630B - 3 Revision 2
September 1994
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test strips. After cleanup, 20 ml of ethanol preservative must be added
to each liter of ether.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
7.0 PROCEDURE
7.1 General Guidance
7.1.1 The procedure contains two cleanup options for the derivatized
phenols and organochlorine pesticides/Aroclors, but only one technique for
the polynuclear aromatic hydrocarbons (PAHs) (standard column
chromatography). Cleanup techniques by standard column chromatography for
all analytes are found in Sec. 7.2. Cleanup techniques by solid-phase
cartridges for derivatized phenols and PAHs are found in Sec. 7.3. The
standard column chromatography techniques are packed with a greater amount
of silica gel adsorbent and, therefore, have a greater cleanup capacity.
A rule of thumb relating to cleanup capacity is that 1 g of sorbent
material will remove 10 to 30 mg of total interferences. (However,
capacity is also dependent on the sorbent retentiveness of the
interferences.) Therefore, samples that exhibit, a greater degree of
sample interference should be cleaned up by the standard column technique.
However, both techniques have limits on the amount of interference that
can be removed. If the interference is caused by high boiling material,
then Method 3640 should be used prior to this method. If the interference
is caused by relatively polar compounds of the same boiling range as the
analytes, then multiple column or cartridge cleanups may be required. If
crystals of sulfur are noted in the extract, then Method 3660 should be
utilized prior to this method. The cartridge cleanup techniques are often
faster and use less solvent, however they have less cleanup capacity.
7.1.2 Allow the extract to reach room temperature if it was in cold
storage. Inspect the extracts visually to ensure that there are no
particulates or phase separations and that the volume is as stated in the
accompanying documents. Verify that the solvent is compatible with the
cleanup procedures. If crystals of sulfur are visible or if the presence
of sulfur is suspected, proceed with Method 3660.
7.1.3 If the extract solvent is methylene chloride, for most cleanup
techniques, it must be exchanged to hexane. (For the PAHs, exchange to
cyclohexane as per Sec. 7.2.1). Follow the standard Kuderna-Danish
concentration technique provided in each extraction method. The volume of
methylene chloride should have been reduced to 1 - 2 mL. Add 40 mL of
hexane, a fresh boiling chip and repeat the concentration as written. The
final volume required for the cleanup techniques is normally 2 mL.
3630B - 4 Revision 2
September 1994
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7.2 Standard Column Cleanup Techniques
7.2.1 Polynuclear aromatic hydrocarbons
7.2.1.1 Before the silica gel cleanup technique can be
utilized, the extract solvent must be exchanged to cyclohexane. The
exchange is performed by adding 4 ml of cyclohexane following
reduction of the sample extract to 1-2 ml using the macro Snyder
column. Attach the two ball micro Snyder column and reduce the
volume to 2 ml.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost. If the
extract goes to dryness, the extraction must be
repeated.
7.2.1.2 Prepare a slurry of 10 g of activated silica gel
(Sec. 5.3.1) in methylene chloride and place this into a 10 mm ID
chromatographic column. Tap the column to settle the silica gel and
elute the methylene chloride. Add 1 to 2 cm of anhydrous sodium
sulfate to the top of the silica gel.
7.2.1.3 Pre-elute the column with 40 ml of pentane. The
rate for all elutions should be about 2 mL/min. Discard the eluate
and, just prior to exposure of the sodium sulfate layer to the air,
transfer the 2 ml cyclohexane sample extract onto the column using
an additional 2 ml cyclohexane to complete the transfer. Just prior
to exposure of the sodium sulfate layer to the air, add 25 ml of
pentane and continue the elution of the column. Discard this
pentane eluate.
7.2.1.4 Next, elute the column with 25 ml of methylene
chloride/pentane (2:3)(v/v) into a 500 ml K-D flask equipped with a
10 ml concentrator tube. Concentrate the collected fraction to
whatever volume is required (1-10 mL). Proceed with HPLC (Method
8310) or GC analysis (Method 8100). Validated components that elute
in this fraction are:
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
3630B - 5 Revision 2
September 1994
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7.2.2 Derivatized Phenols
7.2.2.1 This silica gel cleanup procedure is performed on
sample extracts that have undergone pentafluorobenzyl bromide
derivatization, as described in Method 8040. The sample extract
must be in 2 ml of hexane at this point.
7.2.2.2 Place 4.0 g of activated silica gel (Sec. 5.3.1)
into a 10 mm ID chromatographic column. Tap the column to settle
the silica gel and add about 2 g of anhydrous sodium sulfate to the
top of the silica gel.
7.2.2.3 Pre-elute the column with 6 ml of hexane. The
rate for all elutions should be about 2 mL/min. Discard the eluate
and, just prior to exposure of the sodium sulfate layer to the air,
pipet onto the column 2 mL of the hexane solution that contains the
derivatized sample or standard. Elute the column with 10.0 ml of
hexane and discard the eluate.
7.2.2.4 Elute the column, in order, with 10.0 ml of 15%
toluene in hexane (Fraction 1); 10.0 ml of 40% toluene in hexane
(Fraction 2); 10.0 ml of 75% toluene in hexane (Fraction 3); and
10.0 ml of 15% 2-propanol in toluene (Fraction 4). All elution
mixtures are prepared on a volume:volume basis. Elution patterns
for the phenolic derivatives are shown in Table 1. Fractions may be
combined, as desired, depending upon the specific phenols of
interest or level of interferences. Proceed with GC analysis
(Method 8040).
7.2.3 Organochlorine.Pesticides and Aroclors
7.2.3.1 Transfer a 3 g portion of deactivated silica gel
(Sec. 5.3.2) into a 10 mm ID glass chromatographic column and top it
with 2 to 3 cm of anhydrous sodium sulfate.
7.2.3.2 Add 10 ml of hexane to the top of the column to
wet and rinse the sodium sulfate and silica gel. Just prior to
exposure of the sodium sulfate layer to air, stop the hexane eluate
flow by closing the stopcock on the chromatographic column. Discard
the eluate.
7.2.3.3 Transfer the sample extract (2 ml in hexane) onto
the column. Rinse the extract vial twice with 1 to 2 ml of hexane
and add each rinse to the column. Elute the column with 80 ml of
hexane (Fraction I) at a rate of about 5 mL/min. Remove the
collection flask and set it aside for later concentration. Elute
the column with 50 ml of hexane (Fraction II) and collect the
eluate. Perform a third elution with 15 ml of methylene chloride
(Fraction III). The elution patterns for the organochlorine
pesticides, Aroclor-1016, and Aroclor-1260 are shown in Table 2.
7.2.3.4 Prior to gas chromatographic analysis, the
extraction solvent must be exchanged to hexane. Fractions may be
combined, as desired, depending upon the specific
3630B - 6 Revision 2
September 1994
-------
pesticides/Aroclors of interest or level of interferences. If
mixtures of Aroclors and pesticides are expected, it is best to
analyze Fraction I separately, since it contains the Aroclors
separated from most pesticides. Proceed with GC analysis as per
Method 8081.
7.3 Cartridge Cleanup Techniques
7.3.1 Cartridge Set-up and Conditioning
7.3.1.1 Arrange the 1 g silica cartridges (2 g for phenol
cleanup) on the manifold in the closed-valve position. Other size
cartridges may be used, however the data presented in the Tables are
all based on 1 g cartridges for pesticides/Aroclors and 2 g
cartridges for phenols. Therefore, supporting recovery data must be
developed for other sizes. Larger cartridges will probably require
larger volumes of elution solvents.
7.3.1.2 Turn on the vacuum pump and set pump vacuum to 10
inches (254 mm) of Hg. Do not exceed the manufacturer's
recommendation for manifold vacuum. Flow rates can be controlled by
opening and closing cartridge valves.
7.3.1.3 Condition the cartridges by adding 4 ml of hexane
to each cartridge. Slowly open the cartridge valves to allow hexane
to pass through the sorbent beds to the lower frits. Allow a few
drops per cartridge to pass through the manifold to remove all air
bubbles. Close the valves and allow the solvent to soak the entire
sorbent bed for 5 minutes. Do not turn off the vacuum.
7.3.1.4 Slowly open cartridge valves to allow the hexane
to pass through the cartridges. Close the cartridge valves when
there is still at least 1 mm of solvent above the sorbent bed. Do
not allow cartridges to become dry. If cartridges go dry, repeat
the conditioning step.
7.3.2 Derivatized Phenols
7.3.2.1 Reduce the sample extract volume to 2 ml prior to
cleanup. The extract solvent must be hexane and the phenols must
have undergone derivatization by pentafluorobenzyl bromide, as per
Method 8040.
7.3.2.2 Transfer the extract to the 2 g cartridge that has
been conditioned as described in Sec. 7.3.1. Open the cartridge
valve to allow the extract to pass through the cartridge bed at
approximately 2 mL/minute.
7.3.2.3 When the entire extract has passed through the
cartridges, but before the cartridge: becomes dry, rinse the sample
vials with an additional 0.5 ml of hexane, and add the rinse to the
cartridges to complete the quantitative transfer.
3630B - 7 Revision 2
September 1994
-------
7.3.2.4 Close the cartridge valve and turn off the vacuum
after the solvent has passed through, ensuring that the cartridge
never gets dry.
7.3.2.5 Place a 5 ml vial or volumetric flask into the
sample rack corresponding to the cartridge position. Attach a
solvent-rinsed stainless steel solvent guide to the manifold cover
and align with the collection vial.
7.3.2.6 Add 5 ml of hexane to the cartridge. Turn on the
vacuum pump and adjust the pump pressure to 10 inches (254 mm) of
Hg. Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly open the cartridge valve, and collect the eluate (this is
Fraction 1, and should be discarded).
NOTE: If cartridges smaller than 2 g are used, then Fraction
1 cannot be discarded, since it contains some of the
phenols.
7.3.2.7 Close the cartridge valve, replace the collection
vial, and add 5 mL of toluene/hexane (25/75, v/v) to the cartridge.
Slowly open the cartridge valve and collect the eluate into the
collection vial. This is Fraction 2, and should be retained for
analysis.
7.3.2.8 Adjust the final volume of the eluant to a known
volume which will result in analyte concentrations appropriate for
the project requirements (normally 1-10 ml). Table 3 shows
compound recoveries for 2 g silica cartridges. The cleaned up
extracts are ready for analysis by Method 8040.
7.3.3 Organochlorine Pesticides/Aroclors
NOTE: The silica cartridge procedure is appropriate when
polychlorinated biphenyls are known to be present.
7.3.3.1 Reduce the sample extract volume to 2 ml prior to
cleanup. The extract solvent must be hexane.
7.3.3.2 Use the 1 g cartridges conditioned as described in
Sec. 7.3.1.
7.3.3.3 Transfer the extract to the cartridge. Open the
cartridge valve to allow the extract to pass through the cartridge
bed at approximately 2 mL/minute.
7.3.3.4 When the entire extract has passed through the
cartridges, but before the cartridge becomes dry, rinse the sample
vials with ah additional 0.5 ml of solvent, and add the rinse to the
cartridges to complete the quantitative transfer.
7.3.3.5 Close the cartridge valve and turn off the vacuum
after the solvent has passed through, ensuring that the cartridge
never goes dry.
3630B - 8 Revision 2
September 1994
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7.3.3.6 Place a 5 ml vial or volumetric flask into the
sample rack corresponding to the cartridge position. Attach a
solvent-rinsed stainless steel solvent guide to the manifold cover
and align with the collection vial.
7.3.3.7 Add 5 ml of hexane to the cartridge. Turn on the
vacuum pump and adjust the pump pressure to 10 inches (254 mm) of
Hg. Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly open the cartridge valve and collect the eluate into the
collection vial (Fraction 1).
7.3.3.8 Close the cartridge valve, replace the collection
vial, and add 5 ml of diethyl ether/hexane (50/50, v/v) to the
cartridge. Slowly open the cartridge valve and collect the eluate
into the collection vial (Fraction 2).
7.3.3.9 Adjust the final volume of each of the two
fractions to a known volume which will result in analyte
concentrations appropriate for the project requirements (normally 1
- 10 ml). The fractions may be combined prior to final adjustment
of volume, if analyte fractionation is not required. Table 4 shows
compound recoveries for 1 g silica cartridges. The cleaned up
extracts are ready for analysis by Method 8081.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 A reagent blank (consisting of the elution solvents) must be passed
through the column or cartridge and checked for the compounds of interest, prior
to the use of this method. This same performance check is required with each new
lot of adsorbent or cartridges. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
8.3 The analyst must demonstrate that the compounds of interest are being
quantitatively recovered before applying this method to actual samples. See the
attached Tables for acceptable recovery data. For compounds that have not been
tested, recovery must be > 85%.
8.3.1 Before any samples are processed using the solid-phase
extraction cartridges, the efficiency of the cartridge must be verified.
A recovery check must be performed usi.ng standards of the target analytes
at known concentration. Only lots of cartridges that meet the recovery
criteria for the spiked compounds can be used to process the samples.
8.3.2 A check should also be performed on each individual lot of
cartridges and for every 300 cartridges of a particular lot.
8.4 For sample extracts that are cleaned up using this method, the
associated quality control samples should also be processed through this cleanup
method.
3630B - 9 Revision 2
September 1994
-------
9.0 METHOD PERFORMANCE
9.1 Table 1 provides performance information on the fractionation of
phenolic derivatives using standard column chromatography.
9.2 Table 2 provides performance information on the fractionation of
organochlorine pesticides/Aroclors using standard column chromatography.
9.3 Table 3 shows recoveries of derivatized phenols obtained using 2 g
silica cartridges.
9.4 Table 4 shows recoveries and fractionation of organochlorine
pesticides obtained using 1 g silica cartridges.
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 "Evaluation of Sample Extract Cleanup Using Solid-Phase
Extraction Cartridges," Project Report, December 1989.
3630B - 10 Revision 2
September 1994
-------
TABLE 1
SILICA GEL FRACTIONATION OF PFBB DERIVATIVES
Percent Recovery by Fraction8
Parameter 1 2
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4-Dimethyl phenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-3-methyl phenol
Pentachlorophenol
4-Nitrophenol
90
90
95
95
50 50
84
75 20
1
9
10
7
1
14
1
90
90
a Eluant composition:
Fraction 1 - 15% toluene in hexane.
Fraction 2 - 40% toluene in hexane.
Fraction 3 - 75% toluene in hexane.
Fraction 4 - 15% 2-propanol in toluene.
Data from Reference 1 (Method 604)
3630B - 11 Revision 2
September 1994
-------
TABLE 2
DISTRIBUTION AND PERCENT RECOVERIES OF ORGANOCHLORINE
PESTICIDES AND PCBs AS AROCLORS IN SILICA GEL COLUMN FRACTIONS8'"'0-"'8
Compound
alpha-BHCf
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
Technical chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4,4'-DDDf
Endrin aldehyde
Endosulfan sulfate
4,4'-DDTf
4,4'-Methoxychlor
Toxaphenef
Aroclor-1016
Aroclor-1260
Fraction I
Cone. Cone.
1 2
109(4.1)
97(5.6)
14(5.5)
86(5.4)
86(4.0)
91(4.1)
118(8.7)
104(1.6)
22(5.3)
94(2.8)
87(6.1)
95(5.0)
Fraction II Fraction III
Cone. Cone. Cone.
1 2 1
82(1.7)
107(2.1)
91(3.6)
92(3.5)
95(4.7)
19(6.8) 39(3.6) 29(5.0)
95(5.1)
96(6.0)
85(10.5)
97(4.4)
102(4.6)
81(1.9)
93(4.9)
86(13.4) 73(9.1) 15(17.7)
99(9.9)
15(2.4) 17(1.4) 73(9.4)
Cone.
2
74(8.0)
98(12.5)
85(10.7)
83(10.6)
88(10.2)
37(5.1)
87(10.2)
87(10.6)
71(12.3)
86(10.4)
92(10.2)
76(9.5)
82(9.2)
8.7(15.0)
82(10.7)
84(10.7)
Total Recovery
Cone. Cone.
1 2
82(1.7)
107(2.1)
91(3.6)
92(3.5)
109(4.1)
97(5.6)
95(4.7)
62(3.3)
95(5.1)
86(5.4)
96(6.0)
85(10.5)
97(4.4)
102(4.6)
81(1.9)
93(4.9)
101(5.3)
99(9.9)
88(12.0)
86(4.0)
91(4.1)
74(8.0)
98(12.5)
85(10.7)
83(10.6)
118(8.7)
104(1.6)
88(10.2)
98(1.9)
87(10.2)
94(2.8)
87(10.6)
71(12.3)
86(10.4)
92(10.2)
76(9.5)
82(9.2)
82(23.7)
82(10.7)
101(10.1)
87(6.1)
95(5.0)
3630B - 12
Revision 2
September 1994
-------
TABLE 2
(Continued)
Effluent composition: Fraction I, 80 ml hexane; Fraction II, 50 ml hexane; Fraction III, 15 ml methylene
chloride.
Concentration 1 is 0.5 jug per column for BHCs, Heptachlor, Aldrin, Heptachlor epoxide, and Endosulfan I; 1.0
ng per column for Dieldrin, Endosulfan II, 4,4'-DDD, 4,4'-DDE, 4,4'-DDT, Endrin, Endrin aldehyde, and
Endosulfan sulfate; 5 /jg per column for 4,4'-Methoxychlor and technical Chlordane; 10 />g per column for
Toxaphene, Aroclor-1016, and Aroclor-1260.
For Concentration 2, the amounts spiked are 10 times as high as those for Concentration 1.
Values given represent the average recovery of three determinations; numbers in parentheses are the standard
deviation; recovery cutoff point is 5 percent.
Data obtained with standards, as indicated in footnotes b and c, dissolved in 2 ml hexane.
It has been found that because of batch-to-batch variation in the silica gel material, these compounds cross
over in two fractions and the amounts recovered in each fraction are difficult to reproduce.
3630B - 13 Revision 2
September 1994
-------
TABLE 3
PERCENT RECOVERIES AND ELUTION PATTERNS FOR 18
PHENOLS FROM 2 g SILICA CARTRIDGES8
Fraction 2
Average Percent
Compound Recovery RSD
Phenol
2-Methyl phenol
3-Methylphenol
4-Methylphenol
2, 4-Dimethyl phenol
2-Chlorophenol
2,6-Dichlorophenol
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
2,3,6-Trichlorophenol
2,4,5-Trichlorophenol
2,3,5-Trichlorophenol
2,3,5,6-Tetrachlorophenol
2,3,4,6-Tetrachlorophenol
2,3,4-Trichlorophenol
2,3,4,5-Tetrachlorophenol
Pentachlorophenol
74.1
84.8
86.4
82.7
91.8
88.5
90.4
94.4
94.5
97.8
95.6
92.3
92.3
97.5
97.0
72.3
95.1
96.2
5.2
5.2
4.4
5.0
5.6
5.0
4.4
7.1
7.0
6.6
7.1
8.2
8.2
5.3
6.1
8.7
6.8
8.8
a Silica cartridges (Supelco, Inc.) were used; each cartridge was conditioned
with 4 mL of hexane prior to use. Each experiment was performed in duplicate
at three spiking concentrations (0.05 /zg, 0.2 /zg, and 0.4 /ng per compound per
cartridge). Fraction 1 was eluted with 5 mL hexane and was discarded.
Fraction 2 was eluted with 5 mL toluene/hexane (25/75, v/v).
Data from Reference 2
3630B - 14 Revision 2
September 1994
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TABLE 4
PERCENT RECOVERIES AND ELUTION PATTERNS FOR 17 ORGANOCHLORINE
PESTICIDES AND AROCLORS FROM 1 g SILICA CARTRIDGES8
Compound
Fraction 1
Average Percent
Recovery RSD
Fraction 2
Average Percent
Recovery RSD
alpha-BHC
gamma-BHC
beta-BHC
Heptachlor
delta-BHC
Aldrin
Heptachlor epoxide
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
4, 4' -ODD
Endosulfan II
4,4'-DDT
Endrin aldehyde
Endosulfan sulfate
4,4'-Methoxychlor
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1264
0
0
0
97.3 1.3
0
95.9 1.0
0
0
99.9 1.7
0
0
10.7 41
0
94.1 2.0
0
0
0
124
93.5
118
116
114
108
112
98.7
94.8
94.3
0
90.8
0
97.9
102
0
92.3
117
92.4
96.0
0
59.7
97.8
98.0
2.3
1.9
3.0
2.5
2.1
2.3
2.0
2.6
3.3
2.2
2.6
2.1
2.4
a Silica cartridges (Supelco, Inc. lot SP0161) were used; each cartridge was
conditioned with 4 mL hexane prior to use. The organochlorine pesticides were
tested separately from PCBs. Each organochlorine pesticides experiment was
performed in duplicate, at three spiking concentrations (0.2 jug, 1.0 /^g, and
2.0 p.g per compound per cartridge). Fraction 1 was eluted with 5 mL of
hexane, Fraction 2 with 5 mL of diethyl ether/hexane (50/50, v/v). PCBs were
spiked at 10 p,g per cartridge and were eluted with 3 mL of hexane. The values
given for PCBs are the percent recoveries for a single determination.
Data from Reference 2
3630B - 15
Revision 2
September 1994
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METHOD 3630B
SILICA GEL CLEANUP
OC Pesticide
PCBs & Phenols'
7.2 Standard
Column Claanup
< 10-30 mg,
7.2.2.1 Do PFBB
derivatization on
sampla extract
(8040).
7.2.2.2 Place
activated silica gal
in chromatographie
column; add
anhydrous Na2SO*.
7.2.2.3 Praelute
column with hexane;
pipet hexana
solution onto column;
eluta.
7.2.2.4 Eluta column
with specified
solvents.
Analyze
by GC
(Method
8040).
7.2.3.1 Deactivate
silica gel, prepare
column.
7.2.3.2 Eluta the
GC column
with hexane.
7.2.3.3 Transfer
extract onto column
and elute with
specified solvents.
7.3.4 Exchange the
elution solvent
to hexana (Section
7.1.3). .
7.3 Cartridga
Claanup.
7.3.1 Cartridga
Set-up &
Conditioning.
7.3.2.1 Do PFBB
darivatization on
sample extract
(8040).
7.3.3.1 Exchange
solvent to
haxana.
7.3.2.3 & 7.3.2.4
Transfer extract
to cartridga.
i
7.3.3.3 & 7.3.3.4
Transfer extract
to cartridga.
7.3.2.8 & 7.3.2.7
Rinse cartridge
with hexana &
discard.
7.3.3.8 & 7.3.3.7
Eluta cartridga
with hexane as
Fraction I.
7.3.2.8 Eluta
cartridge with
toluane/haxane. •
7.3.3.8 Elute
cartridge with
ether/hexane as
Fraction II.
Analyze
each fraction
by GC
Method
8081.
.3630B - 16
Revision 2
September 1994
-------
METHOD 3630B
(continued)
0
(PAHs)
7.2 Standard
Column. Cleanup.
7.2.1.1 Exchange
extract solvent to
cyclohexane during
K-D procedure.
7.2.1.2 Prepare
slurry activated
silica gel, prepare
column.
7.2.1.3 Preelute
column with
pentane, transfer
extract onto column
and elute with
pentane.
7.2.1.4 Elute
column with
CH2CI2 /pentane;
concentrate
collected fraction;
adjust volume.
Analyze
by GC Method
8100 or
GC/MS
Method
8270.
3630B - 17
Revision 2
September 1994
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3640A
-------
METHOD 3640A
GEL-PERMEATION CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Gel-permeation chromatography (GPC) is a size exclusion cleanup
procedure using organic solvents and hydrophobic gels in the separation of
synthetic macromolecules (1). The packing gel is porous and is characterized by
the range or uniformity (exclusion range) of that pore size. In the choice of
gels, the exclusion range must be larger than the molecular size of the molecules
to be separated (2). A cross-linked divinylbenzene-styrene copolymer (SX-3 Bio
Beads or equivalent) is specified for this method.
1.2 General cleanup application - GPC is recommended for the elimination
from the sample of lipids, polymers, copolymers, proteins, natural resins and
polymers, cellular components, viruses, steroids, and dispersed high-molecular-
weight compounds (2). GPC is appropriate for both polar and non-polar analytes,
therefore, it can be effectively used to cleanup extracts containing a broad
range of analytes.
1.3 Specific application - This method includes guidance for cleanup of
sample extracts containing the following analytes from the RCRA Appendix VIII and
Appendix IX 1ists:
Compound Name CAS No.'
Acenaphthene 83-32-9
Acenaphthylene 208-96-8
Acetophenone 98-86-2
2-Acetylaminofluorene 53-96-3
Aldrin 309-00-2
4-Aminobiphenyl 92-67-1
Aniline 62r53-3
Anthracene 120-12-7
Benomyl 17804-35-2
Benzenethiol 108-98-5
Benzidine 92-87-5
Benz(a)anthracene 56-55-3
Benzo(b)fluoranthehe 205-99-2
Benzo(a)pyrene 50-32-8
Benzo(ghi)perylene 191-24-2
Benzo(k)fluoranthene 207-08-9
Benzoic acid 65-85-0
Benzotrichloride 98-07-7
Benzyl alcohol 100-51-6
Benzyl chloride 100-44-7
alpha-BHC 319-84-6
beta-BHC 319-85-7
3640A - 1 Revision 1
September 1994
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Compound Name
gamma -BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-butyl-4,6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chloro-3-methyl phenol
4-Chloroaniline
Chi orobenzi late
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
3-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Dibenzo(a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a, j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzothiophene
1 ,2-Dibromo-3-chloropropane
1,2-Dibromoethane
trans- l,4-Dichloro-2-butene
cis-l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3, 3 '-Dichl orobenzi dine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
CAS No.8
58-89-9
319-86-8
101-55-3
85-68-7
88-85-7
86-74-8
10605-21-7
5103-71-9
5566-34-7
59-50-7
106-47-8
510-15-6
111-91-1
111-44-4
108-60-1
91-58-7
95-57-8
106-48-9
108-43-0
7005-72-3
542-76-7
218-01-9
95-48-7
108-39-4
106-44-5
50-18-0
72-54-8
72-55-9
50-29-3
84-74-2
2303-16-4
192-65-4
189-55-9
224-42-0
53-70-3
132-64-9
132-65-0
96-12-8
106-93-4
110-57-6
1476-11-5
95-50-1
106-46-7
541-73-1
91-94-1
87-65-0
94-75-7
120-83-2
3640A - 2
Revision 1
September 1994
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Compound Name
2,4-Dichlorotoluene
l,3-Dichloro-2-propanol
Dieldrin
Diethyl phthalate
Dimethoate
Dimethyl phthalate
p-Dimethylaminoazobenzene
7, 12-Dimethyl -benz(a)anthracene
2,4-Dimethylphenol
3,3-Dimethylbenzidine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2-Di phenyl hydrazi ne
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methylcholanthrene
CAS No.8
95-73-8
96-23-1
60-57-1
84-66-2
60-51-5
131-11-3
60-11-7
57-97-6
105-67-9
119-93-7
534-52-1
99-65-0
51-28-5
121-14-2
606-20-2
122-39-4
101-84-8
122-66-7
298-04-4
1031-07-8
959-98-8
33213-65-9
72-20-8
7421-93-4
53494-70-5
62-50-0
97-63-2
117-81-7
52-85-7
86-73-7
206-44-0
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
1888-71-7
193-39-5
465-73-6
78-59-1
17627-76-8
4043-71-4
143-50-0
109-77-3
150-50-5
72-43-5
56-49-5
3640A - 3
Revision 1
September 1994
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Compound Name
2-Methyl naphthal ene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodi ethyl ami ne
N-Nitrosodi methyl ami ne
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorpholine
N-Nitrosopiperidine
N-Nitrosopyrolidine
Di-n-octyl phthalate
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
1,2-Phenylenediamine
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1 , 2 , 4 , 5-Tetrachl orobenzene
2,3,5,6-Tetrachloronitrobenzene
2,3,5,6-Tetrachlorophenol
2 , 3 , 4 , 6-Tetrachl orophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
CAS No.8
91-57-6
298-00-0
101-14-4
91-20-3
130-15-4
91-59-8
134-32-7
99-55-8
88-74-4
99-09-2
100-01-6
98-95-3
79-46-9
100-02-7
924-16-3
1116-54-7
55-18-5
62-75-9
86-30-6
621-64-7
10595-95-6
59-89-2
100-75-4
930-55-2
117-84-0
56-38-2
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
95-54-5
298-02-2
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
117-18-0
935-95-5
58-90-2
3689-24-5
79-19-6
106-49-0
95-53-4
3640A - 4
Revision 1
September 1994
-------
Compound Name CAS No.'
Thiourea, l-(o-chlorophenyl) 5344-82-1
Toluene-2,4-diamine 95-80-7
1,2,3-Trichlorobenzene 87-61-6
1,2,4-Trichlorobenzene 120-82-1
2,4,6-Trichlorophenol 88-06-2
2,4,5-Trichlorophenol 95-95-4
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T) 93-76-5
2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP) 93-72-1
Warfarin 81-81-2
8 Chemical Abstract Services Registry Number.
Table 1 presents average percent recovery and percent RSD data for these
analytes, as well as the retention volumes of each analyte on a single GPC
system. Retention volumes vary from column to column. Figure 1 provides
additional information on retention volumes for certain classes of compounds.
The data for the semivolatiles were determined by GC/MS, whereas, the pesticide
data were determined by GC/ECD or GC/FPD. Compounds not amenable to GC were
determined by HPLC. Other analytes may also be appropriate for this cleanup
technique, however, recovery through the GPC should be >70%.
1.4 Normally, this method is most efficient for removing high boiling
materials that condense in the injection port area of a gas chromatograph (GC)
or the front of the GC column. This residue will ultimately reduce the
chromatographic separation efficiency or column capacity because of adsorption
of the target analytes on the active sites. Pentachlorophenol is especially
susceptible to this problem. GPC, operating on the principal of size exclusion,
will not usually remove interference peaks that appear in the chromatogram since
the molecular size of these compounds is relative similar to the target analytes.
Separation cleanup techniques, based on other molecular characteristics (i.e.,
polarity), must be used to eliminate this type of interference.
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required amount of preswelled
absorbent, and is flushed with solvent for an extended period. The column is
calibrated and then loaded with the sample extract to be cleaned up. Elution is
effected with a suitable solvent(s) and the product is then concentrated.
3.0 INTERFERENCES
3.1 A reagent blank should be analyzed for the compound of interest prior
to the use of this method. The level of interferences must be below the
estimated quantitation limits (EQLs) of the analytes of interest before this
method is performed on actual samples.
3640A - 5 Revision 1
September 1994
-------
3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS
4.1 Gel-permeation chromatography system - GPC Autoprep Model 1002 A
or B, or equivalent, Analytical Biochemical Laboratories, Inc. Systems that
perform very satisfactorily have also been assembled from the following
components - an HPLC pump, an auto sampler or a valving system with sample loops,
and a fraction collector. All systems, whether automated or manual, must meet
the calibration requirements of Sec. 7.2.2.
4.1.1 Chromatographic column - 700 mm x 25 mm ID glass column. Flow
is upward. (Optional) To simplify switching from the UV detector during
calibration to the GPC collection device during extract cleanup, attach a
double 3-way valve (Rheodyne Type 50 Teflon Rotary Valve #10-262 or
equivalent) so that the column exit flow can be shunted either to the UV
flow-through cell or to the GPC collection device.
4.1.2 Guard column - (Optional) 5 cm, with appropriate fittings to
connect to the inlet side of the analytical column (Supelco 5-8319 or
equivalent).
4.1.3 Bio Beads (S-X3) - 200-400 mesh, 70 g (Bio-Rad Laboratories,
Richmond, CA, Catalog 152-2750 or equivalent). An additional5 g of Bio
Beads are required if the optional guard column is employed. The quality
of Bio Beads may vary from lot to lot because of excessive fines in some
lots. The UV chromatogram of the Calibration solution should be very
similar to that in Figure 2, and the backpressure should be within 6-
10 psi. Also, the gel swell ratio in methylene chloride should be in the
range of 4.4 - 4.8 mL/g. In addition to fines having a detrimental effect
on chromatography, they can also pass through the column screens and
damage the valve.
4.1.4 Ultraviolet detector - Fixed wavelength (254 nm) with a semi-
prep flow-through cell.
4.1.5 Strip chart recorder, recording integrator or laboratory data
system.
4.1.6 Syringe - 10 mL with Luerlok fitting.
4.1.7 Syringe filter assembly, disposable - Bio-Rad "Prep Disc"
sample filter assembly #343-0005, 25 mm, and 5 micron filter discs or
equivalent. Check each batch for contaminants. Rinse each filter
assembly (prior to use) with methylene chloride if necessary.
4.2 Analytical balance - 0.0001 g.
4.3 Volumetric flasks, Class A - 10 mL to 1000 mL
4.4 Graduated cylinders
3640A - 6 Revision 1
September 1994
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5.0 REAGENTS .. . .
5.1 Methylene chloride, CH2C12. Pesticide quality or equivalent.
5.1.1 Some brands of methylene chloride may contain unacceptably
high levels of acid (HC1). Check the pH by shaking equal portions of
methylene chloride and water, then check the pH of the water layer.
5.1.1,1 If the pH of the water layer is < 5, filter the
entire supply of solvent through a 2 in. x 15 in. glass column
containing activated basic alumina. This column should be
sufficient for processing approximately 20-30 liters of solvent.
Alternatively, find a different supply of methylene chloride.
5.2 Cyclohexane, C6H12. Pesticide quality or equivalent.
5.3 n-Butyl chloride, CH3CH2CH2CH2C1. .Pesticide quality or equivalent.
5.4 GPC Calibration Solution. Prepare a calibration solution in
methylene chloride containing the following analytes (in elution order):
Compound mq/L
corn oil 25,000
bis(2-ethylhexyl) phthalate 1,000
methoxychlor 200
perylene 20
sulfur 80
NOTE: Sulfur is not very soluble in methylene chloride, however, it is
soluble in warm corn oil. Therefore, one approach is to weigh out
the corn oil, warm it and transfer the weighed amount of sulfur into
the warm corn oil. Mix it and then transfer into a volumetric flask
with methylene chloride, along with the other calibration compounds.
Store the calibration solution in an amber glass bottle with a Teflon lined
screw-cap at 4°C, and protect from light. (Refrigeration may cause the corn oil
to precipitate. Before use, allow the calibration solution to stand at room
temperature until the corn oil dissolves.) Replace the calibration standard
solution every 6 months, or more frequently if necessary.
5.5 Corn Oil Spike for Gravimetric Screen. Prepare a solution of corn
oil in methylene chloride (5 g/100 ml).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
3640A - 7 Revision 1
September 1994
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7.0 PROCEDURE
7.1 It is very important to have consistent laboratory temperatures
during an entire GPC run, which could be 24 hours or more. If temperatures are
not consistent, retention times will shift, and the dump and collect times
determined by the calibration standard will no longer be appropriate. The ideal
laboratory temperature to prevent outgassing of the methylene chloride is 72°F.
7.2 GPC Setup and Calibration
7.2.1 Column Preparation
7.2.1.1 Weigh out 70 g of Bio Beads (SX-3). Transfer them
to a quart bottle with a Teflon lined cap or a 500 ml separatory
funnel with a large bore stopcock, and add approximately 300 ml of
methylene chloride. Swirl the container to ensure the wetting of
all beads. Allow the beads to swell for a minimum of 2 hours.
Maintain enough solvent to sufficiently cover the beads at all
times. If a guard column is to be used, repeat the above with 5 g
of Bio Beads in a 125 ml bottle or a beaker, using 25 ml of
methylene chloride.
7.2.1.2 Turn the column upside down from its normal
position, and remove the inlet bed support plunger (the inlet
plunger is longer than the outlet plunger). Position and tighten
the outlet bed support plunger as near the end as possible, but no
closer than 5 cm (measured from the gel packing to the collar).
7.2.1.3 Raise the end of the outlet tube to keep the
solvent in the GPC column, or close the column outlet stopcock if
one is attached. Place a small amount of solvent in the column to
minimize the formation of air bubbles at the base of poured column
packing.
7.2.1.4 Swirl the bead/solvent slurry to get a homogeneous
mixture and, if the wetting was done in a quart bottle, quickly
transfer it to a 500 ml separatory funnel with a large bore
stopcock. Drain the excess methylene chloride directly into the
waste beaker, and then start draining the slurry into the column by
placing the separatory funnel tip against the column wall. This
will help to minimize bubble formation. Swirl occasionally to keep
the slurry homogeneous. Drain enough to fill the column. Place the
tubing from the column outlet into a waste beaker below the column,
open the stopcock (if attached) and allow the excess solvent to
drain. Raise the tube to stop the flow and close the stopcock when
the top of the gel begins to look dry. Add additional methylene
chloride to just rewet the gel.
7.2.1.5 Wipe any remaining beads and solvent from the
inner walls of the top of the column with a laboratory tissue.
Loosen the seal slightly on the other plunger assembly (long
plunger) and insert it into the column. Make the seal just tight
3640A - 8 Revision 1
September 1994
-------
enough so that any beads on the glass surface will be pushed
forward, but loose enough so that the plunger can be pushed forward.
CAUTION: Do not tighten the seal if beads are between the
seal and the glass surface because this can
damage the seal and cause leakage.
7.2.1.6 Compress the column as much as possible without
applying excessive force. Loosen the seal and gradually pull out
the plunger. Rinse and wipe off the plunger. Slurry any remaining
beads and transfer them into the column. Repeat Sec. 7.2.1.5 and
reinsert the plunger. If the plunger cannot be inserted and pushed
in without allowing beads to escape around the seal, continue
compression of the beads without tightening the seal, and loosen and
remove the plunger as described. Repeat this procedure until the
plunger is successfully inserted.
7.2.1.7 Push the plunger until it meets the gel, then
compress the column bed about four centimeters.
7.2.1.8 Pack the optional 5 cm column with approximately
5 g of preswelled beads (different guard columns may require
different amounts). Connect the guard column to the inlet of the
analytical column.
7.2.1.9 Connect the column inlet to the solvent reservoir
(reservoir should be placed higher than the top of the column) and
place the column outlet tube in a waste container. Placing a
restrictor in the outlet tube will force air out of the column more
quickly. A restrictor can be made from a piece of capillary
stainless steel tubing of 1/16" OD x 10/1000" ID x 2". Pump
methylene chloride through the column at a rate of 5 mL/min for one
hour.
7.2.1.10 After washing the column for at least one hour,
connect the column outlet tube, without the restrictor, to the inlet
side of the UV detector. Connect the system outlet to the outlet
side of the UV detector. A restrictor (same size as in Sec.
7.2.1.9) in the outlet tube from the UV detector will prevent bubble
formation which causes a noisy UV baseline. The restrictor will not
effect flow rate. After pumping methylene chloride through the
column for an additional 1-2 hours, adjust the inlet bed support
plunger until approximately 6-10 psi backpressure is achieved. Push
the plunger in to increase pressure or slowly pull outward to reduce
pressure.
7.2.1.11 When the GPC column is not to be used for several
days, connect the column outlet line to the column inlet to prevent
column drying and/or channeling. If channeling occurs, the gel must
be removed from the column, reswelled, and repoured as described
above. If drying occurs, methylene chloride should be pumped
through the column until the observed column pressure is constant
and the column appears wet. Always recalibrate after column drying
has occurred to verify retention volumes have not changed.
3640A - 9 Revision 1
September 1994
-------
7.2.2 Calibration of the GPC Column
7.2.2.1 Using a 10 ml syringe, load sample loop #1 with
calibration solution (Sec. 5.6). With the ABC automated system, the
5 ml sample loop requires a minimum of 8 ml of the calibration
solution. Use a firm, continuous pressure to push the sample onto
the loop. Switch the valve so that GPC flow is through the UV flow-
through cell.
7.2.2.2 Inject the calibration solution and obtain a UV
trace showing a discrete peak for each component. Adjust the
detector and/or recorder sensitivity to produce a UV trace similar
to Figure 2 that meets the following requirements. Differences
between manufacturers' cell volumes and detector sensitivities may
require a dilution of the calibration solution to achieve similar
results. An analytical flow-through detector cell will require a
much less concentrated solution than the semi-prep cell, and
therefore the analytical cell is not acceptable for use.
7.2.2.3 Following are criteria for evaluating the UV
chromatogram for column condition.
7.2.2.3.1 Peaks must be observed, and should be
symmetrical, for all compounds in the calibration solution.
7.2.2.3.2 Corn oil and phthalate peaks must exhibit
>85% resolution.
7.2.2.3.3 Phthalate and methoxychlor peaks must
exhibit >85% resolution.
7.2.2.3.4 Methoxychlor and perylene peaks must exhibit
>85% resolution.
7.2.2.3.5 Perylene and sulfur peaks must not be
saturated and must exhibit >90% baseline resolution.
7.2.2.3.6 Nitroaromatic compounds are particularly
prone to adsorption. For example, 4-nitrophenol recoveries
may be low due to a portion of the analyte being discarded
after the end of the collection time. Columns should be
tested with the semivolatiles matrix spiking solution. GPC
elution should continue until after perylene has eluted, or
long enough to recover at least 85% of the analytes, whichever
time is longer.
7.2.2.4 Calibration for Semivolatiles - Using the
information from the UV trace, establish appropriate collect and
dump time periods to ensure collection of all target analytes.
Initiate column eluate collection just before elution of
bis(2-ethylhexyl) phthalate and after the elution of the corn oil.
Stop eluate collection shortly after the elution of perylene.
Collection should be stopped before sulfur elutes. Use a "wash"
time of 10 minutes after the elution of sulfur. Each laboratory is
3640A - 10 Revision 1
September 1994
-------
required to establish its specific time sequences. See Figure 2 for
general guidance on retention time. Figure 1 illustrates retention
volumes for different classes of compounds.
7.2.2.5 Calibration for Organochlorine Pesticides/PCBs -
Determine the elution times for the phthalate, methoxychlor,
perylene, and sulfur. Choose a dump time which removes >85% of the
phthalate, but collects >95% of the methoxychlor. Stop collection
after the elution of perylene, but before sulfur elutes.
7.2.2.6 Verify the flow rate by collecting column eluate
for 10 minutes in a graduated cylinder and measure the volume, which
should be 45-55 ml (4.5-5.5 mL/min). If the flow rate is outside of
this range, corrective action must be taken, as described above.
Once the flow rate is within the range of 4.5-5.5 mL/min, record the
column pressure (should be 6-10 psi) and room temperature. Changes
in pressure, solvent flow rate, and temperature conditions can
affect analyte retention times, and must be monitored. If the flow
rate and/or column pressure do not fall within the above ranges, a
new column should be prepared. A UV trace that does not meet the
criteria in Sec. 7.2.2.3 would also indicate that a new column
should be prepared. It may be necessary to obtain a new lot of Bio
Beads if the column fails all the criteria.
7.2.2.7 Reinject the calibration solution after
appropriate collect and dump cycles have been set, and the solvent
flow and column pressure have been established.
7.2.2.7.1 Measure and record the volume of collected
GPC eluate in a graduated cylinder. The volume of GPC eluate
collected for each sample extract processed may be used to
indicate problems with the system during sample processing.
7.2.2.7.2 The retention times for bis(2-ethylhexyl)
phthalate and perylene must not vary more than +5% between
calibrations. If the retention time shift is >5%, take
corrective action. Excessive retention time shifts are caused
by:
7.2.2.7.2.1 Poor 1 aboratory temperature control or
system leaks.
7.2.2.7.2.2 An unstabilized column that requires
pumping methylene chloride through it for several more
hours or overnight.
7.2.2.7.2.3 Excessive laboratory temperatures,
causing outgassing of the methylene chloride.
7.2.2.8 Analyze a GPC blank by loading 5 ml of methylene
chloride into the GPC. Concentrate the methylene chloride that
passes through the system during the collect cycle using a Kuderna-
Danish (KD) evaporator. Analyze the concentrate by whatever
detectors will be used for the analysis of future samples. Exchange
3640A - 11 Revision 1
September 1994
-------
the solvent, if necessary. If the blank exceeds the estimated
quantitation limit of the analytes, pump additional methylene
chloride through the system for 1-2 hours. Analyze another GPC
blank to ensure the system is sufficiently clean. Repeat the
methylene chloride pumping, if necessary.
7.3 Extract Preparation
7.3.1 Adjust the extract volume to 10.0 ml. The solvent extract
must be primarily methylene chloride. All other solvents, e.g.
1:1 methylene chloride/acetone, must be concentrated to 1 ml (or as low as
possible if a precipitate forms) and diluted to 10.0 ml with methylene
chloride. Thoroughly mix the extract before proceeding.
7.3.2 Filter the extract through a 5 micron filter disc by attaching
a syringe filter assembly containing the filter disc to a 10 mL syringe.
Draw the sample extract through the filter assembly and into the 10 ml
syringe. Disconnect the filter assembly before transferring the sample
extract into a small glass container, e.g. a 15 ml culture tube with a
Teflon lined screw cap. Alternatively, draw the extract into the syringe
without the filter assembly. Attach the filter assembly and force the
extract through the filter and into the glass container. The latter is
the preferred technique for viscous extracts or extracts with a lot of
solids. Particulate larger than 5 microns may scratch the valve, which
may result in a system leak and cross-contamination of sample extracts in
the sample loops. Repair of the damaged valve is quite expensive.
NOTE: Viscosity of a sample extract should not exceed the viscosity
of 1:1 water/glycerol. Dilute samples that exceed this
viscosity.
7.4 Screening the Extract
7.4.1 Screen the extract to determine the weight of dissolved
residue by evaporating a 100 nl aliquot to dryness and weighing the
residue. The weight of dissolved residue loaded on the GPC column cannot
exceed 0.500 g. Residues exceeding 0.500 g will very likely result in
incomplete extract cleanup and contamination of the GPC switching valve
(which results in cross-contamination of sample extracts).
7.4.1.1 Transfer 100 juL of the filtered extract from
Sec. 7.3.2 to a tared aluminum weighing dish.
7.4.1.2 A suggested evaporation technique is to use a heat
lamp. Set up a 250 watt heat lamp in a hood so that it is
8 + 0.5 cm from a surface covered with a clean sheet of aluminum
foil. Surface temperature should be 80-100°C (check temperature by
placing a thermometer on the foil and under the lamp). Place the
weighing dish under the lamp using tongs. Allow it to stay under
the lamp for 1 min. Transfer the weighing dish to an analytical
balance or a micro balance and weigh to the nearest 0.1 mg. If the
residue weight is less than 10 mg/100 juL, then further weighings are
not necessary. If the residue weight is greater than 10 mg/100 /zL,
3640A - 12 Revision 1
September 1994
-------
then determine if constant weight has been achieved by placing the
weighing dish and residue back under the heat lamp for 2 or more
additional 0.5 min. intervals. Reweigh after each interval.
Constant weight is achieved when three weights agree within ±10%.
7.4.1.3 Repeat the above residue analysis on a blank and
a spike. Add 100 juL of the same methylene chloride used for the
sample extraction to a weighing dish and determine residue as above.
Add 100 juL of a corn oil spike (5 g/100 ml) to another weighing dish
and repeat the residue determination.
7.4.2 A residue weight of 10 mg/100 pi of extract represents 500 mg
in 5 ml of extract. Any sample extracts that exceed the 10 mg/100 p.1
residue weight must be diluted so that the 5 ml loaded on the GPC column
does not exceed 0.500 g. When making the dilution, keep in mind that a
minimum volume of 8 ml is required when loading the ABC GPC unit.
Following is a calculation that may be used to determine what dilution is
necessary if the residue exceeds 10 mg.
Y ml taken = 10 ml final x 10 mq maximum
for dilution volume X mg of residue
Example:
Y ml taken = 10 ml final x 10 mq maximum
for dilution volume 15 mg of residue
Y ml taken for dilution = 6.7 ml
Therefore, taking 6.7 ml of sample extract from Sec. 7.3.2, and
diluting to 10 ml with methylene chloride, will result in 5 ml of diluted
extract loaded on the GPC column that contains 0.500 g of residue.
NOTE: This dilution factor must be included in the final calculation
of analyte concentrations. In the above example, the dilution
factor is 1.5.
7.5 GPC Cleanup
7.5.1 Calibrate the GPC at least once per week following the
procedure outlined in Sees. 7.2.2 through 7.2.2.6. Ensure that UV trace
requirements, flow rate and column pressure criteria are acceptable.
Also, the retention time shift must be <5% when compared to retention
times in the last calibration UV trace.
7.5.1.1 If these criteria are not met, try cleaning the
column by loading one or more 5 ml portions of butyl chloride and
running it through the column. Butyl chloride or 9:1 (v/v)
methylene chloride/methanol removes the discoloration and
particulate that may have precipitated out of the methylene chloride
extracts. Backflushing (reverse flow) with methylene chloride to
dislodge particulates may restore lost resolution. If a guard
column is being used, replace it with a new one. This may correct
3640A - 13 Revision 1
September 1994
-------
the problem. If column maintenance does not restore acceptable
performance, the column must be repacked with new Bio Beads and
calibrated.
7.5.2 Draw a minimum of 8 ml of extract (diluted, if necessary, and
filtered) into a 10 ml syringe.
7.5.3 Attach the syringe to the turn lock on the injection port.
Use firm, continuous pressure to push the sample onto the 5-mL sample
loop. If the sample is difficult to load, some part of the system may be
blocked. Take appropriate corrective action. If the back pressure is
normal (6-10 psi), the blockage is probably in the valve. Blockage may be
flushed out of the valve by reversing the inlet and outlet tubes and
pumping solvent through the tubes. (This should be done before sample
loading.)
NOTE: Approximately 2 ml of the extract remains in the lines between
the injection port and the sample loop; excess sample also
passes through the sample loop to waste.
7.5.4 After loading a,loop, and before removing the syringe from the
injection port, index the GPC to the next loop. This will prevent loss of
sample caused by unequal pressure in the loops.
7.5.5 After loading each sample loop, wash the loading port with
methylene chloride in a PTFE wash bottle to minimize cross-contamination.
Inject approximately 10 ml of methylene chloride to rinse the common
tubes.
7.5.6 After loading all the sample loops, index the GPC to the 00
position, switch to the "RUN" mode and start the automated sequence.
Process each sample using the collect and dump cycle times established in
Sec. 7.2.2.
7.5.7 Collect each sample in a 250 ml Erlenmeyer flask, covered with
aluminum foil to reduce solvent evaporation, or directly into a Kuderna-
Danish evaporator. Monitor sample volumes collected. Changes in sample
volumes collected may indicate one or more of the following problems:
7.5.7.1 Change in solvent flow rate, caused by channeling
in the column or changes in column pressure.
7.5.7.2 Increase in column operating pressure due to the
absorption of particles or gel fines onto either the guard column or
the analytical column gel, if a guard column is not used.
7.5.7.3 Leaks in the system or significant variances in
room temperature.
7.6 Concentrate the extract by the standard K-D technique (see any of the
extraction methods, Sec. 4.2.1 of this chapter). See the determinative methods
(Chapter Four, Sec. 4.3) for the final volume.
3640A - 14 Revision 1
September 1994
-------
7.7 It should be remembered that only half of the sample extract is
processed by the GPC (5 ml of the 10 ml extract is loaded onto the GPC column),
and thus, a dilution factor of 2 (or 2 multiplied by any dilution factor in Sec.
7.4.2) must be used for quantitation of the sample in the determinative method.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 3600 for specific quality control
procedures.
8.2 The analyst should demonstrate that the compound(s) of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Refer to Table 1 for single laboratory performance data.
10.0 REFERENCES
1. Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges"; U.S. EPA
Municipal Environmental Research Laboratory: Cincinnati, Ohio 45268.
2. Czuczwa, J.; Alford-Stevens, A. "Optimized Gel Permeation Chromatographic
Cleanup for Soil, Sediment, Waste and Waste Oil Sample Extracts for GC/MS
Determination of Semivolatile Organic Pollutants, JAOAC, submitted April
1989.
3. Marsden, P.O.; Taylor, V.; Kennedy, M.R. "Evaluation of Method 3640 Gel
Permeation Cleanup"; Contract No. 68-03-3375, U.S. Environmental
Protection Agency, Cincinnati, Ohio, pp. 100, 1987.
3640A - 15 Revision 1
September 1994
-------
TABLE 1
GPC RECOVERY AND RETENTION VOLUMES FOR RCRA
APPENDIX VIII ANALYTES
Compound
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetyl ami nof 1 uorene
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Benomyl
Benzenethiol
Benzidine
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzo(k)fluoranthene
Benzoic acid
Benzotrichloride
Benzyl alcohol
Benzyl chloride
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2 -sec-butyl -4, 6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chloro-3-methyl phenol
4-Chloroaniline
Chi orobenzi late
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chloronaphthalene
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
% Rec1
97
72
94
97
99
96
93
89
131
92
95
100
93
93
90
91
66
93
95
99
84
94
93
102
93
104
103
99
131
97
93
87
88
92
89
76
83
89
90
86
87
98
80
102
91
% RSD2
2
10
7
2
9
7
4
2
8
11
5
3
5
3
6
4
7
7
17
4
13
9
4
7
1
3
18
5
8
2
2
1
3
5
1
2
2
1
1
3
2
2
5
1
1
Ret. Vol.3 (ml
196-235
196-235
176-215
156-195
196-215
176-215
196-235
196-235
146-195
196-235
176-215
196-235
196-235
196-235
196-235
196-235
176-195
176-215
176-215
176-215
196-215
196-215
196-215
216-255
176-215
136-175
176-195
196-255
146-195
196-235
196-215
196-255
196-235
176-235
156-195
156-215
156-195
196-235
196-215
196-215
196-215
176-215
176-215
196-235
196-215
3640A - 16
Revision 1
September 1994
-------
TABLE 1 (continued)
Compound
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial! ate
Dibenzo(a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzothiophene
I,2-Dibromo-3-chloropropane
1,2-Dibromoethane
trans -l,4-Dich1oro-2-butene
cis-l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotoluene
l,3-Dichloro-2-propanol
Dieldrin
Diethyl phthalate
Dimethoate
3,3'-Dimethoxybenzidine°
Dimethyl phthalate
p-Dimethylaminoazobenzene
7,12-Dimethyl-benz(a)anthracene
2,4-Dimethylphenol
3,3' -Dimethyl benzi dine
4,6-Dinitro-o-cresol
1,3-D.i nitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2-Di phenyl hydrazi ne
Disulfoton
Endosulfan sulfate
Endosulfan I
% Rec1
70
88
114
94
94
96
104
97
94
99
117
92
94
94
83
121
107
106
81
81
81
98
86
80
87
70
73
100
103
79
15
100
96
77
93
93
100
99
118
93
101
95
67
92
81
94
99
%RSD2
3
2
10
4
2
6
3
6
10
8
9
5
1
3
2
8
6
6
1
1
1
3
3
NA
2
9
13
5
3
15
11
1
1
1
2
2
1
2
7
4
2
6
12
1
15
2
8
Ret. Vol.3 (ml
196-215
196-215
146-185
196-235
196-235
176-215
136-175
156-175
216-235
216-235
176-195
196-235
176-235
196-235
176-215
196-215
176-195
176-215
196-235
196-235
196-235
176-215
196-215
76-215
96-215
196-235
176-215
196-215
136-195
146-185
156-195
156-195
176-215
176-215
176-215
156-215
156-195
156-195
176-195
156-195
156-175
176-235
196-215
176-215
146-165
176-195
176-215
3640A - 17 Revision 1
September 1994
-------
TABLE 1 (continued)
Compound
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methylcholanthrene
2-Methyl naphthalene
Methyl parathion,
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
% Rec1
92
95
97
94
62
126
101
99
95
94
85
91
108
86
89
85
91
79
98
68
90 "
88
102
111
93
94
74
67
84
96
95
73
94
96
77
96
96
103
86
95
77
89
104
94
86
99
85
%RSD2
6
6
1
4
7
7
1
NA
1
1
2
11
2
2
3
1
2
13
5
7
4
16
NA
9
12
6
12
6
13
1
7
7
8
6
2
8
2
8
2
3
3
4
3
2
13
2
4
Ret. Vol.3 (ml
196-215
196-215
176-215
176-215
176-235
176-195
120-145
126-165
176-235
196-235
195-215
156-195
196-235
176-215
176-215
196-235
196-235
216-255
196-235
156-195
176-215
156-195
196-235
156-195
126-165
156-195
176-195
196-215
146-185
176-215
196-215
176-215
196-235
196-235
176-195
176-215
176-215
176-215
176-195
176-195
196-215
156-175
146-185
156-175
156-195
156-195
156-175
3640A - 18
Revision 1
September 1994
-------
TABLE 1 (continued)
Compound
N-Nitrosomethyl ethyl ami ne
N-Nitrosomorpholine
N-NHrosopiperidine
N-Nitrosopyrolidine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1,2-Phenylenediamine
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
Streptozotocin"
1,2,4, 5-Tetrachl orobenzene
2,3,5,6-Tetrachloro-nitrobenzene
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
Thiourea, l-(o-chlorophenyl)
Toluene- 2, 4-di ami ne
1, 2, 3-Trichl orobenzene
1, 2, 4-Trichl orobenzene
2, 4, 5-Trichl orophenol
2, 4, 6-Trichl orophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid
Warfarin
% Rec1
83
86
84
92
83
109
95
74
91
102
100
94
83
91
74
99
105
98
70
93
6
96
85
95
96
89
74
92
87
75
69
87
89
77
95
71
67
94
%RSD2
7
4
4
1
4
14
2
1
8
1
3
2
2
1
NA
14
15
2
6
1
48
2
9
1
7
14
3
3
8
11
7
1
1
1
1
23
NA
2
Ret. Vol.3 (ml
156-175
156-195
156-195
156-175
120-156
146-170
196-235
196-235
156-195
196-215
156-195
196-235
156-195
196-215
116-135
156-215
156-195
215-235
196-215
176-215
225-245
196-235
176-215
196-215
196-215
116-135
146-185
176-235
176-235
166-185
176-215
196-235
196-235
216-235
216-235
156-235
216-215
166-185
NA = Not applicable, recovery presented as the average of two determinations.
8 Not an appropriate analyte for this method.
1 The percent recovery is based on an average of three recovery values.
2 The % relative standard deviation is determined from three recovery values.
3 These Retention Volumes are for guidance only as they will differ from column to
column and from system to system.
3640A - 19
Revision 1
September 1994
-------
Figure 1
6PC RETENTION VOLUME OF CLASSES OF ANALYTES
PHTHAIATB -«-
OHOANOPHOSPHATE
PESTICIDES
CORN OIL-*
PAH'«
CHLOR08ENZENES
NITR03AMINE3, NITROAROMATICS
AROMATIC AMINES
NITROPH6NOL3
CHLOROPHENOLS
ORQANOCHUORINE
PESTICIDES/PCS'*
HERBICIDES (6150)
—POP
C-Collect
10
20
30 40
TIME (minutes)
50
60
70
3640A - 20
Revision 1
September 1994
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Figure 2
UV CHROMATOGRAM OF THE CALIBRATION SOLUTION
Injection
5 mis
on column
— 0 minutes
Corn oil
25 rag/nL
Bis(2-ethyIhesy 1)" phth*iate
1.0 mg/raL
Methoxychlor
0.2 mg/mL
Perylene
0.02 mg/mL .
Sulfur
0.08 rng/oL '—
15 minuces
. . ._..!.."' 30 minutes
45 minutes
700 mm X25 no col
70 g Bio-Beads SX
Bed length = 490
CH2C12 at 5.0 uL
254 ma
"...'...'.—I..'. "1_ "ll'.l_"J..'....."— 60 minutes
"
3640A - 21
Revision 1
September 1994
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METHOD 3640A
GEL-PERMEATION CLEANUP
7.1 Ensure ambient temp, consistent
throughout GPC run.
7.2 QPC Setup and Calibration
I
7.2.1 Column Preparation
7.2.1.1 Place Bio Beads and MeCI
in a container. Swirl and
allow beads to swell.
I
7.2.1.2 Remove column inlet bed
support plunger. Position and tighten
outlet bed support plunger to column end.
I
7.2.1.3 Ensure GPC column outlet
contains solvent. Place small amount
solvent in column to minimize
bubble formation.
I
7.2.1.4 Transfer bead mixture into
sep. funnel. Drain excess solvent;
drain beads into' column. Keep
beads wet throughout.
7.2.1.5 Loosen seal on opposite
plunger assembly, insert into column.
7.2.1.6 Compress column. Slurry
remaining beads and repeat Section
7.2.1.5 and column compression.
7.2.1.7 Compress column bed
approximately four cm.
I
7.2.1.8 Pack option 5 cm. guard
column w/ roughly 5 gm.
pres welled beads.
7.2.1.9 Connect column inlet to
solvent reservoir. Pump MeCI at
5 ml/min. for 1 hr.
7.2.1.10 Connect column outlet to
UV-Vis detector. Place restrictor
at detector outlet. Run MeCI for
additional!-2hrs. Compress
column bed to provide 6-10 psi
backpressure.
7.2.1.11 Connect outlet line to column
inlet when column not in use. Repack
column when channeling is observed.
Assure consistent backpressure when
beads are rewetted after drying.
3640A - 22
Revision 1
September 1994
-------
METHOD 3640A
continued
7.2.2 Calibration of the GPC column
7.2.2.1 Load sample loop with
calibration solution.
1
7.2.2.2 Inject calibration soln.; adjust
recorder or detector sensitivity
to produce similar UV trace as Fig. 2.
7.2.2.3 Evaluation criteria for
UV chromatogram.
I
7.2.2.4 Calibration for Semivolatiles
Use information from UV trace to
obtain collect and dump times.
Initiate collection before bis(2-ethylhexyl)
phthalate, stop after perylene. Stop run
before sulfur elutes.
7.2.2.5 Calibration for Organochlorine
Pesticides/PCBs
Choose dump time which removes
> 85% phthalate, but collects at
times > 95% methoxychlor. Stop
collection between perylene and
sulfur elution.
7.2.2.6 Verify column flow rate and
backpressure. Correct
inconsistencies when criteria
are not met.
7.2.2.7 Reinject calibration soln. when
collect and dump cycles are set,
and column criteria are met.
7.2.2.7.1 Measure and record
volume of GPC eluate.
7.2.2.7.2 Correct for retention time
shifts of > +/- 5% for
bis(2-ethylhexyl) phthalate
and perylene.
7.2.2.8 Inject and analyze GPC blank
for column cleanliness. Pump
through MeCI as column wash.
3640A - 23
Revision 1
September 1994
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METHOD 3640A
continued
7.3 Extract Preparation
7.3.1 Adjust extract volume to 10 mL.
Primary solvent should be MeCI.
7.3.2 Filter extract through 5 micron filter
disc/syringe assembly into small
glass container.
7.4 Screening the Extract
I
7.4. 1 Screen extract by determining
residue wt. of 100 uL aliquot.
7.4.1.1 Transfer 100 uL of filtered
extract from Section 7.3.2 to tared
aluminum weighing dish.
7.4.1 .2 Evaporate extract solvent under
heating lamp. Weigh residue to nearest
0.1 mg.
7.4.1 .3 Repeat residue analysis of Section
7.4.1.2 w/blank and spike sample.
7.4.2 Use dilution example to determine
necessary dilution when residue
wts. > 10mg.
7.5 GPC Cleanup
7.5.1 Calibrate GPC weekly. Assure
column criteria, UV trace, retention
time shift criteria are met.
I
7.5.1.1 Clean column w/butyl chloride
loadings, or replacement of
guard column.
I
7.5.2 Draw 8 mL extract into syringe.
7.5.3 Load sample into injection loop.
I
7.5.4 Index GPC to next loop to
prevent sample loss.
7.5.5 Wash sample port w/MeCI
between sample loadings.
I
7.5.6 At end of loadings, index GPC to
00, switch to "RUN" mode, start
automated sequence.
7.5.7 Collect sample into aluminum foil
covered Erlenmeyer flask or into
Kuderna-Danish evaporator.
7.6 Concentrate extract by std.
Kuderna-Danish technique.
7.7 Note dilution factor of GPC method
into final determinations.
3640A - 24
Revision 1
September 1994
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3650A
-------
METHOD 3650A
ACID-BASE PARTITION CLEANUP • ^
1.0 SCOPE'AND APPLICATION
1.1 Method 3650 was formerly Method 3530 in the second edition of this
manual.
1.2 Method 3650 is a liquid-liquid partitioning cleanup method to
separate acid analytes, e.g. organic acids and phenols, from base/neutral
analytes, e.g. amines, aromatic hydrocarbons,^and halogenated organic compounds,
using pH adjustment. It may be used for cleanup of petroleum waste prior to
analysis or further cleanup (e.g., alumina cleanup). The following compounds can
be separated by this method:
Compound Name
CAS No.'
Fraction
Benz(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Chlordane
Chlorinated dibenzodioxins
2-Chlorophenol
Chrysene
Creosote
Crespl(s)
Dichlorobehzene(s)
Dichlorophenoxyacetic acid
2,4-Dimethylphenol
Di nitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrotoluene
Heptachlor
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Hexachl orocycl opentadi ene
Naphthalene
Nitrobenzene
4-Nitrophenol
Pentachlprophenol
Phenol
Phorate
2-Picoline
Pyridine
Tetrachlorobenzene(s)
Tetrachlorophenol(s)
Toxaphene
Trichlorophenol (s)
2,4,5-TP (Silvex)
56-55-3
50-32-8
205-99-2
57-74-9
1
. 95-57-8^
218-01-9
8001-58-9
94-75-7
105-67-9
25154-54-5,
534-52-1
121-14-2
76-44-8
118-74-1
87-68-3
67 -.72-1
77-47-4
* 91-20-3
98-95-3
100-02-7
87-86-5
108-95-2
298-02-2
109-06-8
110-86-1
8001-35-2
93-72-1
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Base-neutral
Base-neutral and Acid
Acid
Base-neutral
Acid
Acid
Base-neutral
Acid
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral '.
Base-neutral
Acid
Acid
Acid
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Base-neutral
Acid
Acid
Chemical Abstract Services Registry Number.
3650A - 1
Revision 1
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2.0 SUMMARY OF METHOD . . . . ,
2.1 The solvent extract from a prior solvent extraction method is shaken
with water that is strongly basic. The acid analytes partition into the aqueous
layer, whereas, the basic and neutral compounds stay in the organic solvent. The
base/neutral fraction is concentrated and is then ready for further cleanup, if
necessary, or analysis. The aqueous layer is acidified and extracted with an
organic solvent. Thi,s extract is concentrated (if necessary) and is then ready
for analysis of the acid analytes.
3.0 INTERFERENCES v
3.1 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
3.2 A method blank must be run for the compounds of interest prior to
use of the method. The interferences must be below the method detection limit.
before this method is applied to actual samples.
4.0 APPARATUS AND MATERIALS
4.1 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom, or equivalent.
NOTE: Fritted glass discs are difficult to clean after highly contaminated
extracts have been passed through,them. Columns without frits are
recommended. Use a small pad of Pyr£x 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. . .,
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube - 10 ml graduated (Kontes K570050-1025 or
equivalent). A ground glass stopper Is used to prevent evaporation of the
extracts. -
4.2.2 Evaporation flask - 500 ml (K-570001-0500 or equivalent).
Attach to concentrator tube with springs, clamps, or equivalent.
4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K569001-0219 or
equivalent). ,
tops.
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 .Vials - Glass, 2 mL capacity with Teflon lined screw-caps or crimp
4.4 Water bath.'- Heated, concentric ring cover, temperature control of
± 2°C. Use this bath in a hood.
3650A - 2 Revision 1
July 1992
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4.5 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 pH indicator paper - pH range including the desired extraction pH.
4.7 Separatory funnel - 125 ml.
4.8 Erlenmeyer flask - 125 ml.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all inorganic reagents shall
conform to the specifications of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are available. Other grades
may be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5.2 Organic-free reagent water - AVI references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
, 5.3 Sodium hydroxide, NaOH, (ION) - Dissolve 40 g of sodium hydroxide
in 100 ml of organic-free reagent water.
5.4 Sulfuric acid, H,S04, (1:1 v/v in water) - Slowly add 50 ml H2SOA to
50 ml of organic-free reagent water.
5.5 Sodium sulfate (granular, anhydrous), Na2SO, - Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.6 Solvents:
5.6.1 MethyTene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.2 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.6.3 Methanol, CH3OH - Pesticide quality or equivalent.
5:6.4 Diethyl Ether, C2H5OC2H5 - Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
i " - . - *
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3650A - 3 . Revision 1
July 1992
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7.0 PROCEDURE
7.L Place 10 ml of the solvent extract from a prior extraction procedure
into a 125 ml separatory funnel.
7'.2 Add 20 ml of methylene chloride to the separatory funnel.
7.3 Slowly add 20 ml of prechilled organic-free reagent water which has
been previously adjusted to a pH of 12-13 with ION sodium hydroxide.
• 7.4 Seal and shake the separatory funnel for at least 2 minutes with
Aperiodic venting to release excess pressure.
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once. The separatory
funnel should be vented into a hood to prevent unnecessary exposure
of the analyst to the organic vapor. ,
7.5 Allow the, organic layer to separate from the aqueous phase for a
minimum of 10 minutes. If the emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques,to complete the phase separation. The optimum technique depends upon
the sample, and may include stirring, filtration of the emulsion through glass
wool, centrifugation, or other physical methods.
7.6 Separate the aqueous phase and transfer it to a 125 ml Erlenmeyer
flask. Repeat the extraction two more times using 20 mL aliquots of dilute
sodium hydroxide (pH 12-13). Combine the aqueous extracts.
7.7 .Water soluble organic acids and phenols will be primarily in the
aqueous phase. Base/neutral analytes will be in the methylene chloride. If the
analytes of interest are only in the aqueous phase, discard the methylene
chloride and proceed to Section 7.8. If the analytes of interest are only in the
methylene chloride, discard the aqueous phase and proceed to Section 7.10.
7.8 Externally cool the 125 ml Erlenmeyer flask with, ice while adjusting
the aqueous phase to a pH of 1-2 with sulfur.ic acid (1:1). Quantitatively
transfer the cool aqueous phase to a clean 125 ml separatory funnel. Add 20 ml
of methylene chloride to the separatory funnel.and shake for at least 2 minutes.
Allow the methylene chloride to separate from the aqueous phase and collect the
methylene chloride in an Erlenmeyer flask.
7.9 Add 20 ml of methylene chloride to the separatory funnel and extract
at pH 1-2 a second time. Perform a third extraction in the same manner combining
the extracts in the Erlenmeyer flask. .
7.10 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10 ml concentrator tube to a 500 ml evaporation flask.
7.11 Dry both acid and base/neutral fractions by passing them through a
drying column containing about 10 cm of anhydrous sodium sulfate. Collect the
dried fractions in K-D concentrators. Rinse the Erlenmeyer flasks which
~\
3650A -'4 ' " Revision 1
July 1992
-------
contained the solvents and the columns with 20 ml of methylene chloride to
complete the quantitative transfer.
7.12 Concentrate both acid and base/neutral fractions as follows: Add
one or two boiling chips to the flask and attach a three ball macro-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 (80-90°C) so
that the concentrator tube is partially immersed in the warm water. Adjust the
vertical position of the apparatus and the water temperature as required to
complete the concentration in 15-20 minutes. At the proper rate of distillation,
the balls of the column will' actively chatter but the chambers will hot flood.
When the apparent volume of liquid reaches 1 ml, remove the K-D apparatus from
the water bath and allow it to cool. Remove the Snyder column and rinse the
flask and its lower joints into the concentrator tube with 1-2 ml of methylene
chloride. Concentrate the extract to the final volume using either the micro-
Snyder column technique (7.12.1) or nitrogen blowdown technique (7.12.2)1
7.12.1 Micro-Snyder Column Technique
7.12.1.1 Add another one or two 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 to the top of the
column. Place the K-D apparatus in a hot water bath (80-90°C) so
that the concentrator tube is partially immersed in the hot water.
Adjust the vertical position .of • the apparatus and the water
temperature as required to complete the concentration in 5-10
minutes. At the proper rate of distillation the balls of the column
will actively chatter but the chambers will not flood. When the
apparent volume of the liquid reaches 0.5 ml, remove the K-D
apparatus and allow it to cool. Remove the Snyder column and rinse
the flask and its lower joints into the concentrator tube with Oi2
ml of methylene chloride. Adjust the final volume to 1 ml with
methylene chloride.
7.12.2 Nitrogen Blowdown Technique
7.12.2.1 Place the concentrator tube in a warm water bath
(35°C) and evaporate the solvent volume.to 1.0-2.0 ml using a gentle
stream of clean, dry nitrogen (filtered through a column of
activated carbon).
CAUTION; Do not use plasticized tubing between the carbon
• trap and the sample.
7.12.2.2 The internal wall of the concentrator tube must be
.rinseld down several times with the appropriate solvent during the
operation. During evaporation, the tube solvent level must be
positioned to avoid condensation water. Under normal procedures,
the extract must not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.13 The acid fraction is now ready for analysis. If the base/neutral
3650A - 5 Revision 1
..'••- July 1992
-------
fraction requires further cleanup by the alumina column cleanup for petroleum
waste (Method 3611), the solvent may have to be changed to hexane. If a solvent
exchange is required, momentarily remove the Snyder column, add approximately 5
ml of the exchange, solvent and a new boiling chip, and reattach the Snyder
column. Concentrate the extract as described in Section 7.12.1.1, raising the
temperature of the water bath, if necessary, to maintain proper distillation.
When the apparent volume again reaches 1 ml, remove the K-D apparatus from the
water bath and allow it to drain and cool for at least 10 minutes. Repeat the
exchange 2 more times. If no further cleanup of the base/neutral extract is
required, it is also ready for analysis.
j \ ' • '
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for general quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For samples that are cleaned using this method, the associated
quality control samples must be processed through this cleanup method.
9.0 METHOD PERFORMANCE '
9.1 Refer to the determinative methods for performance data.
/ .
10.0 REFERENCES
1. 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.
3650A - 6 Revision 1
July 1992
-------
METHOD 3650A
ACID-BASE PARTITION CLEANUP
START
7 1 Plac« attract
or organic liquid
•aale into
>*paratory funnel
? 2 Add »«lhyl«n«
cnloridi
1 3 Add pr»chill«d
dilute todiun
hydroKid*
7 A' Seat and ihake
•eparalory funnel
7 5 Atlo.
. taparation of
organic layer from
• •
•— "^
7 S Comol«t« pha*«
separation with
mechanica I
techniques
1 6 Tr*n»f«r
qu*ou* ph«f« to
f U»lt. ' r*p«at
Mtraction l»ict:
••tract*
Aquvou*
7 1C Ais*moi« K-0
aopa ra'. ut
7 7 On card organic
phaa*
1 9 Adjvil pH »ith
• ulfunc acid; Irani •
f*r JQU«OU» phaat to
clvan icparatory fun-
n«l. add mathy1«n«
ehl or id*; «hak«.
•llov *phaa« tapara-
Uon collect lolvvni
oha»« in f1a*«
7 9 P'trform 2 mor»
• •t raction»
comb in* aii
• •.tracti
3650A - 7
Revision 1
July 1992
-------
METHOD 3650A
(Continued)
7 11 3 r y exlrac'. s.
coilec', extracts in
X - Q can centra*, or.
-rinse flasl< «*;^h
'.TI e 1 h y '. e n e c h I a r L a e
' 12 Concenlrale y
both fraction s
3650A - 8
Revision 1
July 1992
-------
3660 A
-------
METHOD 3660A
SULFUR CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Elemental sulfur is encountered in many sediment samples (generally
specific to different areas in the country), marine algae, and some industrial
wastes. The solubility of sulfur in various solvents is very similar to the
organochlqrine and organophosphorus pesticides. Therefore, the sulfur
interference follows along with the pesticides through the normal extraction and
cleanup techniques. In general, sulfur will usually elate entirely in Fraction
1 of the Florisil cleanup (Method 3620)..
1.2 Sulfur will be quite evident in gas chromatograms obtained from
electron capture detectors, flame photometric detectors .operated in the sulfur
or phosphorous mode, and Coulson electrolytic conductivity detectors in the
sulfur mode. If the gas chromatograph is operated at the normal' conditions for
pesticide analysis, the sulfur interference can completely mask the region from
the solvent peak through Aldrin.
1.3 Three techniques for the elimination of sulfur are detailed within
this method: (1) the use of copper powder; (2) the use of mercury; and (3) the
use of tetrabutylammonium sulfite. .Tetrabutylammonium sulfite causes the least
amount of degradation of a broad range of pesticides and organic compounds, while
copper and mercury may degrade organophosphorus and some organochlorine
pesticides. .-.,/..'
2.0, SUMMARY OF METHOD
2.1 The sample to undergo cleanup is mixed with either copper, mercury,
or tetrabutylammonium (TBA) sulfite. The mixture is shaken and the extract is
removed from the sulfur cleanup reagent. ,
3.0 INTERFERENCES '" ••
3.1 Removal of sulfur using copper:
3.1.1 The copper must be very reactive. Therefore, all oxides of
copper mus't be removed so that the copper has a shiny, bright appearance.
3.1.2 The sample extract must be vigorously agitated with the
reactive copper for at least one minute.
4.0 APPARATUS AND MATERIALS
4.1 Mechanical shaker or mixer - Vortex Genie or.equivalent.
4.2 Pi pets, disposable - Pasteur type.
3660A - 1 Revision 1
; July 1992
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4.3 Centrifuge tubes, calibrated - 12 ml.
4,4 Glass bottles or vials - 10 mi and 50 ml, with Teflon-lined screw
caps or crimp tops.
4.5 Kuderna-Danish (K-D) apparatus.
4.5.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.5.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.5.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.5.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.5.5 Springs - 1/2 inch (Kontes K-662750 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 Organic-free reagent'water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Nitric acid, HN03, dilute.
5.4 Solvents '
5.4.1 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.4.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.4.3 2-Propanol, CH3CH(OH)CH3 - Pesticide quality or equivalent.
5.5 Copper powder - Remove oxides by treating with dilute nitric acid,
rinse with organic-free reagent water to remove all traces of acid, rinse with
acetone and dry under a stream of nitrogen. (Copper, fine granular Malli.nckrodt
4649 or equivalent).
5.6 Mercury, triple distilled.
5.7 Tetrabutylammoniurn (TBA) sulfite reagent
3660A - 2 Revision 1
July 1992
-------
5.7.1 Tetrabutylammonium hydrogen sulfate, [CH3(CH2)3]4NHS04.
5.7.2 Sodium sulfite, Na2S03. ' .
5.7.3 Prepare reagent by dissolving 3.39 g tetrabutylammonium
hydrogen sulfate in 100 ml organic-free reagent water. To remove
impurities, extract this solution three times with 20 ml portions of
hexane. Discard the hexane extracts, and add 25 g sodium sulfite to the
water solution. Store the resulting solution, which is saturated with
sodium sulfite, in an amber bottle with a Teflon-lined screw cap. This
solution can be stored at room temperature for at least one month.
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 Removal of sulfur using copper
7.1.1 Concentrate the sample to exactly 1.0 mL or other known
volume. Perform concentration using the Kuderna-Danish (K-D) Technique
(Method 3510, Sections 7.10.1 through 7.10.4).
CAUTION: When the volume of solvent is reduced below 1 mL,
semi volatile analytes may be lost.
7.1.2 If the sulfur concentration is such that crystallization
occurs, centrifuge to settle the crystals, and carefully draw off the
sample extract with a disposable pipet leaving the excess sulfur in the K-
D tube. Transfer 1.0 mL of the extract to a calibrated centrifuge tube.
7.1.3 Add approximately 2 g of cleaned copper powder (to the 0.5 mL
mark) to the centrifuge tube. Mix for at least 1-min on the mechanical
shaker.
7.1.4 Separate the extract from the copper by drawing off the
extract with a disposable pipet and transfer to a clean vial. The volume
remaining still represents 1.0 mL of extract.
NOTE: This separation is necessary to prevent further degradation of
the pesticides.
7.2 / Removal of sulfur using mercury . .
NOTE; Mercury is a highly toxic metal. All operations involving mercury
should be performed in a hood. Prior to using mercury, it is
recommended that the analyst become acquainted with proper handling
and cleanup techniques associated with this metal.
7.2.1 Concentrate the. sample extract to exactly 1.0 mL or 'Other
3660A - 3 Revision 1
, July 1992
-------
known volume. Perform concentration using the Kuderna-Danish (K-D)
Technique (Method 3510, Sections 7.10.1 through 7.10.4).
CAUTION; When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.2.2 Pipet 1.0 ml of the extract into a clean concentrator tube or
Teflon-sealed vial.
7.2.3 Add one to three drops of mercury to the vial and seal.
Agitate the contents of the vial for 15-30 sec. Prolonged shaking (2 hr)
may be required. If so, use a mechanical shaker.
7.2.4 Separate the sample from the mercury by drawing off, the
extract with a disposable pipet and transfer to ,a clean vial.
\
7.3 Removal of sulfur using TBA sulfite
7.3.1 Concentrate the sample extract to exactly 1.0 ml or other
known volume. Perform concentration using the Kuderna-Danish (K-D)
Technique (Method 3510, Sections 7.10.1 through 7.10.4).
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
. 7.3.2 Transfer 1.0 ml of the extract to a 50 ml clear glass bottle
or vial with a Teflon-lined screw-cap. Rinse the concentrator tube with
1 ml of hexane, adding the rinsings to the 50 ml bottle:
7.3.3 Add 1.0 ml TBA sulfite reagent and 2 ml 2-propanol, cap the
bottle, and shake for at least 1 min. .If the sample is colorless or if
the initial color is unchanged, and if clear crystals (precipitated sodium
sulfite) are observed, sufficient sodium sulfite is present. If the
precipitated sodium sulfite disappears, add more crystalline sodium
sulfite in approximately 0.100 g portions until a solid residue remains
after repeated shaking.
7.3.4 Add 5 ml organic free reagent water and shake for at least 1
min. Allow the sample to stand for 5-10 min. Transfer the hexane layer
(top) to a concentrator tube and concentrate.the extract to approximately
1.0 ml with the micro K-D Technique (Section 7.3.5) or the Nitrogen
Slowdown Technique (Section 7.3.6). Record the actual volume of the final
extract.
7.3.5 Micro-Snyder Column Technique
7.3:5.1 Add another one or two clean boiling1chips to the
concentrator tube and attach a two ball micro-Snyder column. Prewet
the column by adding about 0.5 ml of hexane to the top of the
column. Place the K-D apparatus in a hot water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete the concentration in 5-10 minutes. At the
proper rate of distillation the balls of the column will actively
3660A - 4 .Revision 1
- ^ , July 1992
-------
chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes. Remove
v the Snyder column and rinse the flask and its lower joints with
about 0.2 ml of solvent and add to the concentrator tube. Adjust
the final volume to approximately 1.0 ml with hexane.
7.3.6 Nitrogen Slowdown Technique
7.3.6.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to 1.0-2.0,ml,
using a gentle stream of clean, dry nitrogen (filtered through a
column of activated carbon). '
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
7.3.6.2 The internal wall of the tube must be rinsed down
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
CAUTION; When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.4 Analyze the cleaned up extracts by gas chromatography (see the
determinative methods, Section 4.3 of this chapter).
8.0 QUALITY CONTROL
• • ' • ' . (
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures. >
8.2 All reagents should be. checked prior to use to verify that
interferences' do not exist. ,
9.0 METHOD PERFORMANCE
9.1 Table 1 indicates the effect of using copper and mercury to remove
sulfur on the recovery of certain pesticides.
10.0 REFERENCES
1. Loy, E.W., private communication.
2. Goerlitz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9 (1971).
3660A - 5 Revision 1
July 1992
-------
3. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, Revision, July 1985.
3660A - 6 Revision 1
July 1992
-------
Table 1.
EFFECT OF MERCURY AND COPPER ON PESTICIDES
Percent Recovery8 using;
Pesticide Mercury Copper
Aroclor 1254
Lindane
Heptachlor
Aldrin
Heptachlor epoxide
DDE
DDT
BHC
Dieldrin
Endrin
Chi orobenzi late
Malathion
Diazinon
Parathion
Ethion.
Trithion
97.10
75.73
39.84
95.52
69.13
92.07
78.78
81.22
79.11
70.83
7.14
0.00 -
0.00
0.00
0.00,
0.00
104.26
94.83
5.39
93.29
96.55
102.91
85.10
98.08
94.90
89.26
0.00
0.00
0.00
0.00
0.00
0.00
a Percent recoveries cited are averages based on duplicate analyses for all
compounds, other than for Aldrin and BHC. For Aldrin, four and three
determinations were averaged to obtain the result for mercury .and copper,
respectively. Recovery of BHC using copper is based on one analysis.
3660A - 7 Revision 1
July 1992
-------
METHOD 3660A
SULFUR CLEANUP
7 l.'l
Concentrate
sample
' extract
7 21
Concentrate
sample
eitract.
7 1 2.
Centrifuge
and draw off
sample
••tract
7 2.2 Pxp.t
••tract into
concentre tor
tube or vial
7 1 2
Transfer
••tract to
centrifuge
tube. '•
7 2. 3 Add
mercury.
agitale
7,4 1
Concentrati
tample
extract.
7.3 2 .
Trantfer
extract to
centrifuge
tub*.
7 3 3 Add
TBA-iulfite
and
2 -propane'!,
agitate.
7 •
1
3660A - 8
Revision 1
July 1992
-------
METHOD 3660A
continued
L
/
7 1 3 Add
copper
powder, mm
724,,
Svpara t«
sample f rom
mercury
71.4-
Separate
K tr»ct from
coppvr
7 3 3
Is
-------
3665
-------
METHOD 3665
SULFURIC AC ID/PERMANGANATE CLEANUP
1.0 SCOPE AND APPLICATION
1.1 This method is suitable for the rigorous cleanup of sample extracts
prior to analysis for polychlorinated biphenyls. This method should be used
whenever elevated baselines or overly complex chromatograms prevent accurate
quantitation of PCBs. This method cannot be used to cleanup extracts for other
target analytes, as it will destroy most organic chemicals including the
pesticides Aldrin, Dieldrin, Endrin, Endosulfan (I and II), and Endosulfan
sulfate.
2.0 SUMMARY OF METHOD
2.1 An extract is solvent exchanged to hexane, then the hexane is
sequentially treated with (1) concentrated sulfuric acid and, if necessary, (2)
5% aqueous potassium permanganate. Appropriate caution must be taken with these
corrosive reagents.
2.2 Blanks and replicate analysis samples must be subjected to the same
cleanup as the samples associated with them.
2.3 It is important that all the extracts be exchanged to hexane before
initiating the following treatments.
3.0 INTERFERENCES
3.1 This technique will not destroy chlorinated benzenes, chlorinated
naphthalenes (Halowaxes), and a number of chlorinated pesticides.
4.0 APPARATUS
4.1 Syringe or Class A volumetric pipet, glass; 1.0, 2.0 and 5.0 mL.
4.2 Vials -1,2 and 10 mL, glass with Teflon lined screw caps or crimp
tops.
4.3 Kuderna-Danish (K-D) apparatus.
4.3.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
3665 - 1 Revision 0
September 1994
-------
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.4 Vortex mixer.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sulfuric acid/Water, H2SO«/H20, (1:1, v/v).
5.4 Hexane, C6HU - Pesticide grade or equivalent.
5.5 Potassium permanganate, KMn04, 5 percent aqueous solution (w/v).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
7.0 PROCEDURE
7.1 Sulfuric acid cleanup
7.1.1 Using a syringe or a volumetric pipet, transfer 1.0 or 2.0 mL
of the hexane extract to a 10 mL vial and, in a fume hood, carefully add
5 mL of the 1:1 sulfuric acid/water solution.
7.1.2 The volume of hexane extract used depends on the requirements
of the GC autosampler used by the laboratory. If the autosampler
functions reliably with 1 mL of sample volume, 1.0 mL of extract should be
used. If the autosampler requires more than 1 mL of sample volume, 2.0 mL
of extract should be used.
CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
3665 - 2 Revision 0
September 1994
-------
7.1.3 Cap the vial tightly and vortex for one minute. A vortex must
be visible in the vial.
CAUTION: Stop the vortexing immediately if the vial leaks, AVOID
SKIN CONTACT, SULFURIC ACID BURNS.
7.1.4 Allow the phases to separate for at least 1 minute. Examine
the top (hexane) layer; it should not be highly colored nor should it have
a visible emulsion or cloudiness.
7.1.5 If a clean phase separation is achieved, proceed to
Sec. 7.1.8.
7.1.6 If the hexane layer is colored or the emulsion persists for
several minutes, remove the sulfuric acid layer from the vial and dispose
of it properly. Add another 5 ml of the clean 1:1 sulfuric acid/water. .
NOTE: Do not remove any hexane at this stage of the procedure.
7.1.7 Vortex the sample for one minute and allow the phases to
separate.
7.1.8 Transfer the hexane layer to a clean 10 mL vial.
7.1.9 Add an additional 1 ml of hexane to the sulfuric acid layer,
cap and shake. This second extraction is done to ensure quantitative.
transfer of the PCBs and Toxaphene.
7.1.10 Remove the second hexane layer and combine with the
hexane from Sec. 7.1.8.
7.2 Permanganate cleanup
7.2.1 Add 5 ml of the 5 percent aqueous potassium permanganate
solution to the combined hexane fractions from 7.1.10.
CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
7.2.2 Cap the vial tightly and vortex for 1 minute. A vortex must
be visible in the vial.
CAUTION: Stop the vortexing immediately if the vial leaks. AVOID
SKIN CONTACT, POTASSIUM PERMANGANATE BURNS.
7.2.3 Allow the phases to separate for at least 1 minute. Examine
the top (hexane) layer, it should not be highly colored nor should it have
a visible emulsion or cloudiness.
7.2.4 If a clean phase separation is achieved, proceed to
Sec. 7.2.7.
3665 - 3 Revision 0
September 1994
-------
7.2.5 If^ the hexane layer is colored or the emulsion persists for
several minutes, remove the permanganate solution from the vial via a
glass pipette and dispose of it properly. Add another 5 mi of the clean
aqueous permanganate solution.
NOTE: Do not remove any hexane at this stage of the procedure.
7.2.6 Vortex the sample and allow the phases to separate.
7.2.7 Transfer the hexane layer to a clean 10 ml vial.
7.2.8 Add an additional 1 ml of hexane to the permanganate layer,
cap the vial securely and shake. This second extraction is done to ensure
quantitative transfer of the PCBs and Toxaphene.
7.2.9 Remove the second hexane layer and combine with the hexane
from Sec. 7.2.7.
7.3 Final preparation
7.3.1 Reduce the volume of the combined hexane layers to the
original volume (1 or 2 ml) using the Kuderna-Danish Technique
(Sec. 7.3.1.1).
7.3.1.1 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 hexane to the top of the column. Place the K-D
apparatus on a hot water bath (15-20°C above the boiling point of
the solvent) so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is
bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the
concentration in 10-20 minutes. At the proper rate of distillation
the balls of the column will actively chatter, but the chambers will
not flood. When the apparent volume of liquid reaches 1-2 ml,
remove the K-D apparatus from the water bath and allow it to drain
and cool for at least 10 minutes.
7.3.1.2 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 mL of hexane.
The extract may be further concentrated by using either the micro
Snyder column technique (Sec. 7.3.2) or nitrogen blowdown technique
(Sec. 7.3.3).
7.3.2 Micro Snyder Column Technique
7.3.2.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0.5 ml of hexane to the top of the
column. Place the K-D apparatus in a hot water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete the concentration in 5-10 minutes. At the
3665 - 4 Revision 0
September 1994
-------
proper rate of distillation the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes. Remove
the Snyder column and rinse the flask and its lower joints with
about 0.2 ml of hexane and add to the concentrator tube. Adjust the
final volume to 1.0-2.0 ml, as required, with hexane.
7.3.3 Nitrogen Blowdown Technique
7.3.3.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
7.3.3.2 The internal wall of the tube must be rinsed down
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
7.3.4 Remove any remaining organochlorine pesticides from the
extracts using Florisil Column Cleanup (Method 3620) or Silica Gel Cleanup
(Method 3630).
7.3.5 The extracts obtained may now be analyzed for the target
analytes using the appropriate organic technique(s) (see Sec. 4.3 of this
Chapter). If analysis of the extract will not be performed immediately,
stopper the concentrator tube and store in a refrigerator. If the extract
will be stored longer than 2 days, it should be transferred to a vial with
a Teflon lined screw cap or crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
9.0 METHOD PERFORMANCE
9.1 No performance data are currently available.
10.0 REFERENCES
None required.
3665 - 5 Revision 0
September 1994
-------
METHOD 3665
SULFURIC ACID/PERMANGANATE CLEANUP
{ Start j
7.1.1 Carefully
combine hexane
with 1:1
H2SO4/H2O
solution.
7.1.2
Transfer the
appropriate
volume to
vial.
7.1.3 - 7.1.4
Cap. vortex
and allow
phaae
separation.
7.1.8
. Transfer
hexane layer
to clean vial.
7.1.10
Combine two
hexane layers.
7.1.5 Is
phase
separation
clean?
7.1.6 Remove
and dispose
H2S04 solution,
add clean H2S04
solution.
7.1.7 Cap,
vortex, and
allow phase
separation.
7.1.9 Add
hexane to
H2SO4 layer,
cap and shake.
7.2.1 Add
KMn04
solution.
7.2.2 - 7.2.3
Cap, vortex,
and allow
phase
separation.
7.2.4 Is
phase
separation
clean?
7.2.3 Remove
and dispose
KMn04 solution,
add clean KMn04
solution.
7.2.7
Transfer
hexane layer
to clean vial.
7.2.8 Add
hexane to
KMnO4 layer.
cap and shake.
7.2.9 Combine
two hexane
layers.
7.'2.6 Cap
vortex and
allow phase
separation.
7.3.1 • 7.3.3
Reduce volumn
using K-D
and/or nitrogen
blowdown tech.
7.3.4 Use
Method 3620 or
Method 3630 to
further remove
contaminants.
7.3.5 Stopper
and
refrigerate
for further
analysis.
Stop
3665 - 6
Revision 0
September 1994
-------
4010
-------
METHOD 4010 i
SCREENING FOR PENTACHLOROPHENOL BY IMMUNOASSAY
1.0 SCOPE AND APPLICATION
1.1 Method 4010 Is a procedure for screening solids such as soils,
sludges, and aqueous media such as waste water and leachates for
pentachlorophenol (PCP) (CAS Registry 87-86-5).
1.2 Method 4010 is recommended for screening samples to determine whether
PCP is likely to be present at concentrations above 0.5 mg/Kg for solids or
0.005 mg/L for aqueous samples. Method 4010 provides an estimate for the
concentration of PCP by comparison with a standard.
1.3 Using the test kits from which this method was developed, 95 % of
aqueous samples containing 2 ppb or less of PCPs will produce a negative result
in the 5 ppb test configuration. Also, 95 % of soil samples containing 125 ppb
or less of PCBs will produce a negative result in the 500 ppb test configuration.
1.4 In cases where the exact concentration of PCP is required, additional
techniques (i.e., gas chromatography (Method 8040) or gas chromatography/mass
spectrometry (Method 8270)) should be used.
2.0 SUMMARY OF METHOD
2.1 Test kits are commercially available for this method. The
manufacturer's directions should be followed. In general, the method is
performed using a water sample or an extract of a soil sample. Sample and an
enzyme conjugate reagent are added to immobilized antibody. The enzyme conjugate
"competes" with PCP present in the sample for binding to immobilized anti-PCP
antibody. The test is interpreted by comparing the response produced by testing
a sample to the response produced by testing standard(s) simultaneously.
3.0 INTERFERENCES
3.1 Compounds that are chemically similar may cause a positive test (false
positive) for PCP. The test kit used in preparation of this method was evaluated
for interferences. Table 1 provides the concentration of compounds found to give
a false positive test at the indicated concentration.
3.2 Other compounds have been tested for cross reactivity with PCP, and
have been demonstrated to not interfere with the specific kit tested. Consult
the information provided by the manufacturer of the kit used for additional
information regarding cross reactivity with other compounds.
3.3 Storage and use temperatures may modify the method performance. Follow
the manufacturer's directions for storage and use.
4010-1 Revision 0
August 1993
-------
4.0 APPARATUS AND MATERIALS
4.1 PENTA RISc Test Kits (EnSys, Inc.), or equivalent. Each commercially
available test kit will supply or specify the apparatus and materials necessary
for successful completion of the test.
5.0 REAGENTS
5.1 Each commercially available test kit will supply or specify the
reagents necessary for successful completion of the test.
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 Follow the manufacturer's instructions for the test kit being used.
Those test kits used must meet or exceed the performance indicated in Tables 2-3.
8.0 QUALITY CONTROL
8.1 Follow the manufacturer's instructions for the test kit being used for
quality control procedures specific to the test kit used. Additionally, guidance
provided in Chapter One should be followed.
8.2 Use of replicate analyses, particularly when results indicate
concentrations near the action level, is recommended to refine information
gathered with the kit.
8.3 Do not use test kits past their expiration date.
8.4 Do not use tubes or reagents designated for use with other kits.
8.5 Use the test kits within their specified storage temperature and
operating temperature limits.
8.6 Method 4010 is intended for field or laboratory use. The appropriate
level of quality assurance should accompany the application of this method to
document data quality.
9.0 METHOD PERFORMANCE
9.1 This method has been applied to a series of groundwater, process
water, and wastewater samples from industries which use PCP, and the results
compared with GC/MS determination of PCP (Method 8270). These results are
provided in Table 2. These results represent determinations by two laboratories.
4010-2 Revision 0
August 1993
-------
9.2 This method has been applied to a series of soils from industries
which use PCP and the results compared with GC/MS determination of PCP via Method
8270. These results are provided in Table 3. These results represent
determinations by two laboratories.
10.0 REFERENCES
1. J.P. Mapes, K.D. McKenzie, L.R. McClelland, S. Movassaghi, R.A. Reddy, R.L.
Allen, and S.B. Friedman, "Rapid, On-Site Screening Test for
Pentachlorophenol in Soil and Water - PENTA-RISc™", Ensys Inc., Research
Triangle Park, NC 27709
2. J.P. Mapes, K.D. McKenzie, L.R. McClelland, S. Movassaghi, R.A. Reddy, R.L.
Allen, and S.B. Friedman, "PENTA-RISc™ - An On-Site Immunoassay for
Pentachlorophenol in Soil", Bull. Environ. Contain. Toxicol., 49:334-341,
1992.
3. PENTA-RISc™ Instructions for Use, Ensys Inc.
4010-3
Revision 0
August 1993
-------
Table 1
Cross Reactivity for PCPa
Compound
2,6-Dichlorophenol
2 , 4 , 6-Tri chl orophenol
2, 4, 5-Trichl orophenol
2, 3, 4-Trichl orophenol
2 , 3 , 5 , 6-Tetrachl orophenol
Tetrachl orohydroqu i none
Concentration (mg/Kg)
in Soil to Cause a
False Positive for PCP
at 0.5 mg/Kg
700
16
100
400
1.2
500
Concentration (ng/i)
in Water to Cause a
False Positive for PCP
at 5 /ng/L
600
100
500
600
7
>1500
for PENTA RISc Test Kit (EnSys, Inc.)
4010-4
Revision 0
August 1993
-------
Table 2
Comparison of Immunoassay* with QC/MS
Water Matrix
Sample Type
groundwater
process water
wastewater
run-off
Screening Results (ppm) |
0.005
>
>
>
>
>
>
>
0.05
<
>
>
>
>
>
<
>
>
>
>
>
<
>
0.1
>
<
>
>
>
<
>
<
>
0.5
<
<
<
<
<
<
1
>
>
>
<
>
<
<
< .
<
<
>
<
>
>
>
5
>
>
<
<
<
>
<
>
>
•
<
<
<
1 Concentration measured
by QC/MS
3.5
0.35
<0.1
8.2
2.8
2.9
0.21
0.17
0.12
0.6
1.4
<0.1
0.17
<0.1
0.034
0.098
0.084
0.086
2.1
0.073
0.026
0.006
0.169
0.239
0.190
0.114
0.346
1.1
19
4.3
Does screening test agree with
QC/MS determination?
no
yes
yes
yes
yes
yes
no
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
yes
no
yes
no
yes
no
yes
no
no
yes
yes
yes
yes
> - screening test Indicates that the sample concentration Is greater than the test concentration
< • screening test Indicates that the sample concentration Is less than the test concentration
• for PENTA RISC Test Kit (EnSys. Inc.) '.
4010-5
Revision 0
August 1993
-------
Table 3
Comparison of Immunoassay* with GC/MS
Soil Matrix
Screening Results (ppm)
0.5
>
>
<
<
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
<
<
<
>
<
>
>
<
>
>
5
>
>
<
<
>
<
>
>
<
>
<
>
<
>
>
>
>
>
>
>
>
<
>
<
<
<
<
<
<
>
<
>
>
50
>
<
<
<
>
<
<
<
<
>
<
<
<
<
<
<
<
>
>
>
>
<
<
<
<
<
<
t
<
>
<
>
<
Concentration measured by GC/MS
1100
68
0.31
0.72
315
1.5
6.4
9
1.9
46
<1
21
3.3
4
11
18
33
54
65
74
83
1.1
14.3
<1
<1
<1
3.9
<1
1.4
48
<1
142
108
Does screening test agree with
GC/MS determination?
yes
no
yes
no
yes
yes
yes
yes
yes
no
yes
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
yes
no
yes
yes
no
4010-6
Revision 0
August 1993
-------
Table 3
Continued
Screening Results (ppm)
0.5
>
>
>
>
>
<
<
>
5
>
>
<
>
>
<
<
<
SO
>
>
<
<
>
<
<
<
Concentration measured by GC/MS
117
56
2.5
3.5
143
nd
0.02
5
Does screening test agree with
GC/MS determination?
yes
yes
yes
no
yes
yes
yes
yes
> • screening test Indicates that the sample concentration Is greater than the test concentration
< - screening test Indicates that the sample concentration Is less than the test concentration
• for PENTA RISc Test Kit (EnSys, Inc.)
4010-7
Revision 0
August 1993
-------
5030A
-------
METHOD 5030A
PURGE-AND-TRAP
1.0 SCOPE AND APPLICATION
1.1. This method describes sample preparation and extraction for the
analysis of volatile orgahics by a purge-and-trap procedure. The gas
chromatographic determinative steps are found in Methods 8010, 8015, 8020, 8021
and 8030. Although applicable" to Methods 8240 and 8260, the purge-and-trap
procedure is already incorporated into Methods 8240 and 8260.
1.2 Method 5030 can be used for most volatile organic compounds that have
boiling points below 200°C and are insoluble or slightly soluble in water.
Volatile water-soluble compounds can be included in this analytical technique;
however, quantitation limits (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds that
elute as sharp peaks from a GC column packed with graphitized carbon lightly
coated with a carbowax or a coated capillary column. Such compounds include low
molecular weight halogenated hydrocarbons, aromatics, ketones, nitriles,
acetates, acrylates, ethers, and sulfides.
1.3 Water samples can be analyzed directly for volatile organic compounds
by purge-and-trap extraction and gas chromatography. Higher concentrations of
these analytes in water can be determined by direct injection of the sample into
the chromatographic system.
1.4 This method also describes the preparation of water-miscible liquids,
non-water-miscible liquids, solids, wastes, and soils/sediments for analysis by
the purge-and-trap procedure.
2.0 SUMMARY OF METHOD •
2.1 The purge-and-trap process: An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the volatile components are adsorbed. After
purging is completed, the sorbent column is heated and backflushed with inert gas
to desorb the components onto a gas chromatographic column.
2.2 If the sample introduction technique in Section 2.1 is not
applicable, a portion of the sample is dispersed in methanol to dissolve the
volatile organic constituents. A portion of the methanolic solution is combined
with water in a specially .designed purging chamber. It is then analyzed by
purge-and-trap GC following the normal water method.
3.0 INTERFERENCES ; ' • .
3.1 Impurities in the purge gas, and from,organic compounds out-gassing
from thex plumbing ahead of the trap, account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
5030A - 1 Revision 1
July 1992
-------
contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-TFE plastic coating, non-TFE thread sealants, or flow
controllers with rubber components 'in the purging device should be avoided.
3.2 Samples can be contaminated by diffusion Of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the sample vial during shipment and storage. A trip blank prepared from
organic-free reagent water and'carried through sampling and handling protocols
serves as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by an analysis of
organic-free reagent water to check for cross-contamination. The trap and other
parts of the system are subject to contamination. Therefore, frequent bake-out
and purging of the entire system may be required.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
' '
4.0 APPARATUS AND MATERIALS ; .-
4.1 Microsyringes - 10 jiL, 25 /iL, 100 /iL, 250 pi, 500 /iL, and 1,000 /iL.
These syringes should be equipped with a 20 gauge (0.006 in ID) needle having a
length sufficient to extend from the sample inlet to within 1 cm of the glass
frit in the purging device. The needle length will depend upon the dimensions
of the purging device employed.
4.2 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Syringe - 5 ml, gas-tight with shutoff valve.
4.4 Analytical balance - 0.0001 g.
4.5 Top-loading balance - 0.1 g.
4.6 Glass scintillation vials - 20 ml, with screw-caps and Teflon liners
-or glass culture tubes with screw-caps and Teflon liners.
4.7 Volumetric flasks, Class A - 10 ml and, 100 ml, with ground-glass
stoppers.
4.8 Vials - 2 ml, for GC autosampler.
4.9 Spatula - Stainless steel.
4.10 Disposable pipets - Pasteur.
4.11 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available. i
5030A - 2 ' Revision 1
July 1992
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4.11.1 The recommended purging chamber is designed to accept 5
ml samples with a water column at least 3 cm deep. The gaseous headspace
between the water column and the trap must have a total volume of less
than 15 ml. The purge gas must pass through the water column as finely
divided bubbles with a diameter of less than 3 mm at the origin. The
purge gas must be introduced no more than 5 mm from the base of the water
column. The sample purger, illustrated in Figure 1, meets these design
criteria. Alternate sample purge devices may be used, provided equivalent
performance is demonstrated.
4.11.2 The trap must be at least 25 cm long and have an inside
diameter ,of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of adsorbents: 1/3 of 2;6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is
recommended that 1.0 cm of methyl silicone-coated packing be inserted at
the inlet to extend the life of the trap (see Figures 2 and 3). If it is
not necessary,to analyze for dichlorodifluoromethane or other fluoro-
carbons of similar volatility, the charcoal can be eliminated and the
polymer increased to fill 2/3 of the trap. If only compounds boiling
above 35°C are to be analyzed, both the silica gel and charcoal can be
eliminated and the polymer increased to fill the entire trap. Before
initial use, the trap should be conditioned overnight at 180°C by
backflushing with an inert gas flow of at least 20 mL/min. Vent the trap
effluent to the hood, not to the analytical column. Prior to daily use,
the trap should be conditioned for 10 min at 180°C with backflushing. The
trap may be vented to the analytical column during daily conditioning;
however, the column must be run through the temperature, program prior to
analysis of samples.
4.11.3 The desorber should be capable of rapidly heating the
trap to 180°C for desorption. The polymer section, of the trap should not
be heated higher than 180°C, and the remaining sections should not exceed
220°C during bake-out mode. The desorber design illustrated in Figures 2
and 3 meet these criteria.
4.11.4 The purge-and-trap device may be assembled as a separate
unit or may be coupled to a gas chromatograph, .as shown in Figures 4
and 5.
4.11.5 Trap Packing Materials .
4.11.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.11.5.2 Methyl silicone packing - OV-1 (3%) on
Chromosorb-W, 60/80 mesh or equivalent.
4.11.5.3 Silica gel - 35/60 mesh,'. Davison, grade 15 or
equivalent.
4.11.5.4 Coconut charcoal - Prepare from Barnebey Cheney,
CA-580-26 lot #M-2649, or equivalent, by crushing through 26 mesh
screen.
5030A - 3 . Revision 1
July 1992
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4.12 Heater or heated oil bath - capable of maintaining the purging
chamber to within 1°C, over a temperature range from ambient to 100°C.
5.0 REAGENTS ! .
5.1 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CH3OH - Pesticide quality or equivalent. Store away from
other solvents.
5.3 Reagent Tetraglyme - Reagent tetraglyme.is defined as tetraglyme in
which interference is not observed at the method detection limit of the compounds
of interest.
5.3.1 Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich #17,
240-5 or equivalent), OoH1805. Purify by treatment at reduced pressure in
a rotary evaporator. The tetraglyme should have a peroxide content of
less than 5 ppm as indicated by EM Quant Test Strips (available from
Scientific Products Co., Catalog No. P1126-8 or equivalent).
CAUTION: Glycol ethers are suspected carcinogens. All solvent
handling should be done in .a hood while using proper
protective equipment to minimize exposure to liquid and
vapor.
Peroxides may be removed by passing the tetraglyme through a column
of activated alumina. The tetraglyme is placed in a round bottom flask
equipped with a standard taper joint, and the flask is affixed to a rotary
evaporator. The flask is immersed iri a water bath at 90-100°C and a vacuum
is maintained at < 10 mm Hg for at least two hours using a two stage
mechanical pump. The vacuum system is equipped with an all glass trap,
which is maintained in a dry ice/methanol bath. Cool the tetraglyme to
ambient temperature and add 100 mg/L of 2,6-di-tert-butyl-4-methyl-phenol
to prevent peroxide formation. Store the tetraglyme in a tightly sealed
screw cap bottle in an area that is not contaminated by solvent vapors.
5.3.2 In order to demonstrate that all interfering volatiles have
been removed from the tetraglyme, an organic-free reagent water/tetraglyme
blank must be analyzed.
5.4 Polyethylene glycol, H(OCH2CH2)nOH. Free of interferences at the
"detection limit of the analytes.
6.0 SAMPLE COLLECTION, PRESERVATION; AND HANDLING
6.1 Refer to the introductory material to this chapter, Organic Analytes,
Section 4.1. Samples should be stored in capped bottles, with minimum headspace,
at 4°C or less.' . ;
5030A - 4 > , Revision 1
July 1992
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7.0. PROCEDURE
7.1 Initial calibration: Prior to using this introduction technique for
any GC method, the system must be calibrated. General calibration procedures are
discussed in Method 8000, while the specific determinative methods and Method
3500 give details on preparation of standards.
7.1.1 Assemble a purge-and-trap device that meets the specification
in Section 4.10. Condition the trap overnight at 180°C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition the
trap daily for 10 min while backflushing at 180°C w.ith the column at 220°C.
7.1.2 Connect the purge-and-trap device to a gas chromatograph.
7.1.3 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate standards,
directly in the purging device. Add 5.0 ml of organic-free reagent water
to the purging device. The organic-free reagent water is added to the
purging device using a 5 ml glass syringe fitted with a 15 cm 20-gauge
needle. The needle is inserted through the sample inlet shown in
Figure 1. The internal diameter of the 14-gauge needle that forms the
sample inlet will permit insertion of the 20-gauge needle. Next', using a
10 nl or 25 nl micro-syringe equipped with a long needle (Section 4.1),
take a volume of the secondary dilution solution containing appropriate
concentrations of the calibration standards. Add the aliquot of
calibration solution directly to the organic-free reagent water in the
purging device by inserting the needle through the sample inlet. When
discharging the contents of the micro-syringe, be sure that the end of the
syringe needle .is well beneath the surface of the organic-free reagent
water. Similarly, add 10 pi of the internal standard solution. Close the
2-way syringe valve at the sample inlet.
7.1.4 Carry out the purge-and-trap analysis procedure using the
specific conditions given in Table 1.
7.1.5 Calculate response factors or calibration factors for each
analyte of interest using the procedure described in Method 8000.
7.1.6 The average RF must be calculated for each compound. A system
performance check should be made before this calibration curve is used.
If the purge-and-trap procedure is used with Method 8010, the following
five compounds are checked for a minimum average response factor:
chloromethane; 1,1-dichloroethane; bromoform; 1,1,2,2-tetrachloroethane;
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform). These compounds typically have RFs
of 0.4-0.6, and are used to check compound stability and to check for
degradation caused, by contaminated lines or active sites in the system.
Examples of these occurrences are:
7.1.6.1 Chloromethane: This compound is the most likely.
compound to be lost if the purge flow is too fast.
7.1.6.2 Bromoform: This compound is.one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
5030A - 5 Revision 1
July 1992
-------
Cold spots and/or active sites in the transfer lines may adversely
affect response.
7.1.6.3 Tetrachloroethane and 1,1-dichloroethane: These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active .sites in trapping materials.
7.2 On-going calibration: Refer to Method 8000 for details on continuing
calibration. .
7.3 Sample preparation ;
7.3.1 Water samples
7.3.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be utilized are: the use
of an automated headspace sampler (modified Method 3810), interfaced
to a gas chromatograph (GC), equipped with a photo ionization
detector (PID), in series with an electrolytic conductivity detector
(HECD); and extraction of the sample with hexadecane (Method 3820)
and analysis of the extract on a GC with a FID and/or an ECO.
.' 7.3.1.2 All samples and standard solutions must be allowed
to warm to ambient temperature before analysis.
7.3.1.3 Assemble the purge-and-trap device. The operating
conditions for the GC are given in Section 7.0 of the specific
determinative method to be employed.
7.3.1.4 Daily GC calibration criteria must be met (Method
8000) before analyzing samples.
, 7.3.1.5 Adjust the purge gas flow rate (nitrogen or
helium) to that shown in Table 1, on the purge-and-trap device.
Optimize the flow rate to provide the best response for
chloromethane and bromoform', if these compounds are analytes.
Excessive flow rate reduces chloromethane response, whereas
insufficient flow reduces bromoform response.
7.3.1.6 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. Open the sample or standard bottle, which
has been allowed to come to ambient temperature, and carefully pour
the sample into the syringe barrel to just short of overflowing.
Replace the syringe plunger and compress the sample. Open the
syringe valve and vent any residual air while adjusting the sample
volume,to 5.0 ml. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis;- therefore, if
there is only one VOA vial, the analyst should fill a second syringe.
at this time to protect against possible loss of sample integrity.
This second sample is maintained only until such time when the
analyst has determined that the first sample has been analyzed
properly. Filling one 20 ml syringe would allow the use of only one
5030A - 6 Revision 1
July 1992
-------
syringe. If a second analysis is needed from a syringe, it, must be
analyzed within 24 hr. Care must be taken to prevent air from
leaking into the syringe.
7.3.1.7 The following procedure is appropriate for
diluting purgeable samples. All steps must be performed without
delays until the diluted sample is in a gas-tight syringe.
7.3.1.7.1 Dilutions may be made in volumetric flasks
(10 ml to 100 ml). Select the volumetric flask that will
allow for the necessary dilution. Intermediate dilutions may
be necessary for extremely large dilutions.
7.3.1.7.2 Calculate the approximate volume of
organic-free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of organic-
free reagent water to the flask.
7.3.1.7.3 Inject the proper aliquot of samples from
the syringe prepared in Section 7.3.1.5 into the flask.
Aliquots of less than 1 ml are not recommended. Dilute the
sample to the mark with organic-free reagent water. Cap the
flask, invert, and shake three times. Repeat the above
procedure for additional dilutions.
7.3.1.7.4 Fill a 5 ml syringe with the diluted sample
as in Section 7.3.1.5.
7.3.1.8 Add 10.0 /iL of surrogate spiking solution (found
in each determinative method, Section 5.0) and, if applicable, 10 /nL
of internal standard spiking, solution through the valve bore of the
syringe; then close the valve. The surrogate and internal standards
may be mixed and added as a single spiking solution. Matrix spiking
solutions, if indicated, should be added (10 juL) to the sample at
this time.
7.3.1.9 Attach the syringe-syringe valve assembly to the
syringe valve on the purging device. Open the syringe valves and
inject the sample into the purging chamber.
7.3.1.10 , Close both valves and purge the-sample for the
time and at the temperature specified in Table 1.
7.3.1.11 At the conclusion of the purge time, attach the
trap to the chromatograph, adjust the device to the desorb mode, and
begin the gas chromatographic temperature program and GC data
acquisition. Concurrently, introduce the trapped materials to, the
gas chromatographic column by rapidly heating the trap to 180°C
while backflushing the trap with inert gas between 20 and 60 mL/min
for the time specified in Table 1.
7.3.1.12 While the trap is being desorbed1into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5 ml flushes of organic-free reagent water (or
5030A - 7 Revision 1
July 1992
-------
methanol followed by organic-free reagent water) to avoid'carryover
of pollutant compounds into subsequent analyses.
7.3.1.13 After desorbing the sample, recondition the trap
by returning the,purge-and-trap device to the purge mode. Wait 15
sec; then close the syringe valve on the purging device to begin gas
flow through the/trap. The trap temperature should be maintained at
180°C for Methods 8010, 8020, 8021, 8240 and 8260 and 210°C for
Methods 8015 and 8030. Trap temperatures up to 220°C may be
.employed. However, the higher temperatures will shorten the useful
life of the trap. After approximately 7 min, turn off the trap
heater and open the syringe valve to stop the gas flow through the
trap. When cool, the trap is ready for the next sample.
7.3.1.14 If the initial analysis of a sample or a dilution
of the sample has a concentration of analytes that exceeds the
initial calibration range, the sample must be reanalyzed at a higher
dilution. When a sample is analyzed that has saturated response
from a compound, this analysis must be followed by a blank organic-
free reagent water analysis. If the blank analysis is not free of
interferences, the system must be decontaminated. Sample analysis
may not resume until a blank can be analyzed that is free of
interferences.
7.3.L15 All dilutions should keep the response of the
major constituents (previously saturated peaks) in the upper half of
the linear range of vthe curve. Proceed to Method 8000 and the
specific determinative method for details on calculating analyte
response.
7.3.2 Water-miscible liquids:
7.3.2.1 Water-miscible liquids are analyzed as water
samples after first diluting them at least 50-fold with organic-free
reagent water.
7.3.2.2 Initial and serial dilutions can be prepared by
pipetting 2 ml of the sample into a 100 ml volumetric flask and
diluting to volume with organic-free reagent water. Transfer
immediately to a 5 ml gas-tight syringe.
7.3.2.3 Alternatively, prepare dilutions directly in a 5
ml syringe filled with organic-free reagent water by adding at least
20 /iL, but not more than 100 jiL of liquid sample. The sample is
ready for addition of surrogate and, if applicable, internal and
matrix spiking standards. .•'••' .
7.3.3 Sediment/soil and waste samples: It is highly recommended
that all samples of this type be screened prior to the purge-and-trap GC
analysis. These samples may contain percent quantities of purgeable
organics that will contaminate the purge-and-trap system, and require
extensive cleanup and instrument downtime. See Section 7.3.1.1 for
recommended screening techniques. Use the screening data to determine
whether to use the low-concentration method (0.005-1 mg/kg) or the high-
5030A - 8 '• Revision 1
July 1992
-------
concentration method (>1 mg/kg). • _,
.''
7.3.3.1 Low-concentration method: This is designed for
samples containing individual purgeable compounds of <1 mg/kg. It
is limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous), the low-concentration method is
based on purging a heated sediment/soil sample mixed with
organic-free reagent water containing the surrogate and, if
applicable, internal and matrix spiking standards. Analyze all
reagent blanks and standards under the same conditions as the
samples.
7.3.3.1.1 Use a 5 g sample if the expected
concentration is <0.1 mg/kg or a 1 g sample for expected
concentrations between 0.1 and 1 mg/kg.
7.3.3.1.2 The GC system should be set up as in
Section 7.0 of the specific determinative method. This should
be done prior to the preparation of the sample to avoid loss
of volatiles from standards and samples. A heated purge
calibration curve must be prepared and used for the
quantitation of all samples analyzed .with the Tow-
concentration method. Follow the initial and daily
calibration instructions, except for the addition of a 40°C
purge temperature for Methods 8010, 8020, and 8021.
7.3.3.1.3 Remove the plunger from a 5 ml Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with organic-free reagent water. Replace the
plunger and compress the reagent water to vent trapped air.
Adjust the volume to 5.0 mL. Add 10 pi each of surrogate
spiking solution and internal standard solution to the syringe
through the valve. (Surrogate spiking solution and internal
standard solution may be mixed together.) Matrix spiking
solutions, if indicated, should be added,(10 pi) to the sample
at this time. ,
.. 7.3,3.1.4 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. Weigh the
amount determined in Section 7.3.3.1.1 into a tared purge
device. Note and record the actual weight to the nearest 0.1
g. '-•.-•
7.3.3.1.5 Determination of sampled dry weight - In
certain cases, sample results are desired based on dry weight
basis. When such data is desired, a portion of sample for
this determination should be weighed out at the, same time as
the portion used for analytical determination.
' WARNING; The drying oven should be contained in a
hood or vented: Significant laboratory
contamination may result from a heavily
5030A - 9 Revision 1
July 1992
-------
contaminated hazardous waste sample.
7.3.3.1.5.1 Immediately after weighing the sample
for extraction, weigh 5-10 g of the sample into a tared
crucible. Determine the % dry weight of the sample by
drying overnight at 105°C. Allow to cool in a
desiccator before weighing:
i- % dry weight = q of dry sample x 100
g of sample
i r '
7.3.3.1.6 Add the spiked organic-free reagent water to
the purge device, which contains the weighed amount of sample,
and connect the device to the purge-and-trap system.
NOTE; Prior to the attachment of the purge device,
Sections 7.3.3.1.4 and 7.3.3.1.6 must be
performed rapidly and without interruption to
•.' avoid Toss of volatile organics. These steps
must be performed in a laboratory free of solvent
'fumes.
7.3.3.1.7 Heat the sample to 40°C ± 1°C (Methods 8010,
8020 and 8021) or to 85°C ± 25C (Methods 8015 and 8030) and
purge the sample for the time shown in Table 1.
7.3.3.1.8 Proceed with the analysis as outlined in
Sections 7.3.1.11-7.3.1.15. Use 5 ml of the same organic-free
reagent water as in the reagent blank. If saturated peaks
occurred or would occur if a 1 g sample were analyzed, the
high-concentration method must be followed.
7.3.3.1.9 For matrix spike analysis of
low-concentration sediment/soils, add 10 nL of the matrix
spike solution to 5 ml of organic-free reagent water (Section
7.3.3.1.3 ). The concentration for a 5 g sample would be
equivalent to 50 ng/kg of each matrix spike standard.
7.3'.3.2 High-concentration method: The method is based on
extracting the sediment/soil with methanol. A waste sample is
either extracted or diluted, depending on its' solubility in
methanol. Wastes (i.e. petroleum and coke wastes) that are
insoluble in methanol. are diluted with reagent tetraglyme or
polyethylene glycol (PEG). An aliquot of the extract is added to
organic-free reagent water containing surrogate and, if applicable,
internal and matrix spiking standards. . This is purged at the
temperatures indicated in Table 1. All samples with an expected
concentration of >1.0 mg/kg should be analyzed by this method.
7.3.3.2.1 , The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a. narrow metal spatula. For
sediment/soiland waste that are insoluble in methanol, weigh
5030A - 10 Revision 1
July 1992
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4 g (wet weight) of sample into a tared 20 ml vial. Use a
top-loading balance. Note and record the actual weight to 0.1
gram and determine the percent dry weight :of the sample using
the procedure in Section 7.3.3.1.5. For waste that is soluble
in methanol, tetraglyme, or PEG, weigh 1 g (wejt weight) into
a tared scintillation vial or culture tube or a 10 ml
volumetric flask. (If a vial or tube is used, it must be
calibrated prior to use. Pipet 10.0 ml of methanol into the
vial and mark the bottom of the meniscus. Discard this
solvent.) ,
7.3.3.2.2 For sediment/soil or solid waste, quickly
add 9.0 ml of appropriate solvent; then add 1.0 ml of the
surrogate spiking solution to the vial. For a "solvent
miscible sample, dilute the sample to 10 ml with-- the
appropriate solvent after adding 1.0 ml of the surrogate
spiking solution. Cap and shake for 2 min.
NOTE: Sections 7.3.3.2.1 and 7.3.3.2.2. must be
performed rapidly and without interruption to
avoid loss ,of volatile organics. These steps
must be performed in a laboratory free^ from
solvent fumes.
7.3.3.2.3 Pipet approximately 1 ml of the extract into
a GC vial for storage, using .a disposable pipet. The
remainder may be discarded. Transfer approximately 1 ml of
reagent methanol to a separate GC vial for use as the method
blank for each set of samples. These extracts may be stored
at 4°C in the dark, prior to analysis.
7.3.3.2.4 The GC system should be set up as in
Section 7.0 of the specific determinative method. This should
be done prior to the addition of the methanol extract to
organic-free reagent water.
7.3.3.2.5 Table 2 can be used to determine the volume
of methanol extract to add to the 5 ml of organic-free reagent
water for analysis.- If a screening procedure was followed,
use the estimated concentration to determine the appropriate
volume. Otherwise, estimate the concentration range of the
sample from the low-concentration analysis to determine the
appropriate volujne. If the sample was .submitted as a high-
concentration sample, start with 100 nl. All dilutions must
keep the response of the major constituents (previously
saturated peaks) in the upper half of the linear range of the
curve.
7.3.3.2.6 Remove the plunger from a 5.0 ml Luerlock
type syringe equipped with a syringe valve and fill until
overflowing with organic-free reagent water. Replace the
plunger and compress the water to vent trapped air. Adjust
the volume to 4.9 mL. Pull the plunger back to 5.0 ml to
allow volume for the addition of the sample extract and of
5030A - 11 Revision 1
, July 1992
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standards. Add 10 /iL of internal standard solution. Also add
the volume of methanol extract determined in Section' 7.3.3.2.5
and a volume of methanol solvent to total 100 jiL (excluding
methanol in standards).
i
7.3.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe
valve and inject the water/methanol sample into the purging
chamber.
7.3.3.2.8 Proceed with the analysis as outlined in the
specific determinative method. Analyze all reagent blanks on
the same instrument as that used for the samples. The
standards and blanks should also contain 100 /LiL of methanol
to simulate the sample conditions.
7.3.3.2.9 For a matrix spike in the high-concentration
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution and 1.0 ml of matrix spike solution.
Add a 100 /*L aliquot of this extract to 5 ml of water for
purging (as per Section 7.3.3.2.6).
7.4 Sample analysis:
7.4.1 The samples prepared by this method may be analyzed by Methods
8010, 8015, 8020, 8021, 8030, 8240, and 8260. Refer to these methods for
appropriate analysis conditions.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3500 for sample preparation procedures.
8.2 ; Before processing any samples, the analyst should demonstrate through
the analysis of a calibration blank that all glassware and reagents are
interference free. Each time a set of samples is extracted, or there is a change
in reagents, a method blank should be processed as a safeguard against chronic
laboratory contamination. The blanks should be carried through all stages of
the sample preparation and measurement.
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the-sampling
technique. Laboratory replicates should be analyzed to validate the precision
of the analysis. Spiked samples should be carried through all stages of sample
preparation and measurement; they should be analyzed to validate the sensitivity
and accuracy of the analysis: If the spiked samples do not indicate sufficient
sensitivity to detect < 1 ng/g of the analytes in the sample, then the
sensitivity of the instrument should be increased, or the sample should be
subjected to additional cleanup.
5030A - 12 Revision 1
. July 1992
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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.
5030A - 13 , Revision 1
July 1992
-------
TABLE 1
PURGE-AND-TRAP OPERATING PARAMETERS
Analysis Method
8010
8015
8020/8021
8030
Purge gas
Purge gas flow rate
(mL/min)
Purge time (min)
Purge temperature (°C)
Desorb temperature (°C)
Backflush inert gas flow
(mL/min)
Desorb time (min)
Nitrogen or Nitrogen or
Helium
40
11.0 ± 0.1
Ambient
180
20-60 ,
4
Helium
20
15.0 ± 0.1
85 ± 2
180
20-60
'1.5
Nitrogen or Nitrogen or
Helium Helium
40
11.0 ± 0.1
Ambient
180
20-60
4
20
15.0 ± 0.1
85 ± 2
180
20-60
1.5
5030A - 14
Revision 1
July 1992
-------
TABLE 2
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract8
500-10,000 MgAg 100 ML
1,000-20,000 Mg/kg so Mt
5,000-100,000 /ig/kg 10 /iL '
25,000-500,000 j^/kg 100 al of 1/50 dilution b
Calculate appropriate dilution factor for concentrations exceeding this table.
"The volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of methanol is
necessary to maintain a volume of 100 pi added to the syringe.
/
Dilute an aliquot of the methanol extract and then take 100 /iL for analysis.
5030A - 15 Revision 1
July 1992
-------
Figure 1
Purging Chamber
OPTIONAL
FOAM TIIAF
i*it * Inch 0. 0
14 mm 0. 0.
v
mlft 'i Inch 0. D.
2-W«v Syrwifi Valvt
1? cm. 20 GMft fyrinp Nw«lt
6 mm 0.0. MuMtf StPtum
* 10 mm P.P.
Inlet
* Inch 0.0
1/ieincftO 0.
5030A - 16
Revision 1
July 1992
-------
Figure 2
Trap Packing and Construction for Method 8010
Packing Procedure
Construction
Otaw Wool B mm
Activated |
Chareoal 7.7 cm
Ktiittanct
Wirt Wr«oo«d
Solid
(OeuMtlJVtr)
Grade 15
Silica Gel 7.7 cm I
Tenaa 7.7 em K;
3% OV
Clan Woo*
II
-1 le^Jil
Rttiitanc*
Wirt Wripptd
Solid
Comprtuion
Nut
and *• rru»*»
Thcrmocogpi*'
Controller
Stmer
Elteuenic
Ttmecnturt
Control and
Pyromtttr
Tubing 2S cm
0.108 In. l.O.
0.128 in. 0.0.
Stainieta Steel
Tr«p Inlet
5030A - 17
Revision 1
July 1992
-------
Figure 3
Trap Packing and Construction for Methods 8020 and 8030
Packing Proctdurt
Construction
Glass Wool 5 mm
Tenix 23 cm
3%OV-1 1cm
Glass Wool 5 mm
I
Compnssion Fitting Nut
ind Ftrrults
14 Ft. ?n/Foet Rtsistanet
Wirt Wrapped Solid
Thermocouple/Controller Sinsor
Electronic
Temperature
Control and
Fyometer
Tubing 25 cm
0.105 In. 1.0.
0.125 In. O.D.
Stainless Steel
Trap Inlet
5030A - 18
Revision 1
July 1992
-------
Figure 4
Purge-and-Trap System
Purge-Sorb Mode
For Method 8010, 8020, and 8030
CARWERGAS
FLOW CONTROL
PRESSURE
REGULATOR
r- UOUIO INJECTION PORTS
COLUMN OVEN
OPTIONAL *PORT COLUMN
SELECTION VALVE
CONFIRMATORY COLUMN
TO ueicCTUR
ANALYTICAL COLUMN
PURGE OAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
NOTE
ALL UNCS BETWEEN TRAP
AND OC SHOULD BE HEATED
TOBJPC.
5030A - 19
Revision 1
July 1992
-------
Figure 5
Purge-and-Trap System
Desorb Mode
For Method 8010, 8020, and 8030
CARRKRGAS
FLO* CONTROL
PRESSURE
REGULATOR
UOUtO INJECTION PORTS
COLUMN OVEN
OPTX3NAL 4PORT COLUMN
SELECTION VALVE
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
NOTE:
ALL LINES BETWEEN TRAP
ANO GC SHOULD BE HEATED
TO WC.
5030A - 20
Revision 1
July 1992
-------
METHOD 5030A
PURGE-ANO-TRAP
Start
7 1 Calibrate
CC system i
712 Assemble
purge • and -trap .
condition trap
; 7 1.2 Connect
to gai
chr oma t ograph
713 Prepare
final
so 1 u 1 1 oni .
714 Corry out
purge - and • trap
analy»i«.
, 7 1 5 Calculate
response or
calibration factors
•for each analyte
' (Method 8000) .
' 7 .1.6
Calculate
averafe RF
for each
compound .
5030A - 21
Revision 1
July 1992
-------
METHOD 5030A
continued
L
1
Lo» con
Sai.1/
7331
Prepare
samples and
set-up CC
sys ten .
-
l^Men.
sediment ^>A. Soil/iediment
/• Typ. of N.
•< method and J—
^v sample /
SMSlMiSl«sa*
7.3 3 2 Add
malhanoi
«Mtract to
reagent water
for analysis .
•ater samples andV/
•ater -miscible vastei
1 "
7.3 3 1.4
Heigh sample
into tared
device.
7 3 3.1.5
Weigh another
sample and
determine %
dry weight
7.3316 Add
• pitted reagent
•ater . connect
device to
sys tern .
7331.7
Heat and
purge sample
7 . 3 T 1 Screen
sample* prior to
purge-and- trap
analysis, dilute
•ater miscible
liquids
i
7.3.1 Prepare
sample and
purg-and- trap
. ' device .
1
7.3.17
Dilute
purgeable
samples.
i -
7. 3.1,8 Add
jur roga t« and
internal spiking
. t olution* [ if
indicated ) -
i
73.1 9
Inject' sample .
into chamber.
purge
7.3 3 2 Set
up CC syi tern .
7 3.1.11
Desorb trap
into CC .
7 3326 Fill
ay r ing* wi th
reagent wa ter ,
vent air and
adjust vo 1 ume
7.3.1.13
Recondition
trap and
start gas
flo»
7 3 3 2.6 Add -
in ternal
i tanda rd . and •
methanol
extract
/ ' /
7 3.1.13 Stop
gas flo« and
. cool trap for
next sample.'
Ana 1 y ze
according to
determinative
method '.
Analyze
according to
da tarmina 1 1 ve
me thod
^
77
5030A - 22
Revision 1
July 1992
-------
5040A
-------
METHOD 5040A
ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST):
GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 5040 was formerly Method 3720 in the Second Edition of this
manual.
1.2 This method covers the determination of volatile principal organic
hazardous constituents (POHCs), collected on Tenax and Tenax/charcoal sorbent
cartridges using a volatile organic sampling train, VOST (1). Much of the
description for purge-and-trap GC/MS analysis is described in Method 8240 of this
chapter. Because the majority of gas streams sampled using VOST will contain a
high concentration of water, the analytical method is based on the quantitative
thermal desorptibn of volatile POHCs from the Tenax and Tenax/charcoal traps and
analysis by purge-and-trap GC/MS. For the purposes of definition, volatile POHCs
are those POHCs with boiling points less than 100°C.
1.3 This method is applicable to the analysis of Tenax and Tenax/
charcoal cartridges used to collect volatile POHCs from wet stack gas effluents
from hazardous waste incinerators.
1.4 The sensitivity of the analytical method for a particular volatile
POHC depends on the level of interferences and the presence of detectable levels
of volatile POHCs in blanks. The desired target detection limit of the
analytical method is 0.1 ng/L (20 ng on a single pair of traps) for a particular
volatile POHC desorbed from either a single pair of Tenax and Tenax/charcoal
cartridges or by thermal desorption of up to six pairs of traps onto a single
pair of Tenax and Tenax/charcoal traps. The resulting single pair of traps is
then thermally desorbed and analyzed by purge-and-trap GC/MS.
1.5 This method is recommended for use only by experienced mass
spectroscopists or under the close1supervision of such qualified persons.
2.0 SUMMARY OF METHOD
2.1 A schematic diagram of the analytical system is shown in Figure 1.
The contents of the sorbent cartridges are spiked with an internal standard and
thermally desorbed for 10 min at 180°C with organic-free nitrogen or helium gas
(at a flow rate of 40 mL/min), bubbled through 5 ml of organic-free reagent
water, and trapped on an analytical adsorbent trap. After the. 10 min.
desorption, the analytical adsorbent trap is rapidly heated to 180°C, with the
carrier gas flow reversed so that the effluent flow from the analytical trap is
directed into the GC/MS. The volatile POHCs are separated by temperature
programmed gas chromatography and detected by low-resolution mass spectrometry.
The concentrations of volatile POHCs are calculated using the internal standard
technique.
5040A - 1 Revision 1
September 1994
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3.0 INTERFERENCES
3.1 Refer to Methods 3500 and 8240.
4.0 APPARATUS AND MATERIALS
4.1 Thermal desorption unit:
4.1.1 The thermal desorption unit (for Inside/Inside VOST
cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user-fabricated unit is required) should be capable of
thermally desorbing the sorbent resin tubes. It should also be capable of
heating the tubes to 180 + 10°C with flow of organic-free nitrogen or
helium through the tubes.
4.2 Purge-and-trap unit:
4.2.1 The purge-and-trap unit consists of three separate pieces of
equipment: the sample purger, trap, and the desorber. It should be
capable of meeting all requirements of Method 5030 for analysis of
purgeable organic compounds from water.
4.3 GC/MS system: As described in Method 8240.
5.0 REAGENTS
5.1 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CH3OH - Pesticide grade, or equivalent.
5.3 Analytical trap reagents:
5.3.1 2,6-Diphenylene oxide polymer: Tenax (60/80 mesh), chromato:
graphic grade or equivalent.
5.3.2 Methyl silicone packing: 3% OV-1 on Chromosorb W (60/80 mesh)
or equivalent.
5.3.3 Silica gel: Davison Chemical (35/00 mesh), Grade 15, or
equivalent.
5.3.4 Charcoal: Petroleum-based (SKC Lot 104 or equivalent).
5.4 Stock standard solution:
5.4.1 Stock standard solutions will be prepared from pure standard
materials or purchased as certified solutions. The stock standards should
be prepared 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. A NIOSH/MESA approved toxic
5040A - 2 Revision 1
September 1994
-------
gas respirator should be used when the analyst handles high concentrations
of such materials.
5.4.2 Fresh stock standards should be prepared weekly for volatile
POHCs with boiling points of <35°C. All other standards must be replaced
monthly, or sooner if comparison with check standards indicates a problem.
5.5 Secondary dilution standards:
5.5.1 Using stock standard solutions, prepare, in methanol,
secondary dilution standards that contain the compounds of interest,
either singly or mixed together. The secondary dilution standards should
be prepared at concentrations such that the desorbed calibration standards
will bracket the working range of the analytical system.
5.6 4-Bromofluorobenzene (BFB) standard:
5.6.1 Prepare a 25 ng/juL solution of BFB in methanol.
5.7 Deuterated benzene:
5.7.1 Prepare a 25 ng/p.1 solution of benzene-de in methanol.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to Method 0030, Chapter Ten.
6.2 Sample trains obtained from the VOST should be analyzed within 2-6
weeks of sample collection.
7.0 PROCEDURE
7.1 Assembly of PTD device:
7.1.1 Assemble a purge-and-trap desorption device (PTD) that meets
all the requirements of Method 5030 (refer to Figure 1).
7.1.2 Connect the thermal desorption device to the PTD device.
Calibrate the PTD-GC/MS system using the internal standard technique.
7.2 Internal standard calibration procedure:
7.2.1 This approach requires the use of deuterated benzene as the
internal standard for these analyses. Other internal standards may be
proposed for use in certain situations. The important criteria for
choosing a particular compound as an internal standard are that it be
similar in analytical behavior to the compounds of interest and that it
can be demonstrated that the measurement of the internal standard be
unaffected by method or matrix interferences. Other internal standards
that have been used are ethylbenzene-d10 and, l-2-dichloroethane-d4. One
adds 50 ng of BFB to all sorbent cartridges (in addition to one or more
5040A - 3 Revision 1
September 1994
-------
internal standards) to provide continuous monitoring of the GC/MS
performance relative to BFB.
7.2.2 Prepare calibration standards at a minimum of three
concentration levels for each analyte of interest.
7.2.3 The calibration standards are prepared by spiking a blank
Tenax or Tenax/charcoal trap with a methanolic solution of the calibration
standards (including 50 ng of the internal standard, such as deuterated
benzene), using the flash evaporation technique. The flash evaporation
technique requires filling the needle of a 5.0 nl syringe with clean
methanol and drawing air into the syringe to the 1.0 ^L mark. This is
followed by drawing a methanolic solution of the calibration standards
(containing 25 fj.g/n\- of the internal standard) to the 2.0 jj.i mark. The
glass traps should be attached to the injection port of a gas
chromatograph while maintaining the injector temperature at 160°C. The
carrier gas flow through the traps should be maintained at about 50
mL/min.
7.2.4 After directing the gas flow through the trap, the contents of
the syringe should be slowly expelled through the gas chromatograph
injection port over about 15 sec. After 25 sec have elapsed, the gas flow
through the trap should be shut off, the syringe removed, and the trap
analyzed by the PTD-GC/MS procedure outlined in Method 8240. The total
flow of gas through the traps during addition of calibration standards to
blank cartridges, or internal standards to sample cartridges, should be 25
ml or less.
7.2.5 Analyze each calibration standard for both Tenax and Tenax/
charcoal cartridges according to Section 7.3. Tabulate the area response
of the characteristic ions of each analyte against the concentration of
the internal standard and calculate the response factor (RF) for each
compound, using Equation 1.
RF = AsCis/AisCs (1)
where:
As = Area of the characteristic ion for the analyte to be
measured.
Ais = Area of the characteristic ion for the internal
standard.
Cis = Amount (ng) of the internal standard.
Cs = Amount (ng) of the volatile POHC in calibration
standard.
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant, and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais versus RF.
5040A - 4 Revision 1
September 1994
-------
7.2.6 The working calibration curve or RF must be verified on each
working day by the measurement of one or more of the calibration
standards. If the response varies by more than +25% for any analyte, a
new calibration standard must be prepared and analyzed for that analyte.
7.3 The schematic of the PTD-GC/MS system is shown in Figure 1. The
sample cartridge is placed in the thermal desorption apparatus (for Inside/
Inside VOST cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user fabricated unit is required) and desorbed in the purge-and-trap
system by heating to 180°C for 10 min at a flow rate of 40 mL/min. The desorbed
components pass into the bottom of the water column, are purged from the water,
and collected on the analytical adsorbent trap. After the 10 min desorption
period, the compounds are desorbed from the analytical adsorbent trap into the
GC/MS system according to the procedures described in Method 8240.
7.4 Qualitative analysis
7.4.1 The qualitative identification of compounds determined by this
method is based on retention time, and on comparison of the sample mass
spectrum, after background correction, with characteristic ions in a
reference mass spectrum. The reference mass spectrum must be generated by
the laboratory using the conditions of this method. The characteristic
ions from the reference mass spectrum are defined to be the three ions of
greatest relative intensity, or any ions over 30% relative intensity if
less than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.4.1.1 The intensities of the characteristic ions of a
compound maximize in the same scan or within one scan of each other.
Selection of a peak by a data system target compound search routine,
where the search is based on the presence of a target
chromatographic peak containing ions specific for the target
compound at a compound-specific retention time, will be accepted as
meeting this criterion.
7.4.1.2 The RRT of the sample component is within
± 0.06 RRT units of the RRT of the standard component.
7.4.1.3 The relative intensities of the characteristic
ions agree within 30% of the relative intensities of these ions in
the reference spectrum. (Example: For an ion with an abundance of
50% in the reference spectrum, the corresponding abundance in a
sample spectrum can range between 20% and 80%.)
7.4.1.4 Structural isomers that produce very similar mass
spectra should be identified as individual isomers if they have
sufficiently different GC retention times. Sufficient GC resolution
is achieved if the height of the valley between two isomer peaks is
less than 25% of the sum of the two peak heights. Otherwise,
structural isomers are identified as isomeric pairs.
7.4.1.5 Identification is hampered when sample components
are not resolved chromatographically and produce mass spectra
5040A - 5 Revision 1
September 1994
-------
containing ions contributed by more than one analyte. When gas
chromatographic peaks obviously represent more than one sample,
component (i.e., a broadened peak with shoulder(s) or a valley
between two or more maxima), appropriate selection of analyte
spectra and background spectra is important. Examination of
extracted ion current profiles of appropriate ions can aid in the
selection of spectra, and in qualitative identification of
compounds. When analytes coelute (i.e., only one chromatographic
peak is apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by the
coeluting compound.
7.4.2 For samples containing components not associated with the
calibration standards, a library search may be made for the purpose of
tentative identification. The necessity to perform this type of
identification will be determined by the type of analyses being conducted.
Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference spectrum
(ions > 10% of the most abundant ion) should be present in the sample
spectrum.
(2) The relative intensities of the major ions should agree within
+ 20%. (Example: For an ion with an abundance of 50% in the standard
spectrum, the corresponding sample ion abundance must be between 30 and
70%).
(3) Molecular ions present in the reference spectrum should be
present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background contamination or
presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because of background contamination or coeluting peaks. Data
system library reduction programs can sometimes create these
discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of the
sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
7.5 Quantitative analysis
7.5.1 When an analyte has been qualitatively identified,
quantitation should be based on the integrated abundance from the EICP of
the primary characteristic ion chosen for that analyte. If the sample
produces an interference for the primary characteristic ion, a secondary
characteristic ion should be used.
5040A - 6 Revision 1
September 1994
-------
7.5.1.1 Using the internal standard calibration procedure,
the amount of analyte in the sample cartridge is calculated using
the response factor (RF) determined in Section 7.2.5 and Equation 2.
Amount of POHC = A8Cis/Ai8RF (2)
where:
A8 = Area of the characteristic ion for the analyte to be
measured.
Ais = Area for the characteristic ion of the internal
standard.
Ci8 = Amount (ng) of internal standard.
7.5.1.2 The choice of methods for evaluating data
collected using VOST for incinerator trial burns is a regulatory
decision. The procedures used extensively by one user are outlined
below.
7.5.1.3 The total amount of the POHCs of interest
collected on a pair of traps should be summed.
7.5.1.4 The observation of high concentrations of POHCs of
interest in blank cartridges indicates possible residual
contamination of the sorbent cartridges prior to shipment to and use
at the site. Data that fall in this category (especially data
indicating high concentrations of POHCs in blank sorbent cartridges)
should be qualified with regard to validity, and blank data should
be reported separately. The applicability of data of this type to
the determination of ORE is a regulatory decision. Continued
observation of high concentrations of POHCs in blank sorbent
cartridges indicates that procedures for cleanup, monitoring,
shipment, and storage of sorbent cartridges by a particular user be
investigated to eliminate this problem.
7.5.1.5 If any internal standard recoveries fall outside
the control limits established in Section 8.4, data for all analytes
determined for that cartridge(s) must be qualified with the
observation.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 0030 for sample preparation procedures.
8.2 Each laboratory that uses this method is required to operate a formal
quality control program. The minimum requirements of this program consist of an
initial demonstration of laboratory capability and the analysis of blank Tenax
and Tenax/charcoal cartridges spiked with the analytes of interest. The
laboratory is required to maintain performance records to define the quality of
5040A - 7 Revision 1
September 1994
-------
data that are generated. Ongoing performance checks must be compared with
established performance criteria to determine if results are within the expected
precision and accuracy limits of the method.
8.2.1 Before performing any analyses, the analyst must demonstrate
the ability to generate acceptable precision and accuracy with .this
method. This ability is established as described in Section 7.2.
8.2.2 The laboratory must spike all Tenax and Tenax/charcoal
cartridges with the internal standard(s) to monitor continuing laboratory
performance. This procedure is described in Section 7.2,
8.3 To establish the ability to generate acceptable accuracy and
precision, the analyst must spike blank Tenax and Tenax/charcoal cartridges with
the analytes of interest at two concentrations in the working range.
8.3.1 The average response factor (RF) and the standard deviation
(s) for each must be calculated.
8.3.2 The average recovery and standard deviation must fall within
the expected range for determination of volatile POHCs using this method.
The expected range for recovery of volatile POHCs using.this method is 50-
150%.
8.4 The analyst must calculate method performance criteria for the
internal standard(s).
8.4.1 Calculate upper and lower control limits for method
performances using the average area response (A) and standard
deviation(s) for internal standard:
Upper Control Limit (UCL) = A + 3s
Lower Control Limit (LCL) = A - 3s
The UCL and LCL can be used to construct control charts that are
useful in observing trends in performance. The control limits must be
replaced by method performance criteria as they become available from the
U.S. EPA.
8.5 The laboratory is required to spike all. sample cartridges (Tenax and
Tenax/charcoal) with internal standard.
8.6 Each day, the analyst must demonstrate through analysis of blank
Tenax and Tenax/charcoal cartridges and organic-free reagent water that
interferences from the analytical system are under control.
8.7 The daily GC/MS performance tests required for this method are
described in Method 8240. ..
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
5040A - 8 Revision 1
September 1994
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10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHC's Using VOST.
EPA/600/8-84-007, March 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014a, January 1986.
5040A - 9 Revision 1
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N.
!.A«
fri'J!
Thermal
Desorption
Chamber
Flow to
GC/MS
Frit
/
Heated
Line
Analytical Trap
with Heating Coil
(0.3 cm diameter
by 25cm long)
HjO
Purge
Column
HeorN2
IrO
4-a
Vent
T
3
<_>
7
3%OV-| (Um)
Tenax (7.7cm)
Silica Gel (7.7cm)
Charcoal (7.7cm)
Figure 1. Schematic diagram of trap desorplton/analysis system.
5040A - 10
Revision 1
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METHOD 5040A
ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN
GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE
(VOST)
( Start J
7.1.1 Assemble
purge and trap
desorption
device.
7.1.2 Connect
thermal
desorption
device;
calib. system.
7.2.1 Select
internal
standard.
7.2.3 Prepare
calibration
standards using
flash evaporat.
technique.
7.2.4 Direct
gas flow
through traps.
7.2.4 Expel
contents of
syringe through
GC injection
port.
7.2.4 Analyze
trap by P-T-D
GC/MS
procedure.
7.2.5 Analyze
each calib.
•tandard for
both cartridges
(see 7.3).
7.2.5 Tabulate
area response
and calculate
response factor.
7.2.6 Verify
response
factor each
day.
7.3 Place
sample
cartridge in
desorp. apparatus;
desorb in P-T.
7.3 Desorb
into GC/MS
system.
7.4.1
Quantatively
identify
volatile POHCs.
7.5.1 Use
primary
characteristic
ion for
quantitation.
7.5.1.1
Calculate
amount of analyte
in sample.
7.5;1.3 Sum
amount of POHCs
of interest for
each pair of
traps.
7.5.1.4 Examine
blanks data for
signs of residual
contamination.
7.5.1.5 Compare
int. std.
recoveries to
Section 8.4
control limits.
c
Stop
5040A - 11
Revision 1
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5041
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METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN (VOST): WIDE-BORE CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 This method describes the analysis of volatile principal organic
hazardous constituents (POHCs) collected from the stack gas effluents of
hazardous waste incinerators using the VOST methodology (!•). For a comprehensive
description of the VOST sampling methodology see Method 0030. The following
compounds may be determined by this method:
Compound Name
CAS No.1
Acetone
Acrylonitrile
Benzene
Bromodi chl oromethane
Bromoformb
Bromomethane0
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chl orodi bromomethane
Chloroethane0
Chloroform
Chl oromethane0
Di bromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene15
lodomethane
Methylene chloride
Styreneb
1 , 1 , 2 , 2 -Tetrachl oroethaneb
Tetrachloroethene
Toluene
67-64-1
107-1.3-1
71-43-2
75-27-4
75-25-2
74-83-9
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
74-95-3
75-35-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-01-5
10061-02-6
100-41-4
74-88-4
75-09-2
100-42-5
79-34-5
127-18-4
108-88-3
(continued)
5041 - 1
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Compound Name CAS No.'
1,1,1-Trichloroethane 71-55-6
1,1,2-Trichloroethane 79-00-5
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
l,2,3-Trichloropropaneb 96-18-4
Vinyl chloride0 75-01-4
Xylenesb
a Chemical Abstract Services Registry Number.
b Boiling point of this compound is above 132°C. Method 0030 is not
appropriate for quantitative sampling of this analyte.
0 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 for
discussion.
1.2 This method is most successfully applied to the analysis of non-polar
organic compounds with boiling points between 30°C and 100°C. Data are applied
to the calculation of destruction and removal efficiency (ORE), with limitations
discussed below.
1.3 This method may be applied to analysis of many compounds which boil
above 100°C, but Method 0030 is always inappropriate for collection of compounds
with boiling points above 132°C. All target analytes with boiling points greater
than 132°C are so noted in the target analyte list presented in Sec. 1.1. Use
of Method 0030 for collection of compounds boiling between 100°C and 132°C is
often possible, and must be decided based on case by case inspection of
information such as sampling method collection efficiency, tube desorption
efficiency, and analytical method precision and bias. An organic compound with
a boiling point below 30°C may break through the sorbent under the conditions
used for sample collection. Quantitative values obtained for compounds with
boiling points below 30°C must be qualified, since the value obtained represents
a minimum value for the compound if breakthrough has occurred. In certain cases,
additional QC measures may have been taken during sampling very low boilers with
Method 0030. This information should be considered during the data
interpretation stage.
When Method 5041 is used for survey analyses, values for compounds boiling
above 132°C may be reported and qualified since the quantity obtained represents
a minimum value for the compound. These minimum values should not be used for
trial burn ORE calculations or to prove insignificant risk.
1.4 The VOST analytical methodology can be used to quantitate volatile
organic compounds that are insoluble or slightly soluble in water. When
volatile, water soluble compounds are included in the VOST organic compound
analyte list, quantitation limits can be expected to be approximately ten times
5041 - 2 Revision 0
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higher than quantitation limits for water insoluble compounds (if the compounds
can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®) is poor.
1.5 Overall sensitivity of the method is dependent upon the level of
interferences encountered in the sample and the presence of detectable
concentrations of volatile POHCs in blanks. The target detection limit of this
method is 0.1 jug/m3 (ng/L) of flue gas, to permit calculation of a ORE equal to
or greater than 99.99% for volatile POHCs which may be present in the waste
stream at 100 ppm. The upper end of the range of applicability of this method
is limited by the dynamic range of the analytical instrumentation, the overall
loading of organic compounds on the exposed tubes,, and breakthrough of the
volatile POHCs on the sorbent traps used to collect the sample. Table 1 presents
retention times and characteristic ions for volatile compounds which can be
determined by this method. Table 2 presents method detection limits for a range
of volatile compounds analyzed by the wide-bore VOST methodology.
1.6 The wide-bore VOST analytical methodology is restricted to use by,
or under the supervision of, analysts experienced in the use of sorbent media,
purge-and-trap systems, and gas chromatograph/mass spectrometers, and skilled in
the interpretation of mass spectra and their use as a. quantitative tool.
2.0 SUMMARY OF METHOD
2.1 The sorbent tubes are thermally desorbed by heating and purging with
organic-free helium. The gaseous effluent from the tubes is bubbled through
pre-purged organic-free reagent water and trapped on an analytical sorbent trap
in a purge-and-trap unit (Figure 2). After desorption, the analytical sorbent
trap is heated rapidly and the gas flow from the analytical trap is directed to
the head of a wide-bore column under subambient conditions. The volatile organic
compounds desorbed from the analytical trap are separated by temperature
programmed high resolution gas chromatography and detected by continuously
scanning low resolution mass spectrometry (Figure 3). Concentrations of volatile
organic compounds are calculated from a multi-point calibration curve, using the
method of response factors.
3.0 INTERFERENCES
3.1 Sorbent tubes which are to be analyzed for volatile organic compounds
can be contaminated by diffusion of volatile organic compounds (particularly
Freon® refrigerants and common organic solvents) through the external container
(even through a Teflon® lined screw cap on a glass container) and the Swagelok®
sorbent tube caps during shipment and storage. The sorbent tubes can also be
contaminated if organic solvents are present in the analytical laboratory. The
use of blanks is essential to assess the extent of any contamination. Field
blanks must be prepared and taken to the field. The end caps of the tubes are
removed for the period of time required to exchange two pairs of traps on the
VOST sampling apparatus. The tubes are recapped and shipped and handled exactly
as the actual field samples are shipped and handled. At least one pair of field
blanks is included with each six pairs of sample cartridges collected.
5041 - 3 Revision 0
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3.2 At least one pair of blank cartridges (one Tenax-GC®, one
Tenax-GC®/charcoal) shall be included with shipment of cartridges to a hazardous
waste incinerator site as trip blanks. These trip blanks will be treated like
field blanks except that the end caps will not be removed during storage at the
site. This pair of traps will be analyzed to monitor potential contamination
which may occur during storage and shipment.
3.3 Analytical system blanks are required to demonstrate that
contamination of the purge-and-trap unit and the gas chromatograph/mass
spectrometer has not occurred or that, in the event of analysis of sorbent tubes
with very high concentrations of organic compounds, no compound carryover is
occurring. Tenax® from the same preparation batch as the Tenax® used for field
sampling should be used in the preparation of the method (laboratory) blanks.
A sufficient number of cleaned Tenax® tubes from the same batch as the field
samples should be reserved in the laboratory for use as blanks.
3.4 Cross contamination can occur whenever low-concentration samples are
analyzed after high-concentration samples, or when several high-concentration
samples are analyzed sequentially. When an unusually concentrated sample is
analyzed, this analysis should be followed by a method blank to establish that
the analytical system is free of contamination. If analysis of a blank
demonstrates that the system is contaminated, an additional bake cycle should be
used. If the analytical system is still contaminated after additional baking,
routine system maintenance should be performed: the analytical trap should be
changed and conditioned, routine column maintenance should be performed (or
replacement of the column and conditioning of the new column, if necessary), and
bakeout of the ion source (or cleaning of the ion source and rods, if required).
After system maintenance has been performed, analysis of a blank is required to
demonstrate that the cleanliness of the system is acceptable.
3.5 Impurities in the purge gas and from organic compounds out-gassing
in tubing account for the majority of contamination problems. The analytical
system must be demonstrated to be free from contamination under the conditions
of the analysis by analyzing two sets of clean, blank sorbent tubes with organic-
free reagent purge water as system blanks. The analytical system is acceptably
clean when these two sets of blank tubes show values for the analytes which are
within one standard deviation of the normal system blank. Use of plastic
coatings, non-Teflon® thread sealants, or flow controllers with rubber
components should be avoided.
3.6 VOST tubes are handled in the laboratory to spike standards and to
position the tubes within the desorption apparatus. When sorbent media are
handled in the laboratory atmosphere, contamination is possible if there are
organic solvents in use anywhere in the laboratory. It is therefore necessary
to make daily use of system blanks to monitor the cleanliness of the sorbents and
the absence of contamination from the analytical system. A single set of system
blank tubes shall be exposed to normal laboratory handling procedures and
analyzed as a sample. This sample should be within one standard deviation of
normal VOST tube blanks to demonstrate lack of contamination of the sorbent
media.
3.7 If the emission source has a high concentration of non-target organic
compounds (for example, hydrocarbons at concentrations of hundreds of ppm), the
5041 - 4 Revision 0
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presence of these non-target compounds will interfere with the performance of the
VOST analytical methodology. If one or more of the compounds of interest
saturates the chromatographic and mass spectrometric instrumentation, no
quantitative calculations can be made and the tubes which have been sampled under
the same conditions will yield no valid data for any of the saturated compounds.
In the presence of a very high organic loading, even if the compounds of interest
are not saturated, the instrumentation is so saturated that the linear range has
been surpassed. When instrument saturation occurs, it is possible that compounds
of interest cannot even be identified correctly because a saturated mass
spectrometer may mis-assign masses. Even if compounds of interest can be
identified, accurate quantitative calculations are impossible at detector
saturation. No determination can be made at detector saturation, even if the
target compound itself is not saturated. At detector saturation, a negative bias
will be encountered in analytical measurements and no accurate calculation can
be made for the Destruction and Removal Efficiency if analytical values may be
biased negatively.
3.8 The recoveries of the surrogate compounds, which are spiked on the
VOST tubes immediately before analysis, should be monitored carefully as an
overall indicator of the performance of the methodology. Since the matrix of
stack emissions is so variable, only a general guideline for recovery of 50-150%
can be used for surrogates. The analyst cannot use the surrogate recoveries as
a guide for correction of compound recoveries. The surrogates are valuable only
as a general indicator of correct operation of the methodology. If surrogates
are not observed or if recovery of one or more of the surrogates is outside the
50-150% range, the VOST methodology is not operating correctly. The cause of the
failure in the methodology is not obvious. The matrix of stack emissions
contains large amounts of water, may be highly acidic, and may contain large
amounts of target and non-target organic compounds. Chemical and surface
interactions may be occurring on the tubes. If recoveries of surrogate compounds
are extremely low or surrogate compounds cannot even be identified in the
analytical process, then failure to observe an analyte may or may not imply that
the compound of interest has been removed from the emissions with a high degree
of efficiency (that is, the Destruction and Removal Efficiency for that analyte
is high).
4.0 APPARATUS AND MATERIALS
4.1 Tube desorption apparatus: Acceptable performance of the methodology
requires: 1) temperature regulation to ensure that tube temperature during
desorption is regulated to 180°C + 10°; 2) good contact between tubes and the
heating apparatus to ensure that the sorbent bed is thoroughly and uniformly
heated to facilitate desorption of organic compounds; and 3) gas-tight
connections to the ends of the tubes to ensure flow of desorption gas through the
tubes without leakage during the heating/desorption process. A simple clamshell
heater which will hold tubes which are 3/4" in outer diameter will perform
acceptably as a desorption apparatus.
4.2 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: a sample purge vessel, an analytical trap, and a
desorber. Complete devices are commercially available from a variety of sources,
or the separate components may be assembled. The cartridge thermal desorption
5041 - 5 Revision 0
September 1994
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apparatus is connected to the sample purge vessel by 1/8" Teflon® tubing
(unheated transfer line). The tubing which connects the desorption chamber to
the sample purge vessel should be as short as is practical.
4.2.1 The sample purge vessel is required to hold 5 ml of organic-
free reagent water, through which the gaseous effluent from the VOST tubes
is routed. The water column should be at least 3 cm deep. The gaseous
headspace between the water column and the analytical trap must have a
total volume of less than 15 ml. The purge gas must pass through the
water column as finely divided bubbles with a diameter of less than 3 mm
at the origin. The sample purger shown in Figure 4 meets these
requirements. Alternate sample purging vessels may be used if equivalent
performance is demonstrated.
4.2.2 The analytical trap must be at least 25 cm and have an
internal diameter of at least 0.105 in. The analytical trap must contain
the following components:
2,6-diphenylene oxide polymer: 60/80 mesh, chromatograph grade
(Tenax-GC®, or equivalent)
methyl silicone packing: OV-1 (3%) on Chromosorb-W 60/80
mesh, or equivalent
silica gel: 35/60 mesh, Davison grade 15 or
equivalent
coconut charcoal: prepare from Barneby Cheney,
CA-580-26, or equivalent, by
crushing through 26 mesh
screen.
The proportions are: 1/3 Tenax-GC®, 1/3 silica gel, and 1/3
charcoal, with approximately 1.0 cm of methyl silicone packing. The
analytical trap should be conditioned for four hours at 180°C with gas flow
(10 mL/min) prior to use in sample analysis. During conditioning, the
effluent of the trap should not be vented to the analytical column. The
thermal desorption apparatus is connected to the injection system of the
mass spectrometer by a transfer line which is heated to 100°C.
4.2.3 The desorber must be capable of rapidly heating the analytical
trap to 180°C for desorption. The polymer section of the trap should not
exceed 180°C, and the remaining sections should not exceed 220°C, during
bake-out mode.
4.3 Gas chromatograph/mass spectrometer/data system:
4.3.1 Gas chromatograph: An analytical system complete with a
temperature programmable oven with sub-ambient temperature capabilities
and all required accessories, including syringes, analytical columns, and
gases.
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4.3.2 Chromatographic column: 30 m x 0.53 mm ID wide-bore fused
silica capillary column, 3 /Ltm film thickness, DB-624 or equivalent.
4.3.3 Mass spectrometer: capable of scanning from 35-260 amu every
second or less, using 70 eV (nominal) electron energy in the electron
ionization mode and producing a mass spectrum that meets all of the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene (BFB) is injected
into the water in the purge vessel.
4.3.4 Gas chromatograph/mass spectrometer interface: Any gas
chromatograph to mass spectrometer interface that gives acceptable
calibration points at 50 ng or less per injection of each of the analytes,
and achieves the performance criteria for 4-bromofluorobenzene shown in
Table 3, may be used. If a glass jet separator is used with the wide-bore
column, a helium make-up flow of approximately 15 ml, introduced after the
end of the column and prior to the entrance of the effluent to the
separator, will be required for optimum performance.
4.3.5 Data system: A computer system that allows the continuous
acquisition and storage on machine readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
interfaced to the mass spectrometer. The computer must have software that
allows searching any gas chromatographic/mass spectrometric data file for
ions of a specified mass and plotting such ion abundances versus time or
scan number. This type of plot is defined as an Extracted Ion Current
Profile (EICP). Software must also be available that allows the
integration of the ion abundances in any EICP between specified time or
scan number limits. The most recent version of the EPA/NIST Mass Spectral
Library should also be available.
4.4 Wrenches: 9/16", 1/2", 7/16", and 5/16".
4.5 Teflon® tubing: 1/8" diameter.
4.6 Syringes: 25 /xL syringes (2), 10 p.1 syringes (2).
4.7 Fittings: 1/4" nuts, 1/8" nuts, 1/16" nuts, 1/4" to 1/8" union, 1/4"
to 1/4" union, 1/4" to 1/16" union.
4.8 Adjustable stand to raise the level of the desorption unit, if
required.
4.9 Volumetric flasks: 5 ml, class A with ground glass stopper.
4.10 Injector port or equivalent, heated to 180°C for loading standards
onto VOST tubes prior to analysis.
4.11 Vials: 2 ml, with Teflon® lined screw caps or crimp tops.
4.12 Syringe: 5 ml, gas-tight with shutoff valve.
5041 - 7 Revision 0
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5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2.1 It is advisable to maintain the stock of organic-free reagent
water generated for use in the purge-and-trap apparatus with a continuous
stream of inert gas bubbled through the water. Continuous bubbling of the
inert gas maintains a positive pressure of inert gas above the water as a
safeguard against contamination.
5.3 Methanol, CH3OH. Pesticide quality or equivalent. To avoid
contamination with other laboratory solvents, it is advisable to maintain a
separate stock of methanol for the preparation of standards for VOST analysis and
to regulate the .use of this methanol very carefully.
5.4 Stock standard solutions - Can be prepared from pure standard
materials or can be purchased as certified solutions. Stock standard solutions
must be prepared in high purity methanol. All preparation of^standards should
take place in a hood, both to avoid contamination and to ensure safety of the
analyst preparing the standards.
5.4.1 Place about 4 ml of high purity methanol in a 5 ml volumetric
flask. Allow the flask to stand, unstoppered, for about 10 min, or until
all alcohol wetted surfaces have dried.
5.4.1.1 Add appropriate volumes of neat liquid chemicals
or certified solutions, using a syringe of the appropriate volume.
Liquid which is added to the volumetric flask must fall directly
into the alcohol without contacting the neck of the flask. Gaseous
standards can be purchased as methanol solutions from several
commercial vendors.
5.4.1.2 Dilute to volume with high purity methanol,
stopper, and then mix by inverting the .flask several times. Calcu-
late concentration by the dilution of certified solutions or neat
chemicals.
5.4.2 Transfer the stock standard solution into a Teflon® sealed
screw cap bottle. An amber bottle may be used. Store, with minimal
headspace, at -10°C to -20°C, and protect from light.
5.4.3 Prepare fresh standards every two months for gases. Reactive
compounds such as styrene may need to be prepared more frequently. All
other standards must be replaced after six months, or sooner if comparison
with check standards indicates a problem.
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5.5 Secondary dilution standards: Using stock standard solutions,
prepare, in high purity methanol, secondary dilution standards containing the
compounds of interest, either singly or mixed together. Secondary dilution
standards must be stored with minimal headspace and should be checked frequently
for signs of degradation or evaporation, especially just prior to preparing
calibration standards from them.
5.6 Surrogate standards: The recommended surrogates are toluene-d8,
4-bromofluorobenzene, and l,2-dichloroethane-d4. Other compounds may be used as
surrogate compounds, depending upon the requirements of the analysis. Surrogate
compounds are selected to span the elution range of the compounds of interest.
Isotopically labeled compounds are selected to preclude the observation of the
same compounds in the stack emissions. More than one surrogate is used so that
surrogate measurements can still be made even if analytical interferences with
one or more of the surrogate compounds are encountered. However, at least three
surrogate compounds should be used to monitor the performance of the methodology.
A stock surrogate compound solution in high purity methanol should be prepared
as described in Sec. 5.4, and a surrogate standard spiking solution should be
prepared from the stock at a concentration of 250 ^g/lQ ml in high purity
methanol. Each .pair of VOST tubes (or each individual VOST tube, if the tubes
are analyzed separately) must be spiked with 10 /iL of the surrogate spiking
solution prior to GC/MS analysis.
5.7 Internal standards: The recommended internal standards are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d5. Other compounds
may be used as internal standards as long as they have retention times similar
to the compounds being analyzed by GC/MS. The internal standards should be
distributed through the chromatographic elution range. Prepare internal standard
stock and secondary dilution standards in high purity methanol using the
procedures described in Sees. 5.2 and 5.3. The secondary dilution standard
should be prepared at a concentration of 25 mg/L of each of the internal standard
compounds. Addition of 10 jul. of this internal standard solution to each pair
of VOST tubes (or to each VOST tube, if the tubes are analyzed individually) is
the equivalent of 250 ng total.
5.8 4-Bromofluorobenzene (BFB) standard: A standard solution containing
25 ng///L of BFB in high purity methanol should be prepared for use as a tuning
standard.
5.9 Calibration standards: Calibration standards at a minimum of five
concentrations will be required from the secondary dilution of stock standards
(see Sees. 5.2 and 5.3). A range of concentrations for calibration can be
obtained by use of different volumes of a 50 mg/L methanol solution of the
calibration standards. One of the concentrations used should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in field samples but should not exceed the linear range of the GC/MS analytical
system (a typical range for a calibration would be 10, 50, 100, 350, and 500 ng,
for example). Each calibration standard should contain each analyte for
detection by this method. Store calibration standards for one week only in a
vial with no headspace.
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5.10 Great care must be taken to maintain the integrity of all standard
solutions. All standards of volatile compounds in methanol must be stored at
-10° to -20°C in amber bottles with Teflon® lined screw caps or crimp tops. In
addition, careful attention must be paid to the use of syringes designated for
a specific purpose or for use with only a single standard solution since cross
contamination of volatile organic standards can occurs very readily.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Method 0030 for the VOST Sampling Methodology.
6.2 VOST samples are collected on paired cartridges. The first of the
pair of sorbent cartridges is packed with approximately 1.6 g of Tenax-GC®
resin. The second cartridge of the pair is packed with Tenax-GC® and petroleum
based charcoal (3:1 by volume; approximately 1 g of each). In sampling, the
emissions gas stream passes through the Tenax-GC® layer first and then through
the charcoal layer. The Tenax-GC® is cleaned and reused; charcoal is not reused
when tubes are prepared. Sorbent is cleaned and the tubes are packed. The tubes
are desorbed and subjected to a blank check prior to being sent to the field.
When the tubes are used for sampling (see Figure 5 for a schematic diagram of the
Volatile Organic Sampling Train (VOST)), cooling water is circulated to the
condensers and the temperature of the cooling water is maintained near 0°C. The
end caps of the sorbent cartridges are placed in a clean, screw capped glass
container during sample collection.
6.3 After the apparatus is leak checked, sample collection is
accomplished by opening the valve to the first condenser, turning on the pump,
and sampling at a rate of 1 liter/min for 20 minutes. The volume of sample for
any pair of traps should not exceed 20 liters. An alternative set of conditions
for sample collection requires sampling at a reduced flow rate, where the overall
volume of sample collected is 5 liters at a rate of 0.25 L/min for 20 minutes.
The 20 minute period is required for collecting an integrated sample.
6.4 Following collection of 20 liters of sample, the train is leak
checked a second time at the highest pressure drop encountered during the run to
minimize the chance of vacuum desorption of organics from the Tenax®.
6.5 The train is returned to atmospheric pressure and the two sorbent
cartridges are removed. The end caps are replaced and the cartridges are placed
in a suitable environment for storage and transport until analysis. The sample
is considered invalid if the leak test does not meet specifications.
6.6 A new pair of cartridges is placed in the VOST, the VOST is leak
checked, and the sample collection process is repeated until six pairs of traps
have been exposed.
6.7 All sample cartridges are kept in coolers on cold packs after
exposure and during shipment. Upon receipt at the laboratory, the cartridges are
stored in a refrigerator at 4°C until analysis.
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7.0 PROCEDURE
7.1 Recommended operating conditions for cartridge desorber,
purge-and-trap unit, and gas chromatograph/mass spectrometer using the wide-bore
column are:
Cartridge Desorption Oven
Desorb Temperature
Desorb Time
Desorption Gas Flow
Desorption/Carrier Gas
Purqe-and-Trap Concentrator
Analytical Trap Desorption Flow
Purge Temperature
Purge Time
Analytical Trap Desorb Temperature
Analytical Trap Desorb Time
Gas Chromatoqraph
Column
Carrier Gas Flow
Makeup Gas Flow
Injector Temperature
Transfer Oven Temperature
Initial Temperature
Initial Hold Time
Program Rate
Final Temperature
Final Hold Time
Mass Spectrometer
Manifold Temperature
Scan Rate
Mass Range
Electron Energy
Source Temperature
180°C
11 minutes
40 mL/min
Helium, Grade 5.0
2.5 mL/min helium
Ambient
11 minutes
180°C
5 minutes
DB-624, 0.53 mm ID x 30 m thick
film (3 )Ltm) fused silica capillary,
or equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
240°C
1 minute, or until elution ceases
105°C
1 sec/cycle
35-260 amu
70 eV (nominal)
According to
specifications
manufacturer's
7.2 Each GC/MS system must be hardware tuned to meet the criteria in
Table 3 for a 50 ng injection of 4-bromofluorobenzene (2 /zL injection of the BFB
standard solution into the water of the purge vessel). No analyses may be
initiated until the criteria presented in Table 3 are met.
7.3 Assemble a purge-and-trap device that meets the specifications in
Method 5030. Condition the analytical trap overnight at 180°C in the purge mode,
with an inert gas flow of at least 20 mL/min. Prior to use each day, condition
the trap for 10 minutes by backflushing at 180°C, with the column at 220°C.
7.4 . Connect the purge-and-trap device to a gas chromatograph.
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7.5 Assemble a VOST tube desorption apparatus which meets the
requirements of Sec. 4.1.
7.6 Connect the VOST tube desorption apparatus to the purge-and-trap
unit.
7.7 Calibrate the instrument using the internal standard procedure, with
standards and calibration compounds spiked onto cleaned VOST tubes for
calibration.
7.7.1 Compounds in methanolic solution are spiked onto VOST tubes
using the flash evaporation technique. To perform flash evaporation, the
injector of a gas chromatograph or an equivalent piece of equipment is
required.
7.7.1.1 Prepare a syringe with the appropriate volume of
methanolic standard solution (either surrogates, internal standards,
or calibration compo.unds).
7.7.1.2 With the injector port heated to 180°C, and with
an inert gas flow of 10 mL/min through the injector port, connect
the paired VOST tubes (connected as in Figure 1, with gas flow in
the same direction as the sampling gas flow) to the injector port;
tighten with a wrench so that there is no leakage of gas. If
separate tubes are being analyzed, an individual Tenax® or
Tenax®/charcoal tube is connected to the injector.
7.7.1.3 After directing the gas flow through the VOST
tubes, slowly inject the first standard solution over a period of 25
seconds. Wait for 5 sec before withdrawing the syringe from the
injector port.
7.7.1.4 Inject a second standard (if required) over a
period of 25 seconds and wait for 5 sec before withdrawing the
syringe from the injector port.
7.7.1.5 Repeat the sequence above as required until all of
the necessary compounds are spiked onto the VOST.tubes.
7.7.1.6 Wait for 30 seconds, with gas flow, after the last
spike before disconnecting the tubes. .The total time the tubes are
connected to the injector port with gas flow should not exceed 2.5
minutes. Total gas flow through the tubes during the spiking
process should not exceed 25 mL to prevent break through of adsorbed
compounds during the spiking process. To allow more time for
connecting and disconnecting tubes, an on/off valve may be installed
in the gas line to the injector port so that gas is not flowing
through the tubes during the connection/disconnection process.
7.8 Prepare the purge-and-trap unit with 5 ml of organic-free reagent
water in the purge vessel.
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7.9 Connect the paired VOST tubes to the gas lines in the tube desorption
unit. The tubes must be connected so that the gas flow during desorption will
be opposite to the flow of gas during sampling: i.e., the tube desorption gas
passes through the charcoal portion of the tube first. An on/off valve may be
installed in the gas line leading to the tube desorption unit in order to prevent
flow of gas through the tubes during the connection process.
7.10 Initiate tube desorption/purge and heating of the VOST tubes in the
desorption apparatus.
7.11 Set the oven of the gas chromatograph to subambient temperatures by
cooling with liquid nitrogen.
7.12 Prepare the GC/MS system for data acquisition.
7.13 At the conclusion of the tube/water purge time, attach the analytical
trap to the gas chromatograph, adjust the purge-and-trap device to the desorb
mode, and initiate the gas chromatographic program and the GC/MS data
acquisition. Concurrently, introduce the trapped materials to the gas
ehromatographic column by rapidly heating the analytical trap to 180°C while
backflushing the trap with inert gas at 2.5 mL/min for 5 min. Initiate the
program for the gas chromatograph and simultaneously initiate data acquisition
on the GC/MS system.
7.14 While the analytical trap is being desorbed into the gas
chromatograph, empty the purging vessel. Wash the purging vessel with a minimum
of two 5 ml flushes of organic-free reagent water (or methanol followed by
organic-free reagent water) to avoid carryover of analytes into subsequent
analyses.
7.15 After the sample has been desorbed, recondition the analytical trap
by employing a bake cycle on the purge-and-trap unit. The analytical trap may
be baked at temperatures up to 220°C. However, extensive use of high
temperatures to recondition the trap will shorten the useful life of the
analytical trap. After approximately 11 minutes, terminate the trap bake and
cool the trap to ambient temperatures in preparation for the next sample. This
procedure is a convention for reasonable samples and should be adequate if the
concentration of contamination does not saturate the analytical system. If the
organic compound concentration is so high that the analytical system is saturated
beyond the point where even extended system bakeout is not sufficient to clean
the system, a more extensive system maintenance must be performed. To perform
extensive system maintenance, the analytical trap is replaced and the new trap
is conditioned. Maintenance is performed on the GC column by removing at least
one foot from the front end of the column. If the chromatography does not
recover after column maintenance, the chromatographic column must be replaced.
The ion source should be baked out and, if the bakeout is not sufficient to
restore mass spectrometric peak shape and sensitivity, the ion source and the
quadrupole rods must be cleaned.
7.16 Initial calibration for the analysis of VOST tubes: It is essential
that calibration be performed in the mode in which analysis will be performed.
If tubes are being analyzed as pairs, calibration standards should be prepared
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on paired tubes. If tubes are being analyzed individually, a calibration should
be performed on individual Tenax® only tubes and Tenax®/charcoal tubes.
7.16.1 Prepare the calibration standards by spiking VOST tubes
using the procedure described in Sec. 7.7.1. Spike each pair of VOST
tubes (or each of the individual tubes) immediately before analysis.
Perform the calibration analyses in order from low concentration to high
to minimize the compound carryover. Add 5.0 ml of organic-free reagent
water to the purging vessel. Initiate tube desorb/purge according to the
procedure described above.
7.16.2 Tabulate the area response of the characteristic primary
ions (Table 1) against concentration for each target compound, each
surrogate compound, and each internal standard. The first criterion for
quantitative analysis is correct identification of compounds. The
compounds must elute within + 0.06 retention time units of the elution
time of the standard analyzed on the same analytical system on the day of
the analysis. The analytes should be quantitated relative to the closest
eluting internal standard, according to the scheme shown in Table 4.
Calculate response factors (RF) for each compound relative to the internal
standard shown in Table 4. The internal standard selected for the
calculation of RF is the internal standard that has a retention time
closest to the compound being measured. The RF is calculated as follows:
RF - (Ax/Cis)/(Ais/Cx)
where:
Ax = area of the characteristic ion for the compound being
measured.
Ais = area of the characteristic ion for the specific internal
standard.
Cis = concentration of the specific internal standard.
Cx = concentration of the compound being measured.
7.16.3 The average RF must be calculated for each compound. A
system performance check should be made before the calibration curve is
used. Five compounds (the System Performance Check Compounds, or SPCCs)
are checked for a minimum average response factor. These compounds are
chloromethane, 1,1-dichloroethane, bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform). These compounds typically have RFs
of 0.4 - 0.6, and are used to check compound instability and check for
degradation caused by contaminated lines or active sites in the system.
Examples of these occurrences are:
7.16.3.1 Chloromethane: This compound is the most likely
compound to be lost if the purge flow is too fast.
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7.16.3.2 Bromoform: This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in transfer lines may adversely
affect response. Response of the primary quantitation ion (m/z 173)
is directly affected by the tuning for 4-bromofluorobenzene at the
ions of masses 174 and 176. Increasing the ratio of ions 174 and 176
to mass 95 (the base peak of the mass spectrum of
bromofluorobenzene) may improve bromoform response.
7.16.3.3 1,1,2,2-Tetrachloroethane and 1,1-dichloroethane:
These compounds are degraded by contaminated transfer lines in
purge-and-trap systems and/or active sites in trapping materials.
7.16.4 Using the response factors from the initial calibration,
calculate the percent relative standard deviation (%RSD) for the
Calibration Check Compounds (CCCs).
%RSD = (SD/X) x 100
where:
%RSD
RF;
RF
SD
percent relative standard deviation
individua^ RF measurement
mean of 5 initial RFs for a compound (the 5 points
over the calibration range)
standard deviation of average RFs for a compound,
where SD is calculated:
.SD =
A
(RFi-RF)
^-1
The %RSD for each individual CCC should be less than 30 percent.
This criterion must be met in order for the individual calibration to be
valid. The CCCs are: 1,1-dichloroethene, chloroform, 1,2-dichloropropane,
toluene, ethylbenzene, and vinyl chloride.
7.17 Daily GC/MS Calibration
7.17.1 Prior to the analysis of samples, purge 50 ng of the
4-bromofluorobenzene standard. The resultant mass spectrum for the BFB
must meet all of the criteria given in Table 3 before sample analysis
begins^ These criteria must be demonstrated every twelve hours of
operation.
7.17.2 The initial calibration curve (Sec. 7.16) for each compound
of interest must be checked and verified once every twelve hours of
analysis time. This verification is accomplished by analyzing a
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calibration standard that is at a concentration near the midpoint
concentration for the working range of the GC/MS and checking the SPCC
(Sec. 7.16.3) and CCC (Sec. 7.16.4).
7.17.3 System Performance Check Compounds (SPCCs): A system
performance check must be made each twelve hours of analysis. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the initial
calibration. If the minimum response factors are not achieved, the system
must be evaluated, and corrective action must be taken before analysis is
allowed to begin. The minimum response factor for volatile SPCCs is 0.300
(0.250 for bromoform) . If these minimum response factors are not
achieved, some possible problems may be degradation of the standard
mixture, contamination of the injector port, contamination at the front
end of the analytical column, and active sites in the column or
chromatographic system. If the problem is active sites at the front end
of the analytical column, column maintenance (removal of approximately 1
foot from the front end of the column) may remedy the problem.
7.17.4 Calibration Check Compounds: After the system performance
check has been met, CCCs listed in Sec. 7.16.4 are used to check the
validity of the initial calibration. Calculate the percent difference
using the following equation:
- RFC) x 100
% Difference = - ; -
where:
RFj = average response factor from initial calibration
RFC = response factor from current calibration check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. Benzene, toluene, and
styrene will have problems with response factors if Tenax® decomposition
occurs (either as a result of sampling exposure or temperature
degradation), since these compounds are decomposition products of Tenax®.
If the percent difference for each CCC is less than 25%, the initial
calibration is assumed to be valid. If the criterion of percent
difference less than 25% is not met for any one CCC, corrective action
MUST be taken. Problems similar to those listed under SPCCs could affect
this criterion. If a source of the problem cannot be determined after
corrective action is taken, a new five-point calibration curve MUST be
generated. The criteria for the CCCs MUST be met before quantitative
analysis can begin.
7.17.5 Internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last check calibration (12 hr), the
chromatographic system must be inspected for malfunctions and corrections
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must be made, as required. A factor which may influence the retention
times of the internal standards on sample tubes is the level of overall
organic compound loading on the VOST tubes. If the VOST tubes are very
highly loaded with either a single compound or with multiple organic
compounds, retention times for standards and compounds of interest will be
affected. If the area for the primary ion of any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration check, the gas chromatograph and mass spectrometer should be
inspected for malfunctions and corrections must be made, as appropriate.
If the level of organic loading of samples is high, areas for the primary
ions of both compounds of interest and standards will be adversely
affected. Calibration check standards should not be subject to variation,
since the concentrations of organic compounds on these samples are set to
be within the linear range of the instrumentation. If instrument
malfunction has occurred, analyses of samples performed under conditions
of malfunction may be invalidated.
7.18 GC/MS Analysis of Samples
7.18.1 Set up the cartridge desorption unit, purge-and-trap
unit, and GC/MS as described above.
7.18.2 BFB tuning criteria and daily GC/MS calibration check
criteria must be met before analyzing samples.
7.18.3 Adjust the helium purge gas flow rate (through the
cartridges and purge vessel) to approximately 40 mL/min. Optimize the
flow rate to provide the best response for chloromethane and bromoform, if
these compounds are analytes. A flow rate which is too high reduces the
recovery of chloromethane, and an insufficient gas flow rate reduces the
recovery of bromoform.
7.18.4 The first analysis performed after the tuning check and
the calibration or daily calibration check is a method blank. The method
blank consists of clean VOST tubes (both Tenax® and Tenax®/charcoal) which
are spiked with surrogate compounds and internal standards according to
the procedure described in Sec. 7.7.1. The tubes which are used for the
method blanks should be from the same batch of sorbent as the sorbent used
for the field samples. After the tubes are cleaned and prepared for
shipment to the field, sufficient pairs of tubes should be retained from
the same batch in the laboratory to provide method blanks during the
analysis.
7.18.5 The organic-free reagent water for the purge vessel for
the analysis of each of the VOST samples should be supplied from the
laboratory inventory which is maintained with constant bubbling of inert
gas to avoid contamination.
7.18.6 If the analysis of a pair of VOST tubes has a
concentration of analytes that exceeds the initial calibration range, no
reanalysis of desorbed VOST tubes is possible. An additional calibration
point can be added to bracket the higher concentration encountered in the
samples so that the calibration database encompasses six or more points.
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Alternatively, the data may be flagged in the report as "extrapolated
beyond the upper range of the calibration." The use of the secondary ions
shown in Table 1 is permissible only in the case of interference with the
primary quantitation ion. Use of secondary ions to calculate compound
concentration in the case of saturation of the primary ion is not an
acceptable procedure, since a negative bias of an unpredictable magnitude
is introduced into the quantitative data when saturation of the mass
spectrum of a compound is encountered. If high organic loadings, either
of a single compound or of multiple compounds, are encountered, it is
vital that a method blank be analyzed prior to the analysis of another
sample to demonstrate that no compound carryover is occurring. If
concentrations of organic compounds are sufficiently high that carryover
problems are profound, extensive bakeout of the purge-and-trap unit will
be required. Complete replacement of the contaminated analytical trap,
with the associated requirement for conditioning the new trap, may also be
required for VOST samples which show excessive concentrations of organic
compounds. Other measures which might be required for decontamination of
the analytical system include bakeout of the mass spectrometer,
replacement of the filament of the mass spectrometer, cleaning of the ion
source of the mass spectrometer, and/or (depending on the nature of the
contamination) maintenance of the chromatographic column or replacement of
the chromatographic column, with the associated requirement for
conditioning the new chromatographic column.
7.19 Data Interpretation
7.19.1 Qualitative analysis:
7.19.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.19.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound specific
retention time will be accepted as meeting this criterion.
7.19.1.1.2 The RRT of the sample component is + 0.06
RRT units of the RRT of the standard component.
7.19.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion with an abundance of 50% in the
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reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.)
7.19.1.1.4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum of
the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
7.19.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds. When
analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.19.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification
are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within ± 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
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Computer generated library search routines should not use
normalization routines that would misrepresent the library or
unknown spectra when compared to each other. Only after visual
comparison of sample with the nearest library searches will the mass
spectral ' interpretation specialist assign a tentative
identification.
7.19.2 Quantitative analysis:
7.19.2.1 When a compound has been identified, the
quantitative analysis of that compound will be based on the
integrated abundance from the extracted ion current profile of the
primary characteristic ion for that compound (Table 1). In the
event that there. is interference with the primary ion so that
quantitative measurements cannot be made, a secondary ion may be
used.
NOTE: Use of a secondary ion to perform quantitative
calculations in the event of the saturation of the
primary ion is not an acceptable procedure because of
the unpredictable extent of the negative bias which is
introduced. Quantitative calculations are performed
using the internal standard technique. The internal
standard used to perform quantitative calculations shall
be the internal standard nearest the retention time of
a given analyte (see Table 4).
7.19.2.2 Calculate the amount of each identified analyte
from the VOST tubes as follows:
Amount (ng) = (A8Cis)/(Ai8RF)
where:
As = area of the characteristic ion for the analyte to be
measured.
A:. = area of the characteristic ion of the internal standard.
•IS
Cis = amount (ng) of the internal standard.
7.19.2.3 The choice of methods for evaluating data
collected using the VOST methodology for incinerator trial burns is
a regulatory decision. Various procedures are used to decide
whether blank correction should be performed and how blank
correction should be performed. Regulatory agencies to which VOST
data are submitted also vary'in their preferences for data which are
or which are not blank corrected.
7.19.2.4 The total amount of the POHCs of interest
collected on a pair of traps should be summed.
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7.19.2.5 The occurrence of high concentrations of analytes
on method blank cartridges indicates possible residual contamination
of sorbent cartridges prior to shipment and use at the sampling
site. Data with high associated blank values must be qualified with
respect to validity, and all blank data should be reported
separately. No blank corrections should be made in this case.
Whether or not data of this type can be applied to the determination
of destruction and removal efficiency is a regulatory decision.
Continued observation of high concentrations of analytes on blank
sorbent cartridges indicates that procedures for cleanup and quality
control for the sampling tubes are inadequate. Corrective action
MUST be applied to tube preparation and monitoring procedures to
maintain method blank concentrations below detection limits for
analytes.
7.19.2.6 Where applicable, an estimate of concentration for
noncalibrated components in the sample may be made. The formulae
for quantitative calculations presented above should be used with
the following modifications: The areas Ax and Ais should be from the
total ion chromatograms, and the Response Factor for the
noncalibrated compound should be assumed to be 1. The nearest
eluting internal standard free from interferences in the total ion
chromatogram should be used to determine the concentration. The
concentration which is obtained should be reported indicating: (1)
that the value is an estimate; and (2) which internal standard was
used.
7.19.2.7 If any internal standard recoveries fall outside
the control limits established in Sec. 8.4, data for all analytes
determined for that cartridge(s) must be qualified with the
observation. Report results without correction for surrogate
compound recovery data. When duplicates are analyzed, report the
data obtained with the sample results.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum quality control requirements are
specified in Chapter One. In addition, this program should consist of an initial
demonstration of laboratory capability and an ongoing analysis of check samples
to evaluate and document data quality. The laboratory must maintain records to
document the quality of the data generated. Ongoing data quality .checks are
compared with established performance criteria to determine if the results of
analyses meet the performance characteristics of the method. When sample
analyses indicate atypical method performance, a quality control check standard
(spiked method blank) must be analyzed to confirm that the measurements were
performed in an in-control mode of instrument operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a method blank (laboratory blank sorbent tubes, reagent
water purge) that interferences from the analytical system, glassware, sorbent
tube preparation, and reagents are under control. Each time a new batch of
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sorbent tubes is analyzed, a method blank should be processed as a safeguard
against chronic laboratory contamination. Blank tubes which have been carried
through all the stages of sorbent preparation and handling should be used in the
analysis.
8.3 The experience of the analyst performing the GC/MS analyses is
invaluable to the success of the analytical methods. Each day that the analysis
is performed, the daily calibration check standard should be evaluated to
determine if the chromatographic and tube desorption systems are operating
properly. Questions that should be asked are: Do the peaks look normal? Is the
system response obtained comparable to the response from previous calibrations?
Careful examination of the chromatogram of the calibration standard can indicate
whether column maintenance is required or whether the column is still usable,
whether there are leaks in the system, whether the injector septum requires
replacing, etc. If changes are made to the system (such as change of a column),
a calibration check must be carried out and a new multipoint calibration must be
generated.
8.4 Required instrument quality control is found in the following
sections:
8.4.1 The mass spectrometer must be tuned to meet the specifications
for 4-bromofluorobenzene in Sec. 7.2 (Table 3).
8.4.2 An initial calibration of the tube desorption/purge-and-trap/
GC/MS must be performed as specified in Sec. 7.7.
8.4.3 The GC/MS system must meet the SPCC criteria specified in Sec.
7.16.3 and the CCC criteria in Sec. 7.16.4 each twelve hours of instrument
operation.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality control (QC) check sample concentrate is required
containing each analyte at a concentration of 10 mg/L in high purity
methanol. The QC check sample concentrate may be prepared from pure
standard materials or purchased as certified solutions. If the QC check
sample concentrate is prepared by the laboratory, the QC check sample
concentrate must be prepared using stock standards prepared independently
from the stock standards used for calibration.
8.5.2 Spike four pairs of cleaned, prepared VOST tubes with 10 /xL
of the QC check sample concentrate and analyze these spiked VOST tubes
according to the method beginning in Sec. 7.0.
8.5.3 Calculate the average recovery (X) in ng and the standard
deviation of the recovery (s) in ng for each analyte using the results of
the four analyses.
8.5.4 The average recovery and standard deviation must fall within
the expected range for determination of volatile organic compounds using
the VOST analytical methodology. The expected range for recovery of
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volatile organic compounds using this method is 50-150%. Standard
deviation will be compound dependent, but should, in general, range from
15 to 30 ng. More detailed method performance criteria must be generated
from historical records in the laboratory or from interlaboratory studies
coordinated by the Environmental Protection Agency. Since the additional
steps of sorbent tube spiking and desorption are superimposed upon the
methodology of Method 8260, direct transposition of Method 8260 criteria
is questionable. If the recovery and standard deviation for all analytes
meet the acceptance criteria, the system performance is acceptable and the
analysis of field samples may begin. If any individual standard deviation
exceeds the precision limit or any individual recovery falls outside the
range for accuracy, then the system performance is unacceptable for that
analyte.
NOTE: The large number of analytes listed in Table 1 presents a
substantial probability that one or more will fail at least
one of the acceptance criteria when all analytes for this
method are determined.
8.5.5 When one or more of the analytes tested fails at least one of
the acceptance criteria, the analyst must proceed according to one of the
alternatives below.
8.5.5.1 Locate and correct the source of any problem with
the methodology and repeat the test for all the analytes beginning
with Sec. 8.5.2.
8.5.5.2 Beginning with Sec. 8.5.2, repeat the test only
for those analytes that have failed to meet acceptance criteria.
Repeated failure, however, will confirm a general problem either
with the measurement system or with the applicability of the
methodology to the particular analyte (especially if the analyte in
question is not listed in Table 1). If the problem is identified as
originating in the measurement system, locate and correct the source
of the problem and repeat the test for all compounds of interest
beginning with Sec. 8.5.2.
8.6 To determine acceptable accuracy and precision limits for surrogate
standards, the following procedure should be performed.
8.6.1 For each sample analyzed, calculate the percent recovery of
each surrogate compound in the sample.
8.6.2 Once a minimum of thirty samples has been analyzed, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (s) for each of the surrogate compounds.
8.6.3 Calculate the upper and lower control limits for method
performance for each surrogate standard. This calculation is performed as
follows:
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
5041 - 23 Revision 0
September 1994
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For reference, the comparable control limits for recovery of the
surrogate compounds from water and soil in Method 8240 are:
4-Bromofluorobenzene Water: 86-115% Soil: 74-121%
l,2-Dichloroethane-d4 Water: 76-114% Soil: 70-121%
Toluene-d8 Water: 88-110% Soil: 81-117%
The control limits for the VOST methodology would be expected to be
similar, but exact data are not presently available. Individual laboratory
control limits can be established by the analysis of replicate samples.
8.6.4 If surrogate recovery is not within the limits established by
the laboratory, the following procedures are required: (1) Verify that
there are no errors in calculations, preparation of surrogate spiking
solutions, and preparation of internal standard spiking solutions. Also,
verify that instrument performance criteria have been met. (2) Recalculate
the data and/or analyze a replicate sample, if replicates are available.
(3) If all instrument performance criteria are met and recovery of
surrogates from spiked blank VOST tubes (analysis of a method blank) is
acceptable, the problem is due to the matrix. Emissions samples may be
highly acidic and may be highly loaded with target and non target organic
compounds. Both of these conditions will affect the ability to recover
surrogate compounds which are spiked on the field samples. The surrogate
compound recovery is thus a valuable indicator of the interactions of
sampled compounds with the matrix. If surrogates spiked immediately
before analysis cannot be observed with acceptable recovery, the
implications for target organic analytes which have been sampled in the
field must be assessed very carefully. If chemical or other interactions
are occurring on the exposed tubes, the failure to observe an analyte may
not necessarily imply that the Destruction and Removal Efficiency for that
analyte is high.
8.7 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples analyzed. Field duplicates may be analyzed to assess the precision of
the environmental measurements. When doubt exists over the identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography with
a dissimilar column or a different ionization mode using a mass spectrometer may
be used, if replicate samples showing the same compound are available. Whenever
possible, the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined in Chapter One. The MDL
concentrations listed in Table 2 were obtained using cleaned blanked VOST tubes
and reagent water. Similar results have been achieved with field samples. The
MDL actually achieved in a given analysis will vary depending upon instrument
sensitivity and the effects of the matrix. Preliminary spiking studies indicate
that under these conditions, the method detection limit for spiked compounds in
extremely complex matrices may be larger by a factor of 500-1000.
5041 - 24 Revision 0
September 1994
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10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHCs Using VOST.
EPA/600/8-84-007, March, 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014A, January, 1986.
3. U. S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
Analysis of Pollutants Under the Clean Water Act, Method 624," October 26,
1984.
4. Bellar, T. A., and J. J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
5. Bellar, T. A., and J. J. Lichtenberg, "Semi-Automated Headspace Analysis
of Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp 108-129, 1979.
5041 - 25 Revision 0
September 1994
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TABLE 1.
RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
WHICH CAN BE ANALYZED BY METHOD 5041
Retention
Compound Time (min)
Acetone
Acrylonitrile
Benzene
Bromochl oromethane
Bromodi chl oromethane
4-Bromof 1 uorobenzene
Bromoform
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chl orodi bromomethane
Chloroethane
Chloroform
Chl oromethane
Di bromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Di chl oroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,4-Difl uorobenzene
Ethyl benzene
lodomethane
Methylene chloride
Styrene
1,1,2, 2 -Tetrachl oroethane
Tetrachl oroethene
Toluene
1,1,1-Trichloroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl chloride
Xylenes*
7.1
8.6
13.3
12.0
16.0
23.4
22.5
4.1
7.1
12.6
20.5
19.3
4:2
12.2
3.0
15.4
10.0
13.3
6.4
8.6
15.2
17.0
18.2
14.2
21.1
7.0
8.1
22.3
24.0
18.6
17.4
12.4
18.4
14.5
5.1
24.0
3.2
22.2
Primary Ion
Mass
43
53
78
128
83
95
173
94
76
117
112
129
64
83
50
93
63
62
96
96
63
75
75
114
106
142
84
104
83
164
92
97
97
130
101
75
62
106
Secondary Ion(s)
Mass(es)
58
52, 51
52, 77
49, 130, 51
85, 129
174, 176
171, 175, 252
96, 79
78
119, 121
114, 77
208, 206
66, 49
85, 47
52, 49
174, 95
65, 83
64, 98
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
91
127, 141
49, 51, 86
78, 103
85, 131, 133
129, 131, 166
91, 65
99, 117
83, 85, 99
95, 97, 132
103, 66
110, 77, 61
64, 61
91
The retention time given is for m- and p-xylene, which coelute on the wide-bore
column. o-Xylene elutes approximately 50 seconds later.
5041 - 26
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September 1994
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TABLE 2.
PRELIMINARY METHOD DETECTION LIMITS AND BOILING POINTS
FOR VOLATILE ORGANICS ANALYZED BY METHOD 5041*
Compound
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
trans-l,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodi chl oromethane
1,1,2,2-Tetrachloroethane*"
1,2-Dichloropropane
trans- 1,3-Di chl oropropene
Trichloroethene
Di bromochl oromethane
1 , 1 ,2-Tri chloroethane
Benzene
cis- 1,3-Di chl oropropene
Bromoform""
Tetrachloroethene
Toluene
Chlorobenzene^
Ethyl benzene"
Styrene"*
Tri chl orof 1 uoromethane
lodomethane
Acrylonitrile
Dibromomethane
1 ,2,3-Trichloropropane*1'
total Xylenes"
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-35-3
156-60-5
67-66-3
107-06-2
71-55-6
56-23-5
75-27-4
79-34-5
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
75-25-2
127-18-4
108-88-3
108-90-7
100-41-4
100-42-5
75-69-4.
74-88-4
107-13-1
74-95-3
96-18-4
Detection
Limit, ng
58
26
1-4
21
9
35
11
14
12
11
11
13
8
8
11
23
12
17
11
21
26
26
27
26
11
15
15
21
46
17
9
13
14
37
22
Boiling
Point, °C
-24
4
-13
13
40
56
46
32
57
48
62
83
74
77
88
146
95
112
87
122
114
80
112
150
121
111
132
136
145
24
43
78
97
157
138-144
* The method detection limit (MDL) is defined as 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 analysis of a sample in
a given matrix containing the analyte. The detection limits cited above were
determined according to Title 40 CFR, Part 136, Appendix B, using standards spiked
onto clean VOST tubes. Since clean VOST tubes were used, the values cited above
represent the best that the methodology can achieve. The presence of an emissions
matrix will affect the ability of the methodology to perform at its optimum level.
** Not appropriate for quantitative sampling by Method 0030.
5041 - 27
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September 1994
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TABLE 3.
KEY ION ABUNDANCE CRITERIA FOR 4-BROMOFLUOROBENZENE
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance .
96 5 to 9% of mass 95 ..'•-.•
173 less than 2% of mass 174
174 . greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95%, but less than 101% of mass 174
177 5 to 9% of mass 176
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September 1994
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TABLE 4.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
Brbmochloromethane
Acetone
Acrylbriitrile
Broriiomethane
Carbon disulfide
Chibroethane
Chloroform
Chioromethane
1,1-Dichloroethane
1,2-Dichioroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
Trichlorbethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Trichlorofluoromethane
Vinyl chloride
1,4-Diflubrobenzene
Benzene
Bromodichloromethane
Bromoform,
Carbon .tetrachloride
Chiorodi brombmethane
Dibromomethane
Ii2-Dichloropropane
cis-l,3-Dichloropropene
trans-1,3-Di chloropropene
1,1,1-Trichlbroethahe
1,1,2-Tri chloroethane
Ch1oroberizene-d5
4-Bromofludrdbenzehe (surrogate)
Chlorobenzene
Ethyl benzene
Styrene
1,1,2,2-tetrachloroethane
Tetrachloroethene
toluene
Toluene-d8 (surrogate)
1,2,3-Trichloropropane
Xylenes
5041 - 29
Revision 0
September 1994
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1/4" le 1/fl" Union
Tenax ^
N—
Purg* Flow
1/4" lo 1/4" Union
1/4" lo 1/16" Union (Connec?°to &Hom .1
purg* llaiti)
1/16" Teflon Tubing
1/16" nut
0 1/4" nut
(5) 1/8" nut
Figure 1. Cartridge Desorption Flow
5041 - 30
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September 1994
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Cartridge Desorplion Unit
1/8" Teflon Tubing
Stand to Raise
Clam Shell Oven
Figure 2. Cartridge Desorption Unit with Purge and Trap Unit
5041 - 31
Revision 0
September 1994
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Tube
Oesorplion
Unit
^
Purge and Trap
Apparatus
Gas
Chroma tograph
•^Interface
^
Mass
Spectrometer
\
i
I Data System I
Storage Media
for Archive
Figure 3. Schematic Diagram of Overall Analytical System
5041 - 32
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September 1994
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Water Fill Line
Sintered Glass Frit
Gas Flow
Figure 4. Sample Purge Vessel
5041 - 33
Revision 0
September 1994
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Gloss Wool
Porjiculqle
Slock
(or lest system)
Silico Gel
Condensole
Trap
Impinger
Figure 5. Schematic of Volatile Organic Sampling Train (VOST)
Cxhoust
5041 - 34
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September 1994
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METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN: WIDE-BORE CAPILLARY COLUMN TECHNIQUE
1
r
7.1 Condition* for
cartridge
desorption oven,
purge-end-trap
concentrator, GC,
and MS.
7.2 Daily, tune
the GC/MS with
BFB and check
calibration curve
(see Section 7.17).
7.3 • 7.6
Assemble the
system.
7.7.1 Calibrate the
instrument system
using the internal std.
procedure. Stds. and
calibration compounds
are spiked into cleaned
VOST tubes using the
flash evaporation
technique.
7.8 Prep the
purge-and-trap
unit with 5 ml
organic-free
reagent water.
7.9 Connect
paired VOST
tubas to the
gas lines for
desorption.
7.10 Initiate
tube desorption/
purge and
heating.
I
7.11 Set the GC
oven to subambient
temperature
with liquid
nitrogen.
7.12 Prep the
GC/MS system
for data
aquiiition.
7.13 After the tube/
water purge time,
attach the
analytical trap to
the GC/MS for
deiorption.
7.14 Waeh purging
vessel with two
5 ml flushes of
organic-free
reagent water.
7.16 Recondition the
analytical trap by
making it cut at
temps up to 220 C for
11 min. Trap replacement
may be necessary
if the analytical trap
is saturated beyond
cleanup.
7.16.1 Prep
calibration stds.
as in 7.7.1. Add
water to vessel
and desorb.
7.16.2
Tabulate the
area response
of all compounds
of interest.
7.16.3
Calculate the
average RF for
each compound
of interest.
7.16.4 Calculate
the %RSD
for the CCCe.
The %RSD must
be <30%.
7.18 GC/MS
analysis of
samples.
7.19.1 Qualitative
analysis of date
and ident. guidelines
of compounds.
7.19.2 Quantitative
analysis of data for
the compounds of
interest.
| Stop J
5041 - 35
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September 1994
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5050
-------
METHOD 5050
BOMB PREPARATION METHOD FOR SOLID WASTE
1.0 SCOPE AND APPLICATION
1.1 This method describes the sample preparation steps necessary to
determine total chlorine in solid waste and virgin and used oils, fuels and
related materials, including: crankcase, hydraulic, diesel, lubricating and fuel
oils, and kerosene by bomb oxidation and titration or ion chromatography.
Depending on the analytical finish chosen, other halogens (bromine and fluorine)
and other elements (sulfur and nitrogen) may also be determined.
1.2 The applicable range of this method varies depending on the
analytical finish chosen. In general, levels as low as 500 jug/g chlorine in the
original oil sample can be determined. The upper range can be extended to
percentage levels by dilution of the combustate.
1.3 This standard may involve hazardous materials, operations, and
equipment. This standard does not purport to address all of the safety problems
associated with its use. It is the responsibility of the user of this standard
to establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to use. Specific safety statements
are given in Section 3.0.
2.0 SUMMARY OF METHOD
2.1 The sample is oxidized by combustion in a bomb containing oxygen
under pressure. The liberated halogen compounds are absorbed in a sodium
carbonate/sodium bicarbonate solution. Approximately 30 to 40 minutes are
required to prepare a sample by this method. Samples with a high water content
(> 25%) may not combust efficiently and may require the addition of a mineral oil
to facilitate combustion. Complete combustion is still not guaranteed for such
samples.
2.2 The bomb combustate solution can then be analyzed for the following
elements as their anion species by one or more of the following methods:
Method Title
9252 Chloride (Titrimetric, Mercuric Nitrate)
9253 Chloride (Titrimetric, Silver Nitrate)
9056 Inorganic Anions by Ion Chromatography (Chloride, Sulfate,
Nitrate, Phosphate, Fluoride, Bromide)
5050 - 1 Revision 0
September 1994
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NOTE: Strict adherence to all of the provisions prescribed hereinafter
ensures against explosive rupture of the bomb, or a blowout, provided the
bomb is of proper design and construction and in good mechanical
condition. It is desirable, however, that the bomb- be enclosed in a
shield of steel plate at least 1/2 in. (12.7 mm) thick, or equivalent
protection be provided against unforeseeable contingencies.
3.0 INTERFERENCES
3.1 Samples with very high water content (> 25%) may not combust
efficiently and may require the addition of a mineral oil to facilitate
combustion.
3.2 To determine total nitrogen in samples, the bombs must first be
purged of ambient air. Otherwise, nitrogen results will be biased high.
4.0 APPARATUS AND MATERIALS
4.1 Bomb, having a capacity of not less than 300 ml, so constructed
that it will not leak during the test, and that quantitative recovery of the
liquids from the bomb may be readily achieved. The inner surface of the bomb may
be made of stainless steel or any other material that will not be affected by the
combustion process or products. Materials used in the bomb assembly, such as the
head gasket and lead-wire insulation, shall be resistant to heat and chemical
action and shall not undergo any reaction that will affect the chlorine content
of the sample in the bomb.
4.2 Sample cup, platinum or stainless steel, 24 mm in outside diameter
at the bottom, 27 mm in outside diameter at the top, 12 mm in height outside, and
weighing 10 to 11 g.
4.3 Firing wire, platinum or stainless steel, approximately No. 26 B
& S gage.
4.4 Ignition circuit, capable of supplying sufficient current to ignite
the nylon thread or cotton wicking without melting the wire.
NOTE: The switch in the ignition circuit shall be of the type that remains
open, except when held in closed position by the operator.
4.5 Nylon sewing thread, or Cotton Wicking, white.
4.6 Funnel, to fit a 100-mL volumetric flask.
4.7 Class A volumetric flasks, 100-mL, one per sample.
4.8 Syringe, 5- or 10-mL disposable plastic or glass.
4.9 Apparatus for specific analysis methods are given in the methods.
4.10 Analytical balance: capable of weighing to 0.0001 g.
5050 - 2 Revision 0
September 1994
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5.0 REAGENTS
5.1 Purity of reagents. 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. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Oxygen. Free of combustible material and halogen compounds,
available at a pressure of 40 atm.
WARNING: Oxygen vigorously accelerates combustion (see Appendix Al.l)
5.4 Sodium bicarbonate/sodium carbonate solution. Dissolve 2.5200 g
NaHC03 and 2.5440 g Na2C03 in reagent water and dilute to 1 L.
5.5 White oil. Refined.
5.6 Reagents and materials for specific analysis methods are given in
the methods.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.
6.2 Ensure that the portion of the sample used for the test is repre-
sentative of the sample.
6.3 To minimize losses of volatile halogenated solvents that may be
present in the sample, keep the field and laboratory samples as free of headspace
as possible.
6.4 Because used oils may contain toxic and/or carcinogenic substances
appropriate field and laboratory safety procedures should be followed.
7.0 PROCEDURE
7.1 Sample Preparation
7.1.1 Preparation of bomb and sample. Cut a piece of firing wire
approximately 100 mm in length and attach the free ends to the terminals.
Arrange the wire so that it will be just above and not touching the sample
cup. Loop a cotton thread around the wire so that the ends will extend
into the sampling cup. Pipet 10 mL of the NaHC03/Na2C03 solution into the
bomb, wetting the sides. Take an aliquot of the oil sample of approxi-
mately 0.5 g using a 5- or 10-mL disposable plastic syringe, and place in
the sample cup. The actual sample weight is determined by the difference
5050 - 3 Revision 0
September 1994
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between the weight of the empty and filled syringe. Do not use more than
1 g of sample.
NOTE: After repeated use of the bomb for chlorine determination,
a film may be noticed on the inner surface. This dullness should
be removed by periodic polishing of the bomb. A satisfactory
method for doing this is to rotate the bomb in a lathe at about
300 rpm and polish the inside surface with Grit No. 2/0 or
equivalent paper1 coated with a light machine oil to prevent
cutting, and then with a paste of grit-free chromic oxide2 and
water. This procedure will remove all but very deep pits and put
a high polish on the surface. Before using the bomb, it should
be washed with soap and water to remove oil or paste left from the
polishing operation. Bombs with porous or pitted surfaces should
never be used because of the tendency to retain chlorine from
sample to sample.
NOTE; If the sample is not readily combustible, other
nonvolatile, chlorine-free combustible diluents such as white oil
may be employed. However, the combined weight of sample and
nonvolatile diluent shall not exceed 1 g. Some solid additives
are relatively insoluble but may be satisfactorily burned when
covered with a layer of white oil.
NOTE: The practice of alternately running samples high and low
in chlorine content should be avoided whenever possible. It is
difficult to rinse the last traces of chlorine from the walls of
the bomb, and the tendency for residual chlorine to carry over
from sample to sample has been observed in a number of
laboratories. When a sample high in chlorine has preceded one low
in chlorine content, the test on the low-chlorine sample should
be repeated, and one or both of the low values thus obtained
should be considered suspect if they do not agree within the
limits of repeatability of this method.
NOTE: Do not use more than 1 g total of sample and white oil or
other chlorine-free combustible material. Use of excess amounts
of these materials could cause a buildup of dangerously high
pressure and possible rupture of the bomb.
7.1.2 Addition of oxygen. Place the sample cup in position
and arrange the thread so that the end dips into the sample. Assemble the
bomb and tighten the cover securely. Admit oxygen slowly (to avoid
blowing the oil from the cup) until a pressure is reached as indicated in
Table 1.
NOTE: Do not add oxygen or ignite the sample if the bomb has been
jarred, dropped, or tiled.
Ornery Polishing Paper grit No. 2/0 may be purchased from the Behr-Manning
Co., Troy, NY.
2Chromic oxide may be purchased from J.T. Baker & Co., Phillipsburg, NJ.
5050 - 4 Revision 0
September 1994
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7.1.3 Combustion. Immerse the bomb in a cold water bath.
Connect the terminals to the open electrical circuit. Close the circuit
to ignite the sample. Remove the bomb from the bath after immersion for
at least 10 minutes. Release the pressure at a slow, uniform rate such
that the operation requires at least 1 min. Open the bomb and examine the
contents. If traces of unburned oil or sooty deposits are found, discard
the determination, and thoroughly clean the bomb before using it again.
7.1.4 Collection of halogen solution. Using reagent water and
a funnel, thoroughly rinse the interior of the bomb, the sample cup, the
terminals, and the inner surface of the bomb cover into a 100-mL
volumetric flask. Dilute to the mark with reagent water.
7.1.5 Cleaning procedure for bomb and sample cup. Remove any
residual fuse wire from the terminals and the cup. Using hot water, rinse
the interior of the bomb, the sample cup, the terminals, and the inner
surface of the bomb cover. (If any residue remains, first scrub the bomb
with Alconox solution). Copiously rinse the bomb, cover, and cup with
reagent water.
7.2 Sample Analysis. Analyze the combustate for chlorine or other
halogens using the methods listed in Step 2.2. It may be necessary to dilute the
samples so that the concentration will fall within the range of standards.
7.3 Calculations. Calculate the concentrations of each element
detected in the sample according to the following equation:
Ccom x Vcom x DF (1)
C =
"o
W.
o
where:
C0 = concentration of element in the sample,
Ccom = concentration of element in the combustate, jug/mL
VCom = total volume of combustate, ml
DF = dilution factor
W0 = weight of sample combusted, g.
Report the concentration of each element detected in the sample in
micrograms per gram.
5050 - 5 Revision 0
September 1994
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Example: A 0.5-g oil sample was combusted, yielding 10 ml of combustate.
The combustate was diluted to 100 ml total volume and analyzed for chloride,
which was measured to be 5 /xg/mL. The concentration of chlorine in the original
sample is then calculated as shown below:
5 ug x (10 ml) x (10)
C0 = ml (2)
0.5 g
C0 = 1,000 nfl (3)
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 One sample in ten should be bombed twice. The results should agree
to within 10%, expressed as the relative percent difference of the results.
8.3 Analyze matrix spike and matrix spike duplicates - spike samples with
the elements of interest at a level commensurate with the levels being
determined. The spiked compounds should be similar to those expected in the
sample. Any sample suspected of containing > 25% water should also be spiked
with organic chlorine.
8.4 For higher levels (e.g.. percent levels), spiking may be
inappropriate. For these cases, samples of known composition should be
combusted. The results should agree to within 10% of the expected result.
8.5 Quality control for the analytical method(s) of choice should be
followed.
9.0 PERFORMANCE
See analytical methods referenced in Step 2.2.
10.0 REFERENCES
1. ASTM Method D 808-81, Standard Test Method for Chlorine in New and Used
Petroleum Products (Bomb Method). 1988 Annual Book of ASTM Standards. Volume
05.01 Petroleum Products and Lubricants.
2. Gaskill, A.; Estes, E. D.; Hardison, D. L.; and Myers, L. E. Validation
of Methods for Determining Chlorine in Used Oils and Oil Fuels. Prepared for
U.S. Environmental Protection Agency, Office of Solid Waste. EPA Contract No.
68-01-7075, WA 80. July 1988.
t
5050 - 6 Revision 0
September 1994
-------
TABLE 1.
GAGE PRESSURES
Capacity of bomb, ml
Minimum
gage
pressure8
atm
Maximum
gage
pressure8, atm
300 to 350
350 to 400
400 to 450
450 to 500
38
35
30
27
40
37
32
29
"The minimum pressures are specified to provide sufficient oxygen for complete
combustion, and the maximum pressures represent a safety requirement. Refer to
manufacturers' specifications for appropriate gage pressure, which may be lower
than those listed here.
5050 - 7
Revision 0
September 1994
-------
APPENDIX
Al. PRECAUTIONARY STATEMENTS
Al.1 Oxygen
Warning--Oxygen vigorously accelerates combustion.
Keep oil and grease away. Do not use oil or grease on regulators, gages,
or control equipment.
Use only with equipment conditioned for oxygen service by careful cleaning
to remove oil, grease, and other combustibles.
Keep combustibles away from oxygen and eliminate ignition sources.
Keep surfaces clean to prevent ignition or explosion, or both, on contact
with oxygen.
Always use a pressure regulator. Release regulator tension before opening
cylinder valve.
All equipment and containers used must be suitable and recommended for
oxygen service.
Never attempt to transfer oxygen from cylinder in which it is received to
any other cylinder. Do not mix gases in cylinders.
Do not drop cylinder. Make sure cylinder is secured at all times.
Keep cylinder valve closed when not in use.
Stand away from outlet when opening cylinder valve.
For technical use only. Do not use for inhalation purposes.
Keep cylinder out of sun and away from heat.
Keep cylinders from corrosive environment.
Do not use cylinder without label.
Do not use dented or damaged cylinders.
See Compressed Gas Association booklets G-4 and G4.1 for details of safe
practice in the use of oxygen.
5050 - 8 Revision 0
September 1994
-------
METHOD 5050
BOMB PREPARATION METHOD FOR SOLID WASTE
START
7.1.1 Prepare bomb
and sample
1
7.1.2 Slowly add
oxygen to sample
cup
1
7.1.3 Immerse bomb
in cold water ;
igni te sample ;
remove bomb from
water ; release
pressure; open bomb
7.1.4 Rinse bomb,
sample cup,
terminals , and bomb
cover with water
P+
7.1.5 Rinse bomb ,
sample cup,
terminals, and bomb
cover with hot
water
1
7 . 2 Analyze
combus tate
1
7.3 Calculate
concentration of
each element
detected
^ ^\
/ \
( STOP 1
\. J
5050 - 9
Revision 0
September 1994
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6010A
-------
METHOD 6010A
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY
1.0 SCOPE AND APPLICATION , <
I
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. '•'..'v. •
6010A - 1 Revision 1
1 July 1992
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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. 6l6
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
1 4.
10
.7
7
6
7
42
5
30 .
2
8
15
51
See note c
75
7
29
0.3
40
8
2
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.
6010A -2 Revision 1
: July 1992
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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. " . •
6010A - 3 Revision 1
July 1992
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TABLE 2.
ANALYTE CONCENTRATION EQUIVALENTS ARISING FROM
INTERFERENCE AT THE 100-mg/L LEVEL
Interferenta>b \
Wavelength —- - r
Analyte (nm) Al Ca Cr ' Cu Fe Mg Mn Ni
Tl
Aluminum
Antimony
Arsenic
308.215
206.833
193.696
0.47 --
1.3 --
2.9 --
0.44 --
0.08 --
_.
0.21 -- -- 1.4
0.25 0.45
1.1
Barium 455.403
Beryllium 313.042
0.04 0.05
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Selenium
Sodium
Thallium
Vanadium
Zinc
226.
317.
267.
228.
324.
259.
220.
279.
257.
202.
231.
196.
588.
190.
292.
213.
502
933
716
616
754
940
353
079
610
030
604
026 '
995
864
402
856
..
. . •
' - - •• - -
i - -
..
.
0.17 --
0.02
0.005 -.-
0.05 --
..
0.23 --
...
0.30 --
. .
—
0.08
0.03
--
_ .
—
0.11
0.01
--
- -
-'-
--.
0.05
-- '
0
0
0
0
0
- -' -
.-
0
0
0
--
0
_-
. .
0
0.14 -
.03 --
.01 0.01
.003 --
.005 --
.003 --
- - - '
.
.13 --
.002 0.002
.03 --
. •
.09 '--
- •
.
.005 --
--
0.04
0.04
--
0.12
. - >
0.25
.-
--
--
- -
--
- - •
0.02 -
0
__
.0.03 0
0
_ -
.-
0
- -
.-
.-
0
_-
o
0.29 -
-
.03
-
.15
.05
.
-
.07
-
-
- . _
-
.08
-
.02
-
-
0
0
.
0
.
-
0
-
-
-
-
-
-
.-
-
- ••
.03
.04
-
.02
.
-
.12
-
-
-
-
-
-
-
-
Cashes indicate that no interference was observed even when interferents were
introduced at the following levels:
Al -
Ca -
Cr. -
Cu '-
Fe -
1000 mej/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
Revision 1
July 1992
-------
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, the.se 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.
i i
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 Tine 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
6010A - 5 Revision 1
July 1992
-------
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), HCl. '
5.1.2 Hydrochloric acid (1:1), HCl. Add 500 ml concentrated HCl 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 (Ul), 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
Metal salts ' ' t
. Concentration (pp.)' "^ °e fract1°n
5.3.1 Aluminum solution, stock, 1 ml = 1000 ug Al : Dissolve l.Og
of aluminum metal, weighed accurately to at least four significant
figures, in an acid mixture of 4 ml of (1:1) HCl 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
July 1992
-------
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 « 100,0 ug As: Dissolve 1.30 g
of AsJ33 (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 tig 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) HNO,. 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
pf 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
July 1992
-------
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
1.7.0 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 (NHJgMo/J^^HpO (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 Ni: Dissolve 1.00 g
of nickel metal, weighed accurately to at least four significant figures,
in 10.0 mL hot concentrated HN03, cool, and dilute to volume in a 1,000 mL
volumetric flask with water. s
I . ' •
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
KC] (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
-.-'.. • . July 1992
-------
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(NCL)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 TV: 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 HNO,. 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 solutions1- Prepare mixed calibration
tandard solutions by combining,appropriate volumes of the stock solutions in
olumetric flasks (see Table 3). Matrix match with the appropriate acids and
ilute to 100 mL with water. Prior to preparing the mixed standards, each stock
olution should be analyzed . separately to determine possible spectral
nterference or the presence of impurities. Care should be taken when preparing
he mixed standards to ensure that the elements are compatible and stable
ogether. Transfer the mixed standard solutions to FEP fluorocarbon or previously
nused polyethylene or polypropylene bottles for storage. Fresh mixed standards
hould be prepared, as needed, with the realization that concentration can change
n aging. Calibration standards must be initially verified using a quality
ontrol sample (see Step 5.8) and monitored weekly for stability. Some typical
alibration standard combinations are listed in Table 3. All mixtures should then
e scanned using a sequential spectrometer to verify the absence of interelement
pectral interference in the recommended mixed standard solutions.
6010A - 9 Revision 1
July 1992
-------
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 arid 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.
1 . TABLE 3.
MIXED STANDARD SOLUTIONS
Solution Elements
I Be, Cd, Mn, Pb, Se and Z'n
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.
i . . "
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 eTements of interest at approximate
6010A - 10 Revision 1
July 1992
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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.
6010A - 11 . Revision 1
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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.
6010A - 12 Revision 1
•',-:. . • July 1992
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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:
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
.July 1992
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10.0 REFERENCES <
1. -. Winge. R.K.; Peterson. V.J.; Fassel. V.A. Inductively Coupled Plasma-Atomic
Emission Spectroscopy: Prominent Lines (final report, March 1977 -February 1978);
EPA-600/4-79-0.17, 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 198,4. . .
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, 1.986; Prepared
by Arthur D. Little, Inc. .
5. Bowmand, P.W.J.M. Line Coincidence Tables for Inductively Coupled Plasma
Atomic Emission Spectrometrv, 2nd ed.; Pergamon: 1984. -
6. Rohrbough, W.G.; et a!. 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
July 1992
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TABLE 4.
ICP PRECISION AND ACCURACY DATA
a
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 Mean.
Value Value SD °
(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
1 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
20
15
69
19
10
11
19
62
2.9
20
28
30
19
8,5
Mean Re- Mean Re-
Mean. True ported Mean.
SD° 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,0
acidified, \ No
pre-filtered?
I* (ample
water?
7.1 U«.
Method 3005
7.2 Set up
and itabilii
instrument
Ii (ample
oil* ,grea(B(
axe*?
7.1 U*e
M.thod 3040
I*
•ample
analyied by
FLAA/ICP or
CFM?
7.1 U..
M.thod 3020
and Method
\ 7000
aqueou* or
•olid?
7.1 U..
Mathod 3050
7.1 U..
Method 3010
7.3 Profile
and calibrate .
initruaent
7.. 4 Reanalyie
highest nixed
calibration
•tandard
Adju»t
instrument p.r
manufacturer
recommendation*
No
7.5 Flu.h
• tyitem and
analyie
, (ample
7 . 5 Analyze
check itandard
and calibration
blank after .
each 10 (ample*
7 6 Calculate
concentration*
Stop
6010A - 16
Revision 1
July 1992
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6020
-------
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-ywg/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/yg/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, 169Tb, 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
9ZZrO+ 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
September 1994
-------
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,H]'.
Concentrations of antimony and silver between 50-500 //g/L require 1% (v/v) HC1
for stability; for concentrations above 500 jjg/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 fjg 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 jjg In:
Dissolve 0.1000 g indium metal in 10 ml cone. HN03. Dilute to 1,000 ml
with reagent water.
6020-4 Revision 0
September 1994
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5.3.4 Lithium internal standard solution, stock, 1 mL = 100 /yg 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/yg Rh:
Dissolve 0.3593 g ammonium hexachlororhodate (III) (NH4)3RhCle 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/yg 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/yg 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 /yg 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, 115In, 159Tb, f69Ho, 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.
6020-5 Revision 0
September 1994
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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.
6020-6 Revision 0
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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-jwg/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-/yg/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 fjg/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-coritrol calibration must be reanalyzed. During
the course of an analytical run, the instrument may.be "resloped" or recalibrated
to correct for instrument dr.ift. 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 ahalyte (or species heeded 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 Oug/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) = r-*-
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 jjg/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 apportion
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
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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 IOL 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.
8.10 Analyze one duplicate sample for every matrix in a batch at a
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.
DT = 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).
6020-12 Revision 0
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5. Hoi den, 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
N1
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, 5_Z, 58 Iron (I)
139 Lanthanum (I)
208, 207. 206. 204 Lead
6*77 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. " 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
Comparability8
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
1.0
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. 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 I'DL value). c S is the number of samples with results greater
than the limit of quantitation. 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 MULTI-LABORATORY PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Element
Comparability8
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
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. 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
7.1 Arwly»
by Method
7000 or
Mithod 6010.
7.11
Cctoulat*
concentration.
>
1
6020-19
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7000A
-------
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
datavShown 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 oh 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). . v
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
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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.
v '
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.
7000A - 2 Revision 1
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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 (l,OOO.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.
7000A - 3 •- Revision 1'
July 1992
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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 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-produc.ing sample matrix can
sometimes be Deduced 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 witfr 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.
'..•'. - 7000A - 4 Revision 1
July 1992
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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, photomultipl ier
detector, adjustable slits, a wavelength range of 190 to 800 hm, 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 Tamps 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 - MicrolHer,.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
7000A - 5 Revision 1.
' . , July ,1992
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without lessening the accuracy of the1determination. 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 spectrpgrade 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. .
I
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 cannpt 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 Ol.'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.
7000A - 6 Revision 1
July 1992
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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 corrept 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
1 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
' . % .July 1992
-------
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 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.
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 o'f the graphite tube. Lac.k 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.
. 7000A - 8' - . , Revision 1
-July 1992
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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
cal ibration, 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. i
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.
7000A - 9 ' Revision 1
July 1992
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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. V8 and C, 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 - 1.0 . Revision 1
. ^ July 1992
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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 rionspecific 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; 01193-77.
7000A - 11 . Revision 1
July 1992
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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 Procedure3 'c
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
NOTE: The symbol (p) indicates the use of pyrolytic graphite with
the furnace procedure.
aFor furnace sensitivity values, consult instrument operating manual.
' ' • v
^Gaseous hydride method. . '
°rhe 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.
) • .
Told vapor technique.
7000A - 12
Revision 1
July 1992.
-------
FIGURE 1.
STANDARD ADDITION PLOT
1
co
•E
o
w
Zero
Absorbance
Concentration
Conc.,of AddnO Addn T Addn2 Addn 3
Sample , NO Addn Addn of 50% Addn of 100% Addn of 150%
of Expected of Expected of Expected
Amount Amount Amount
700.0A - 13
Revision 1
July 1992
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METHOD 7000A. '.
ATOMIC ABSORPTION METHODS
7.2.1 Choo.e
and prepare
hollow tub*
cathode lamp
7.2.1 ndju.t
and align
•quipaant
7.2.1 Light
flama and
ragulata
7.2.1 Run
•tandard*
7.2.1 Conitruct
calibrationi
curve and let
curva eorractor
C
suri
7.1 Selubiliia
and digatt
tampla'(•••
Chapter 3,
Section 3.2)
7.3.1 Follow
operating
instruction*
from instrument
manufacturer
7.2.1
Aipirate
•ample
7.2.1 Run a
check
•tandard
T.i
7.3.3 Clean
tube
7,4 Determine
concentration*
Stop
J
7.3.4 Inject
and atomiie
part of
•ample
7.3.4 Dilute
•ample
7.35 U.. .-
interference
te«t< to verify
.absence of
interference
7.3.6 Run a
check
•tandard •
7000A - 14
Revision 1
July 1992
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7060
-------
METHOD 7060
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7060 1s an atomic absorption procedure approved for
determining the concentration of arsenic 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
, s •
2.1 Prior to analysis by Method 7060, samples must be prepared 1n 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 add digestion procedure described 1n
this method. Sludge samples are prepared using the procedure described 1n
Method 3050.
2.2 Following the appropriate dissolution, of the sample, a
representative aliquot of the dlgestate 1s spiked with a nickel nitrate
solution and 1s placed manually or by means of an automatic sampler Into a
graphite tube furnace. The sample aliquot 1s then slowly evaporated to
dryness, charred (ashed), and atomized. The absorption of holloa cathode or
EDL radiation during atom1zat1pn will be proportional to the arsenic
concentration. .
2.3 The typical detection limit for this method 1s 1 ug/L.
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 1s appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times fdr 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, arsenic analysis can suffer from severe nonspecific
absorption and light scattering caused by matrix components during
atomlzatlon. Arsenic analysis 1s particularly susceptible to these, problems
because of Its low analytical wavelength (193.7 nm). Simultaneous background
7060-1
Revision
Date September 1986
-------
correction must be employed to avoid erroneously high results. Aluminum 1s a
severe positive Interferent 1n the analysis of arsenic, especially using 03
arc background correction. Zeeman background correction 1s very useful 1n
this situation.
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 by means of blank burns, the tube should be cleaned by operating the
furnace at full power at regular Intervals 1n the analytical scheme.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beaker; 250 ml.
4.2 Volumetric flasks; 10-mL. ,
4.3 Atomic absorption spectrophotometer; Single or dual channel,
single- or double-beam Instrumenthavinga~ grating monochromator, photo-
multlpHer detector, adjustable slits, a wavelength range of 190 to 800 rim,
and provisions for simultaneous background correction and Interfacing with a
strip-chart recorder.
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 Strip-chart recorder; A recorder 1s- 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 atomlzatlon, losses during
charring, changes in sensitivity, etc., can easily be recognized.
4.7 Plpets; M1crol1ter 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; Add should be analyzed to determine
levels of Impurities. If a method blank using the add 1s
-------
5.4 Arsenic standard stock solution (1,000 mg/L); Either procure a
certified aqueous standard froma supplier and verify by comparison with a
second standard, or dissolve ,1.320 g of arsenic trloxlde (As?07, analytical
reagent grade) or equivalent 1n 100 ml of Type II water containing 4 g NaOH.
Acidify the solution with 20 ml concentrated.HN03 and dilute to 1 liter
(1 ml = 1 mg As).
5.5 Nickel nitrate solution (5%); Dissolve 24.780 g of ACS reagent
grade N1(N03)2*6H20 or equivalent 1n Type II water and dilute to 100 ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5X nickel nitrate
to 100 ml with Type II water.
5.7 Arsenic working standards; Prepare dilutions of the stock solution
to be used as calibrationstandards . at the time of the analysis. Withdraw
appropriate allquots of the stock solution, add 1 ml of concentrated HN03,
2 ml of 30% H202, and 2 ml of the 5X nickel nitrate solution. Dilute to
100 ml with Type II 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 1n Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, adds, 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 arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric add.
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 In Paragraphs 7.1.1-7.1.3. 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.
7.1.1 Transfer 100 mL of well-mixed sample to a 250-mL Griffin
beaker; add 2 mL of 30% H?02 and sufficient concentrated HN03 to result
in an add concentration of 1% (v/v)» Heat for 1 hr at 95*C or until the
volume 1s slightly less than 50 mL.
-7.1.2 Cool and bring back to 50 mL with Type II water.
7060 - 3
Revision 0
Date September 1986
-------
7.1.3 P1pet 5 ml of this digested solution Into a 10-mL volumetric
flask, add 1 ml of the IX nickel nitrate solution, and dilute to 10 mL
with Type II water. The sample 1s now ready for Injection Into the
furnace.
7.2 The 193.7-nm wavelength line and a background correction system are
required. Follow the manufacturer's suggestions for all other spectrophoto-
meter parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperaturcrsenslng 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 1n 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 m1crol1ter aliquot of sample Into the furnace and
atomize. If the concentration found 1s greater than the highest standard, the
sample should be diluted 1n the same add matrix and reanalyzed. The use of
multiple Injections can Improve accuracy and help detect furnace pipetting
errors.
7.5 Analyze allEP extracts, all samples analyzed as part of a dellsting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions.
7,6 Run a check standard after every 10 Injections of samples. (
Standards are run 1n part to monitor the life and performance of the graphite
tube. Lack of reproduc1bH1ty or significant change 1n the signal for the
standard Indicates that the tube should be replaced.
<. • ' \
- , 7.7 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 multlphased samples
must br appropriately qualified (e.g., 5 ug/g aqueous phase).
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed. ,
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 analysts.
i . ~
7060-4 .;
' Revision 0
Date September 1986
-------
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 20 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 del1st1ng petition, and whenever a new sample matrix is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 206.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The optimal concentration range for this method 1s 5-100 ug/L:
9.3 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 206.2.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
'Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7060 - 5
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Contaminated soil 3050 ; 2.0, 1.8 ug/g
01ly soil - 3050 3.3, 3.8 ug/g
NBS SRM 1646 Estuarlne sediment 3050 8.1, 8.33 ug/.ga
Emission control dust 3050 430, 350 ug/g
aB1as of -30 and -28%. from expected, respectively.
7060 - 6
Revision
Date September 1986
-------
METHOD 7060
ARSENIC (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
samples
. >. Sludge-type
Type of semple^w samples
for sample
preparttlon
7.1.1
Transfer
sample to
Deafer; add
H,Oi and cone.
- neat
7.1.2
Prepare samples
according to
Method 303O
Cool: increase
voVuma
7.1.3
I Plpet
solution
Into flailc: add
nickel nltrete;
dilute
7060 - 7
Revision 0
Date September 1986
-------
METHOD 7060
ARSENIC (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
(Continued)
Set uo
spectroonoto-
meter with
correct
parameters
7.3
7.3
Anolyza
by mecnoo of
standard
additions
Periodically
verify furnace
parameters.
7. 4
7.6
Run
checK standard
after every 10
Injection!
Inject
aliouot of
sample into
furnaca:
atomize
is
concentration
> nignest
standard?
Dilute aample
and reanalyze
7.7
Calculate metal
concentration*
7.8
Analyze
dupl icatet,
spiked aamples
and check
standards
f Stop J
7060 - 8
Revision 0
Date' September 1986
-------
7060A
-------
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 aricl 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
-------
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 Transfer
•aaplo to
beaker,add H.O,
and cone. HtiOi,
heat
7.1 Prepare
•aaplao
according to
Method 3050
7.1.2 Cool
•nd bring to
volvura with
reagent w«t«r
7.1.3 Pipct
•olution into
fl..k, add
niekcl nitrate,
dilute
7.2 Set up
initruBont
operating
paraaatcr
7-3
Periodically
verify
furnace
parameter*
7.4 Inject
aliquot of
aaaple into
furnace,
atoaiie
7.4 Beoord A*
eonoentration
7.4 Dilute
•aaple and
reanalvie
( Stop J
7060A - 6
Revision 1
September 1994
-------
7061A
-------
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 js 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 trivaleht
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.
(
i
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
-------
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 fnicro'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 si its,.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 ac|d (concentrated), UNO,. Acid should be analyzed to
determine levels of impurities. If a methocT blank is < MDL, the acid can be
used. . : '
7061A - 2 x Revision 1
July 1992
-------
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-rnL volumetric flask and bring to volume with water
containing 1.5 ml concentrated HNOj/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
1 July 1992
-------
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
absoroances 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-rim 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
-------
METHOD 7061A .
ARSENIC (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
7.1 Turn off
haat,oool,
and add HHO,
7.3 Tranafar
•tandarda to
fla«k«,add
• aaipla, bring
to voluM
C
surt
7.1 Plae.
aliquot of
digaatad
•••pi* in
b.ak.r
7.1 Add
coneantratad
HNO, and H.SO,
avaporata
••upla .
7.1 Continue
adding HHO,
to eoaplata
digaation
7.1 Cos)
•anpla,add
raagant H.O,
•vaporata,cool
7.1 Transfer
digaatad aaapla
to flaik.add
cone HC1 bring
to voluaa
7.2 Prepare
'• tandarda.,
tranifar to
flaaka,bring
to voluaa
74 Add
praparad *aopla
to flaak,bring
to voluma,uaa
at blank
7.5 Tranafar
portion of
digaitad aaaipla
or atandard to
raaction vaatal
7.S Add XI
aolution, and
SnCl,
•olution
7.S Raduoa
aatal to it*
loxaat
oxidation'
atata
7.5 Attach
vaaaal to gar
glaaavar*,fill
droppar vith Zn
•lurry
75 Introduea
Zn •lurry
into aaoipla
or standard
•olution
7.6 Uaa
193.7-nm wava-
langth and
background
eorraotion
7.7 To oparata
argon hydrogan
fl»«a,folio.
•anufacturar ,
instruction*
7.8 Plot ,
abaorfaaneaa of
•pikad «ampla»
blank v».
concantration*
7,8 Hava
concentration
ba part of
calibration
C
Stop
7061A - 6
Revision 1
July 1992
-------
7062
-------
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/vg/L
to 400jjg/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 1.0/yg/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 a-nd 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 OURNER
CONDENSER
MIXING
TEC*
OAS/LIQIMO
SEPARAT
VALUE
(SAMPLING)
•OlSCONNECTE
DURING S*X9n
ANALYSIS
_—» DRAIN
THERMOMETER
20 TURN COIL
(TEFLON)
HOTPLATE
VALVE .
(•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 jug 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 /yg 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 400fjg/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 antimony1 and arsenic solution to three 25 ml aliquots
of each unknown, Spiking volumes shoulci be kept'less than 0.250 ml to avoid
excessive spiking dilution errors.
r
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 6.7-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
-------
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 fjg/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
-------
METHOD 7062
ANTIMONY AND ARSENIC (ATOMIC ABSORPTION, BOROHYDRIDE REDUCTION)
7.1 Use Method
3060 (furnace AA
option) to digest
1.0 g sample.
7.1 Add
concentrated
HCI.
7.1 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 to
aliquot urea;
L-cysteine, HCI;
heat H20 bath;
bring to volume.
7.3 Prepare
standards from
standard stock
solutions of Sb
and As.
7.4 Uee the
method of
•tandard
additions on EP
extracts, only.
7.6 - 7.6 Analyze
the sample
using hydride
generation
apparatus.
1
r
7.6 • 7.7 Determine
Sb and As cone.
from standard
calibration
curve.
' 1
r
7.6 -7.6 Analyze
the sample
using hydride
generation
apparatus.
1
7.7 Determine
Sb and As
concentrations
by Method of
Standard Additions.
Stop
7062-8
Revision 0
Septenfcer 1994
-------
7080
-------
METHOD 7080
)' '
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 1f 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 1on1zat1on 1n the nitrous oxide/
acetylene flame, resulting 1n a significant decrease 1n sensitivity. All
samples and standards must contain 2 ml of the KC1 1on1zat1on suppressant
(Section 5.2.3 below) per 100 ml of solution.
N
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 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 1.7787 g barium chloride
(BaCl2'2H20, analytical reagent grade in Type II water and dilute to
7080 - 1
Revision
Date September 1986
-------
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 add and at the same
concentration as will result 1n the sample to be analyzed after
processing. All calibration standards and samples should contain
. 2 mL/100 ml of the potassium chloride (1on1zat1on suppressant) solution
described 1n Section 5.2.3. . ;
5.2.3 Potassium chloride solution: Dissolve 95 g potassium
.chloride (KC1) 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 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: 1-20 mg/L with a wavelength of 553.6 nm.
Jei-jill'vlty: 0.4 mg/L.
Detection limit: 0.1 mg/L. .
, i . .
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 ,
K Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055;
December 1982, Method 208.1.
7080-2
Revision 0
Date September 1986
-------
METHOD 7080
BARIUM (ATOMIC A8SOWTION. DIRECT ASPIRATION)
3.0
Pr«p»r«
•tandard*
i
7.1
prcpar
. en
••e
7.8
ror
••mpla
•tipn •••
•Ptar 3..
tlon 3.2
Analyz* u«ing
MtthOd 7000.
Section 7.2
7080 - 3
Revision 0
Date September 1986
-------
7080A
-------
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.
I
7.2 Analyze using
Method 7000
Section 7.2.
{ Stop J
7080A - 3
Revision 1
September 1994
-------
7081
-------
METHOD 7081
BARIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION ' '
.1.1 See Section l.-O of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
' • s
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
-------
4.2.7 Other operating parameters should be set as specified by the
" particular instrument manufacturer. < . • .
i _
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 ''.-•' x .•
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
-------
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.
7081 - 3 Revision 0
July 1992
-------
METHOD 7081 /
BARIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
S.0 Prepare
•tandard*
7.1 For sample
preparation »••_
Chapter 3, Section
32
7.2 Analyze uaing
.Method 7000
Section 7 ..3
Stop
7081 - 4
Revision 0
July 1992 '
-------
7131
-------
METHOD 7131
CADMIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
•' " ' i
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 In addition to the normal Interferences experienced during graphite
furnace analysis, cadmium analysis can suffer from severe nonspecific absorp-
tion and light scattering caused by matrix components during, atomlzatlon.
Simultaneous background correction 1s 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.
3.4 Many plastic p1pet 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 tine 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.
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 atomlzatlon
can be operated using lower atomlzatlon temperatures for shorter
time periods than the above-recommended settings.
7131-1
Revision 0
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 1.000 g of cadmium metal
(analytical reagent grade) 1n 20 ml of 1:1 HMOs 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 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 Annonlua phosphate solution (40%): Dissolve 40 g of ammonium
phosphate, (NH4)2HP04 (analytical reagent grade), 1n Type II 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 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.
'i • '
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 213.2 of Methods
for Chemical Analysis of Water and Wastes.
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.
7131 - 2
Revision
Date September 1986
-------
9.3 The data shown 1n Table 1 were .obtained from records of state anc
contractor laboratories. The data are Intended to show the precision of th€
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. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7131 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Preparation
Method
Laboratory
Replicates
Lagoon soil 3050
NBS SRM 1646 Estuarine sediment 3050
Solvent extract of 61ly waste 3030
0.10, 0.095 ug/g
0.35 ug/ga
1.39, 1.09 ug/L
aBias of -3% from expected value.
7131 - 4
Revision 0
.Date September 1986
-------
METHOD MJl '
CAOXUH (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
s.o
Prepare
standard*
7.1
For
tempi*
preparation at*
chapter 3.
eectlon 3.2
7.2
Analyze using
Method 7000.
Section 7.3. .
calculation 7.4
( v Stop J
7131 - 5
, Revision 0
Date September 1986
-------
7131A
-------
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
Matrix
Preparation
Method
Laboratory
Replicates
Lagoon soil 3050
NBS SRM 1646 Estuarine sediment 3050
Solvent extract of oily waste 3030
0.10, 0.095 ug/g
0.35 ug/g"
1.39, 1.09 ug/L
"Bias of -3% from expected value.
7131A - 4
Revision 1
September 1994
-------
METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
( Start J
^
f
5.2 Prepare
standards.
^
1 '
7.1 For sample
preparation see
Chapter 3, Section
3.2.
>
r
7.2 Analyze using
Method 7000
Section 7.3.
i
r
I Stop J
7131A - 5
Revision 1
Septaiter 1994
-------
7196A
-------
METHOD 7196A
CHROMIUM. HEXAVALENT (COLORIMETRIC)
v . .
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.
Add.ition 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
-------
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, K2Crp07 (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-dipheriylcarbazide
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.Q 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 s,hould 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 ah 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 fiVtrate 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 l,ow 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
Wastewatef 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
-------
Start
METHOD 7196A
CHROMIUM, HEXAVALENT (COLORIMETRIC)
7.1 Tran»fer
entract to
•• flail., add
diphony 1carbeside
tolution.and mi*
for color
development
7.1 Add H.SO.
aolution,dilute,let
•tand.aoaaura the
correct abaorbanee
reading,and
determine Cr
present
7.2.1 Treat Cr
•tandarda by the
•an* procedure aa
•ample,pipet Cr
standard aolution
into beaker
' 2.2 Develop color
for •tandarda,
mcature and correct
reading,eon*truet
calibration curve
7 3.1 Analyse a
itcond aliquot of
pH adjuated
filtrate »piked
with Cr(VI) for
ven f icat ion
7.3.2 Dilute
•piked •••pi*
with blank
aolution,
adjuat reault*
Ye.
Deee
ipike eene "V Ho
eiceed ealibr
curve?
la
aupre»«ive
interference
indicated
Na«
aaaple
produced an
acidic
extract?
la th
recovery
leea than 85*
t
la apike
recovery of
85-115%
obtained?
7.3.3 Dilute
•aaiple and
reanalyie
7.4 Prepare an
alkaline
aliquot «ith 1H
NaOH.epik*
aaaple,analyse
Doee \ Tee
interference
peraiat?
7.4 Analytical
ithod it verified
Stop
7196A - 6
Revision 1
July 1992
-------
7211
-------
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 Sectipn 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 Prepare
•tandards
7.1 For (ample
preparation •••
Chapter 3, Section
32
7.2 Analyze uiing
Method 7000
Section 7.3
Stop
7211 - 4
Revision 0
July 1992
-------
7381
-------
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 (genera,!):
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 HNOj 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 1
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. .
*• ' s
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,N 1983; EPA-600/4-79-020.
7381 - 3 Revision 0
. July 1992
-------
METHOD 7381
IRON (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
5.0 Pr«p»r«
•t»nd»rd»
7.1 Tor laapl*
preparation • ••
Chapter 3, Section
3.2
7.2 An»lyi« uting
M.thod 7000
S.etion 7.3
Stop
7381 - 4
Revision 0
July 1992
-------
7430
-------
METHOD 7430
LITHIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
. ; .s
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 Correct-ion: 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, LuC03, 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:1
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)
St.rt
S.0 Pr»p»r«
•tandard*
7.1 for t»«pl«
preparation, *mm
Chapter 3, Step 3.2
7.2 Analyi* uting.
M.thod 7000, St.p
7.2
Stop
7430 - 3
Revision 0
July 1992
-------
7461
-------
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
N •
. 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, s"ee 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 1-0 mi 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. v
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 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.
7461 - 2 Revision 0
July 1992
-------
METHOD 7461
MANGANESE (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
5.0 Prepari
•tandard*
7.1 For taapl*
preparation !••
Chapter 3, Section
3.2
7.2 Analyie u*ing
Method 7000
Section 7.3
Stop
7461 - 3
Revision 0
July 1992
-------
7470
-------
METHOD 7470
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION -.
i • • .
. i
1.1 Method 7470 1s a cold-vapor atomic absorption procedure approved for
determining the concentration of mercury 1n mobility-procedure extracts, aque-
ous wastes, and ground waters. (Method 7470 can also be used for analyzing
certain solid and sludge-type wastes; however, Method 7471 1s 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 1n this method.
2.2 Method 7470, a cold-vapor atomic absorption technique, 1s based on
the absorption of radiation at 253.7-nm by mercury vapor. The mercury 1s
reduced to the elemental state and aerated from solution 1n a closed system.
The mercury vapor passes through a cell positioned 1n the light path of an
atomic absorption spectrophotometer. Absorbance (peak height) 1s measured as
a function of mercury concentration.
2.3 The typical detection limit for this method 1s 0.0002 mg/L.
3.0 INTERFERENCES ,
3.1 Potassium permanganate 1s added to eliminate possible Interference
from sulflde. Concentrations as high as 20 mg/L of sulflde as sodium sulflde
do not Interfere with the recovery of added Inorganic mercury from Type II
water.
3.2 Copper has also been reported to Interfere; however, copper concen-
trations as high as 16 mg/L had no effect on recovery of mercury from spiked
samples:
3.3 Seawaters, brines, .and Industrial effluents high 1n chlorides
require additional permanganate (as much as 25 mL) because, during the
oxidation step, chlorides are converted to free chlorine, which also absorb's
radiation of 253.7 nm. Care must therefore be taken to ensure that free
chlorine 1s absent before the mercury 1s .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 1n 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.
7470 - 1
Revision
Date September 1986
-------
3.4 Certain volatile organic .materials that absorb at this wavelength
may also cause Interference. A preliminary run without reagents should
determine 1f this type of Interference 1s present.
4.0 APPARATUS AND MATERIALS,
4.1 Atomic absorption spectrophotometer or equivalent: Any atomic
absorption unit with an opensample presentationarea 1n which to mount the
absorption cell 1s suitable. Instrument settings recommended by the partic-
ular 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 electrode!ess discharge lamp.
4.3 Recorder: Any multlrange variable-speed recorder that 1s compatible
with the UV detection system 1s suitable. .
4.4 Absorption cell; Standard spectrophotometer cells 10 cm long with
quartz end windowsmay be used. Suitable cells may be constructed from
Plexlglas tubing, 1 1n. O.D. x 4.5 1n. The ends are ground perpendicular to
the longitudinal axis, and quartz windows (1 1n. diameter x 1/16 In.
thickness) are cemented 1n place., The cell Is strapped to a burner for
support and aligned 1n the light beam by use of two 2-1n. x 2-1n. cards. One-
1n.-diameter holes are cut 1n the middle of each card. The cards are then
placed over each end of the cell. The cell 1s then positioned and adjusted
vertically and horizontally to give the maximum transmlttance.
4.5 Air pump; Any peristaltic pump capable of delivering 1 liter
a1r/m1n 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 Uter/mln.
/
4.7 Aeration tubing; A straight glass, frit with a coarse porosity.
Tygon tubing 1s used for passage of the mercury vapor from the sample bottle
to the absorption cell and return. ,.
4.8 Drying tube; 6-1n. x 3/4-1n.-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 posi-
tioned to shine on the absorption cell so that the air temperature 1n the eel>
1s about 10*C above ambient. '
4.9 The cold-vapor generator 1s assembled as shown 1n Figure 1.
4.9.1 The apparatus shown 1n Figure 1 Is a closed system. An open
system, where the mercury vapor 1s passed through the absorption cell
only once, may be used Instead of the closed system. .
7470 - 2
Revision
Date September 1986
-------
o
I
to
o
Air Pump
£Z~}
Desiccant
•0-
D
i"-"1!.
Absorption Cell
Bubbler
Sample Solution
in BOO Bottle
O
Scrubber
Containing
a Mercury
Absorbing
Media
o> n
rt- <
n -*.
o
^? 3
o
r*
n
§
n
vo
00
o>
Figure 1. Apparatus for ftameless mercury determination.
-------
4.9.2 Because mercury vapor 1s toxic, precaution must be taken to
avoid Its Inhalation. Therefore, a bypass has been Included 1n 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% ^$04; or
2. 0.25% Iodine 1n a 3% KI solution. ' x
A specially treated charcoal that W111- adsorb mercury vapor 1s also
available from Barnebey and Cheney, East 8th Avenue and North Cassldy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22. ,
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Sulfurlc add (^504), concentrated: Reagent grade.
5.3 Sulfurlc add. 0.5 N: Dilute 14.0 ml of concentrated sulfurlc add
to 1.0 liter.
5.4 N1 trie add (HNOs), concentrated: Reagent grade of low mercury
content^ If a high reagent blank 1s obtained, 1t may be necessary to
distill the nitric add.
5.5 Stannous sulfate; Add 25 g stannous sulfate to 250 ml of 0.5 N
H2S04~ This mixture 1s a suspension and should be stirred continuously
during use. (Stannous chloride may be used 1n place of stannous
sulfate.) ,
5.6 Sodium chlor1de-hydroxy1am1ne sulfate solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamlne sulfate 1n Type II water and
dilute to 100 ml. (Hydroxylamlne hydrochlorlde may be used 1n place of
hydroxylamlne sulfate.)
5.7 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate 1n 100 ml of Type II water.
5.8 Potassium persulfate. 5% solution (w/v): Dissolve 5 g of potassium
persulfate 1n 100 ml of ^Type II water.
5.9 Stock mercury solution; Dissolve 0.1354 g of mercuric chloride 1n
75 ml of Type II water. Add 10 ml of concentrated HN03 and adjust the
volume to 100.0 mL (1 ml = 1 mg Hg).
5.10 Mercury working standard; Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 g per mL.
This working standard and the dilutions of the stock mercury solution
should be prepared fresh dally. Acidity of the working standard should
be maintained at 0.15% nitric add. This add should be added to the
flask, as needed, before addition of the aliquot.
7470 - 4
Revision 0
Date September 1986
-------
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 All sample containers must be prewashed with detergents, adds, and
Type II 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 these samples are 38 days 1n glass
containers and 13 days 1n plastic containers.
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. Add 5 mL of
H?S04 and 2.5 mL of concentrated HNO}, 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, 1f necessary, until the purple color persists
for at least 15 m1n. 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
chlor1de-hydroxylam1ne 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 1n Paragraph 7.3.
7.2 Standard preparatlon; Transfer 0-, 0.5-, 1.0-, 2.0-, 5.0-, and
10.0-mL allquots of tnemercury working standard, containing' 0-1.0 ug of
mercury, to a series of 300-mL BOD bottles. Add enough Type II 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 m1n. Add 8 mL
of potassium persulfate to each bottle and heat for 2 hr 1n a water bath
maintained at 95*C. Cool and add 6 mL of sodium chloHde-hydroxylamlne
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 1n Paragraph 7.3.
7.3 Analysis; At this point the sample 1s allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 I1ter/m1n, 1s 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 m1n), open the bypass valve and
7470-;5
Revision
Date September 1986
-------
continue the aeration until the absorbance returns to Us minimum valve.
Close the bypass valve, remove the stopper and frit from the BOD bottle, and
continue the aeration.
7.4 Construct a calibration curve by plotting the absorbances of stan-
dards versus mlcrograms of mercury. Determine the peak height of the unknown
from the chart and read the mercury value from the standard curve.
7.5 Analyze all EP extracts, all samples analyzed as part of a del 1 sting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions.
7.6 Duplicates, spiked samples, and check standards should be 'routinely
analyzed. .
7.7 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 multlphased
or wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).
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 oh 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 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.
7470 - 6
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n 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.
7470 - 7
' Revision
Date September 1986
-------
METHOD 7J7Q
MEBCUR* (MANUAL COLO-VAPOR TECHNIQUE)
7. t
Prepare temple
7.2
,
run circulating
pump
continuously.
•trite
Transfer aliquot* of
mercury working •
•tandero to »erl«» of
bottle* for standard
preparation
7.2
7.5
Conctruct
»tion
curve:o«termln«
height »na
mercury value
AOd
Type II
water to eecn
Dottle: mix: eoa
eoncen. HjSO«
• no HNOj
7.Z
7.6
by netnoa of
(tenaera
aaditions
. Add
solution;
•00 potassium
pereulf ate:
neat: cool
7.3
7.7
Routinely
analyt«
duplicate*.
•piKea *enple*.
ana eneek
•tanoaro*
Reduce
•xceca
permanganate:
•ttecn to
••ration
•pparatui
7.8
Calculate metal
concentratlona
( sto° )
7470 - 8
Revision 0
Date September 1986
-------
7470A
-------
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 1 iter 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.i 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 lisa 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 1.0% H2S04; or
2. 0.25% Iodine in a 3% KI solution.
7470A - 2 Revision 1
September 1994
-------
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
-------
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
-------
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
-------
METHOD 7470A
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
Sample Preparation
Standard Preparation'
7.1 Transfer aliquot
to bottle, add HjSC^
and HNOs, and mix.
1
7.2 Transfer aliquot
of the Hg working
standard to
bottle.
7.2 Add reagent
water, mix, add
oonoantratad
HzSCUend HNOa.
7.1 Add more
permanganate
if necessary.
7.1 Add!
potassium
persulfate, heat
for 2 hrs., cool.
7.2 Add KMn04
potassium
persulfate. heat
for 2 hrs. and cool.
1
7.2 Add sodium
chloride-
hydroxylemine
eulfate, wait 30
eeconds.
7.1 Add sodium
• chloride-
hydroxylamine
sulfate, wait-30
seconds.
I
.7.1 Add stannous
sulfate, attach
to aeration
apparatus.
7.3 Analyze
sample.
I
1:
7.2 Add stannous
sulfata, attach
to aeration
apparatus.
7.4 Construct
calibration
curve, determine
peak height and
HQ value.
I
7.4 Routinely •
analyze duplicates,
spiked samples.
7.5 Calculate
metal
concentrations.
( Stop J
7470A- 6
Revision 1
September 1994
-------
7471
-------
METHOD 7471
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION '
1.1 Method 7471 1s approved for measuring total mercury (organic and
Inorganic) 1n soils, sediments, bottom deposits, and sludge-type materials.
All samples must be subjected to an appropriate dissolution step prior to •
analysis.
2.0 SUMMARY OF METHOD
i •> •
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, 1s based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor. The
mercury 1s reduced to the elemental state and aerated from solution 1n a
closed system. The mercury vapor passes through a cell positioned 1n the
light path of an atomic absorption spectrophotometer. Absorbance (peak
height) 1s measured as a,function of mercury concentration.
2.3 The typical detection limit for this method 1s 0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate 1s added to eliminate possible Interference
from sulflde. Concentrations as high as 20 mg/L of sulflde as sodium sulflde
do not Interfere with the recovery of added Inorganic mercury from Type II
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 1n 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 1s absent before the mercury 1s reduced and swept Into the cell.
This may be accomplished by using an excess of hydroxylamlne sulfate reagent
(25 mL). In addition, the dead air space 1n 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 1f this type of Interference Is present.
7471 - 1
Revision 0
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer or equivalent; Any atomic
absorption unit with an opensample presentationarea 1n which to mount the
absorption cell 1s suitable. Instrument settings recommended by the partic-
ular 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 multlrange variable-speed recorder that 1s compatible
with the UV detection system Is suitable.
4.4 Absorption cell; Standard spectrophotometer cells 10 .cm long with
quartz end windows maybe used. Suitable cells may be constructed from
Plexlglas tubing, 1 1n. O.D. x 4.5 In. The ends are ground perpendicular to
the longitudinal axis, and quartz windows (1 1n. diameter x 1/16 1n.
thickness) are cemented 1n place. The cell 1s strapped to a burner for
support and aligned 1n the light beam by use of two 2-1n. x 2-1n. cards. One-
1n.-diameter holes are cut 1n the middle of each card. The cards are then
placed over each end of the cell. The cell 1s then positioned and adjusted
vertically and horizontally to give the maximum transmlttance.
4.5 Air pump; Any peristaltic pump capable of delivering 1 L/m1n air
may be used~iA Masterflex pump with electronic speed control has been found
to be satisfactory.
4.6 Flowmeter; Capable of measuring an air flow of 1 L/m1n.
4.7 Aeration tubing; A straight glass frit with a coarse porosity.
Tygon tubing 1s used for passage of the mercury vapor from the sample bottle
to the absorption cell and return.
4.8 Drying tube; 6-1n. x 3/4-1n.-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 1n the
cell 1s about 10*C above ambient. ,
4.9 The cold-vapor generator 1s assembled as shown 1n Figure 1.
4.9.1 The apparatus shown In Figure 1 1s a closed system. An open
system, where the mercury vapor 1s passed through the absorption cell
only once, may be used Instead of the closed system.
4.9.2 Because mercury vapor 1s toxic, precaution must be taken to
avoid Its Inhalation. Therefore, a bypass has been Included 1n the
7471 -2
Revision
Date September 1986
-------
Air Pump
Destennt
^
Absorption Cell
Bubbler
Sample Solution
in BOD Bottle
D
Containing
a Mercury
Absorbing
Media
073
ot n
Figure 1. Apparatus for f tameless mercury determination.
n\
co\
-------
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 10X ^04, or
2. 0.25% Iodine 1n a 3% KI solution.
A specially treated charcoal that will adsorb mercury vapor 1s also
available from Barneby and Cheney, East 8th Avenue and North Cassldy
Street, Columbus, Ohio 43219, Cat. 1580-13 of 1580-22.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Aqua regla; . Prepare Immediately before use by carefully adding
three volumes of concentrated.HC1 to one volume of concentrated HN03.
5.3 Sulfurlc add, 0.5 N: Dilute 14.0 ml of concentrated sulfurlc add
to 1 liter;
5.4 Stannous sulfate; Add 25 g stannous sulfate to 250 ml of 0.5 N
sulfurlc add. This mixture 1s a suspension and should be stirred
continuously during use. A 10% solution of stannous chloride can be
substituted for stannous sulfate.
5.5 Sodium chlor1de-hydroxylam1ne sulfate solution; Dissolve 12 g of
sodium chloride and 12 g of hydroxylamlnesulfate 1n Type II water and dilute
to 100 ml. Hydroxylamlne hydrochlorlde may be used 1n place of hydroxylamlne
sulfate.
5.6 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate 1n 100 ml of Type II water.
5.7 Mercury stock solution: Dissolve 0.1354 g of mercuric chloride 1n
75 ml of Type II water. Add 10 ml of concentrated nitric add and adjust the
volume to 100.0 ml (l.O.mL = 1.0 mg Hg).
5.8 Mercury working standard; Make successive dilutions of the stock
mercury solution to obtainaworking standard containing 0.1 ug/mL. This
working standard and the dilution of the stock mercury solutions should be
prepared fresh dally. Acidity of the working standard should be maintained.at
0.15% nitric add. This add should be added to the flask, as needed, before
adding the aliquot.
1 i -
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.
7471 - 4
Revision
Date September 1986
-------
6.2 All sample containers must be prewashed with detergents, aqlds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH <2 with nitric add.
6.4 For solids or semlsollds, moisture may be driven off In a drying
oven at a temperature of 60*C.
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 Type II water and
5 ml of aqua regla. Heat 2 m1n In a water bath at 95*C. Cool; then add 50 ml
Type II water and 15 ml potassium permanganate solution to each sample bottle.
Mix thoroughly and place 1n the water bath for 30 m1n at 95*C. Cool and add 6
ml of sodium chlorlde-hydroxylamlne sulfate to reduce the excess permanganate.
CAUTION: Do this addition under a hood, as Cl£ could be evolved. Add
55 ml of Type II 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 t^SOa 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 m1n. Cool, dilute to a volume of 100 ml
with Type II water, and add 6 ml of sodium chlor1de-hydroxylam1ne sulfate
solution to reduce the excess permanganate. Purge the dead air space and
continue as described under step 7.4.
7.3 Standard preparation; Transfer 0.0-, 0.5-, 1.0-, 2.0-, 5.0-, and
lO-mL allquotsof themercury working standard, containing 0-1.0 ug of
mercury, to a series of 300-mL BOD bottles. Add enough Type II water to each
bottle to make a total volume of 10 ml. Add 5 ml of aqua regla and heat 2 m1n
1n a water bath at 95*C. Allow the sample to cool; add 50 ml Type II water
and 15 ml of KMn04 solution to each bottle and return to the water bath for
30 m1n. Cool and add 6 ml of sodium chlorlde-hydroxylamine sulfate solution
to reduce the excess permanganate. Add 50 ml of Type II water. Treating each
bottle Individually, add 5 ml of stannous sulfate solution, Immediately attach
the bottle to the aeration apparatus, and continue as described 1n
Step 7.4. ' .
7.4 Analysis; At this point, the sample 1s allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 L/m1n, 1s 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 mlh), 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.
t • j • '
7471 - 5
Revision 0
Date September 1986
-------
7.5 Construct a calibration curve by plotting the absorbances of
standards versus micrograms of mercury. Determine the peak height of the
unknown from the chart and read the mercury value from the standard curve.
7.6 Analyze all EP extracts, all samples analyzed as part of a dellsting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions (see Method 7000, Section 8.7).
1 •
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed. -
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. Concentrations reported for multlphased or wet samples must be
appropriately qualified (e.g., 5 ug/g dry weight).
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 if they fall on the plateau of.a calibration cuive.
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 1n Method 245.5 of Methods
for Chemical Analysis of Water and Wastes.
7471 - 6
Revision
Date September 1986
-------
9.2 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 245.5.
2. Gasklll, A., Compilation and Evaluation, of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7471 - 7
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Preparation
Method
Laboratory
Replicates
Emission control dust
Wastewater treatment sludge
Not known
Not known
12, 12 ug/g
0.4, 0.28 ug/g
7471 - 8
Revision 0
Date September 1986
-------
MERCURY IN SOLID OR SENISOUJO WASTE (MANUAL COLO-VAPOR TECHNIQUE)
7. 1
For ••molt
preparation welgn 3
portions of dry
• ample: add Typt II
Mater and ooua regie
to e«cn
Use 1 of 2
digestion proced
for sample
prep.
cone. HiSO* and.
cone. MNOj to
sample: add
KMnO solution
7.1
Heat:
cool: add
Type XI water
and potassium
permonganate
solution
7.2
Autoclave
- • l samples:
cool: dilute:
add sodium
chloride
hydroxylemine
7.1-1 Heat:
Icool: add
sodium cnlorioe
hydroxylamin*
sulfate ana
Type II water
7.1
Aoe
stsnnous
sulfate to ••en
bottle: attach
to aeration
apparatus
7471 - 9
Revision 0
Date September 1986
-------
METHOD 7471
MERCURY IN SOLID OR SEMISOLIO HASTE (MANUAL COLO-VAPOP TECHNIQUE)
(Continued)
Transfer aliquot* of
mercury working
standard to series of
Bottles for standard
preparation
7.3
For
analysis.
run circulating
pumo
continuously.
aerate
Add
Type II
water and aqua
regia to each
bottle; heat
7.3
7.3 I
I Construct
caliOration
Curve: determine
peak height and
mercury value
Cool: add Type II
water and KMn04
solution: neat: cool:
•dd codiun chloride
hydroHylemtne aulfate'
solution
7.6
• Analyze
Oy method of
standard
additions
7.3
Add Type
i II water
and stennous
sulfate: attach
to aereti'on
apparatus
7.7
Routinely
i enelyxe
duol icates.
spiked samples.
end check
.standards
7.B
Calculate metal
concentrations
st°°
3
7471 - 10
Revision 0
Date September 1986
-------
7471A
-------
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 delivering 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 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.
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
-------
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
-------
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 C.12 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
( Dige
\ Met
1
r
iod? .S'
Type
f 1
7.1 Weigh triplicate
samples, and reagent
water and
aqua regia.
>
r
7.1 Heat, cool,
add reagent water
and KMnO4.
1
>
)
r
7.3 Transfer aliquots
of Hg working
standards to
bottles.
>
,
7.3 Add reagent
water to volume,
and aqua regia,
heat and cool.
i
7.2 Add
KMn04, cover,
heat and cool,
dilute with
reagent water.
I
7.1 Heat, cool,
add sodium
chloride-
hydroxylamine
sulfate.
^
7.1 Ad
water,
sulfatt
to a
appi
\
d reagent
stannous
), attach
gration
iratus.
w
'
7.2 Add sodium
chloride-
hydroxylamine
sulfate, purge
dead air space.
i
'
7.4 Analyze
sample.
>
f
7.3 Add reagent
water and KMn04
solution, heat
and cool.
>
r
7.3 Add sodium
chloride-
hydrox'ylamine
sulfate and
reagent water.
i
7.:
stannoi
app
\f
1 Add
is sulfate,
o aeration
gratus.
I
7.5 Construct
calibration
curve; determine
peak height and
Hg value.
I
7.5 Routinely
analyze duplicates,
spiked samples.
7.6 Calculate
metal
concentrations.
( Stop J
7471A - 7
Revision 1
September 1994
-------
7741A
-------
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/HCT
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: Single or dual channel, single-
or double-beam instrument with a grating monochromator, photomultiplier 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.
i
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.
i
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
-------
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
8,1 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
-------
METHOD 7741A
SELENIUM (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
C Start J
Standard Preparation
Sample Preparation
7.2.1 Pipat
• took
•olutien into
flaak; bring
to voluma
7.2.2 Prepare 6
Sa working
atandarda from
atock; bring to
voluma
7.3.1 Tranafer
3 atandard
portion*,add
•ampla,bring to
voluma
7.1.1 Stop
dig«ation,eool,
add HHO.
7.1.1 Add
coneantratad
H.SO, and HNO,
to (ample and
•vaporata
7.1.2 Cool
aampla,add
raagant water,
evaporate,cool
7.3.2 To
prepare blank
add aanpla to a
flaak and bring
to voluma
7.4 Follow
instruction*
for operating
argon-hydrogen
flame
7.S Uaa 196.0
nm wavelength
7.1.2 Add
concentrated
HC1 and bring
to volume
7.6 Tranafer
digeated aampla
to reaction
veaael,add
SnCl,
7.6 Allow to
atand,attach
veaael to
glaaaware,add
2n alurry
7.6 Record Se
concentration
C
Stop
7741A - 5
Revision 1
September 1994
-------
7742
-------
METHOD 7742
SELENIUM (ATOMIC ABSORPTION, BOROHYDRIDE REDUCTION)
1.0 SCOPE AND APPLICATION
1.1 Method 7742 is an atomic absorption procedure for determining 3 /jg/i
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 /vg/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
-------
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 electrode!ess 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
•DISCONNECTS
OUR INO S«X3n
AMALVSIS
20 TURN COIL
(TEFLON)
__—* DRAIN
HOTPLATE
UALWE .
(BLANK)
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 (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 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: Pipet 1 ml selenium
standard stock solution into all volumetric flask and bring to volume
with reagent water containing 1.5 mL concentrated HNOg/liter. The
concentration of this solution is 1 mg Se/L (1 ml = 1 jwg 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 jjg/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
-------
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 jjg 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
-------
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
-------
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 3060.
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
H2O bath;
bring to volume.
7.3 Prepare
working
standards from
standard stock
Se solution.
7.4 Use the
method of
standard
addition* on
extracts, only.
7.4 Spike 3
aliquots 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.
I
Stop
7742-8
Revision 0
September 1994
-------
7760 A
-------
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 spectrophotbmeter: 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
-------
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
concentration!; 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
-------
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. .
5
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
-------
7.3 If plating out of AgCl is suspected, the precipitate can be
red issolved 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.
i '
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
. A
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
-------
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
-------
TABLE 1.
METHOD PERFORMANCE DATA
Sample
Matrix
Preparation Laboratory
Method Replicates
Vlastewater treatment sludge
Emission control dust
3050
3050
2.3, 1.6 mg/Kg
,1.8, 4.2 mg/Kg
7760A - 6
Revision 1
July 1992
-------
METHOD 7760A
SILVER (ATOMIC ABSORPTION, DIRECT ASPIRATION)
7.2.1 Tranafer
•ample aliquot to
beaker,add cone
HNO..evaporate to
near drynaaa,eool,
add cone HNO.,heat
•o gentle reflux
action occur*
7.1 Prapara aanpla
according to Mathod
3040
7.1 Prapara aaapla
according to Mathod
3050
7.2.2 Complete
digeation,evaporate
to near drynaaa „
cool,add cone HHOi ,
varm to diaaolva
any precipitate or
reaidue
7.2:3 Filter aample
if neceaaary,adju«t
voluaa Kith vatar
7.3 Nautraliz* '
tanplt.add cyanogin
iodida to diitolv*
pracipitata ,r»aka .
standard* dnitting
acid , tranifar'
aliquot of atoek
•olution to baakar,
add vatar
7.3 Adju.t pH »ith
NH,OH,rin*a
alactroda into
•olution with
water,add cyanogen
iodide,wait I
hour,transfer to
fla*k.bring to .
volume Kith «atar;
7.4-7.6 Set
inctruaent
parameter*
7.7 Conatruct
calibration curve
7.8 Analyze by
method of itandard
addition if
neceaaary
7.9) Calculate metal
concentration
Stop
7760A - 7
Revision 1
July 1992
-------
7761
-------
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.
. .' ' - x • •
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
-------
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.
i '' • I
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 b9ttle.
. 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
-------
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. 00 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 but 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
1 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/LV 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
spectropho.tometer 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
-------
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 repl.icate sample for every 10 samples or per
analytical batch, whichever 4s 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)
^
damonatrata
applicability of
preparation
technique to other
matrix type* .by
analysing • pi'kad
•amplaa and
reference materials
IAqueoui
7.2.1 Tranafer
•ample.aliquot to
beaker; add cone.
HNO,; evaporate to
near dryneaa; cool;
add cone. HNO.;
heat ao gentle
reflux aetion
. oceura
' 7.2.2 Complete
digeation;
•vaporat* 'to n«ar
dryna»»; cool; add
cone. HNOi; warm to
dittolv* any
preeipitats or
r«*idu« ;
7.2.3 Filt.r tampU
if noc»»»ary;
adjuat volum«'vith
water
7.3 Neutralize
laaple; add'cyanogen
iodide to dinolve
precipitate; remake
•tandarda omitting
acid; transfer
aliquot of ttock /
aolution to beaker;
add water
7:3 Adjuat pH with
NH.OH; rin.e
eleetrodea into
• oln "with water;
add cyanogen
iodide; wait 1
hour; tranafer to
flaak; bring to
volume with water
.7.4-7.6 Set
inttrument
parameter*
7 7 Inject tample
aliquot; dilute if
neeetiary
7.8 Conttruct
calibration curve
7.9-7.10 Analyse
•ampla
7.10 Calculate
•tal concentration
Stop
7761 - 6
Revision.0
July 1992
-------
7780
-------
METHOD 7780
STRONTIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
i
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Meth.od 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. ATI 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 i
7780 - 1 Revision 0
July 1992
-------
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 .
-------
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 +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
5.0 Prepare
•tandarda
7.1 for vaaple
preparation •••
Chapter 3, Section
32
7.2 Analyse uting
Method 7000
Section 7.2
Stop
7780 - 5
Revision 0
July 1992
-------
7951
-------
METHOD 7951
ZINC (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION , .
1.1 See Section 1.0 of Method 7000. . .
V . '
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES ,
** ' i
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 arid 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 ac.id 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.s
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 iig/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
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METHOD 7951
ZINC (ATOMIC' ABSORPTION, FURNACE TECHNIQUE)
Start
5 . 0 Pr«par«
•tandarda
7.1 Tar tanpl*
preparation *••
Chapter 3, Section
32
7.2 Analyza ufing
M.thod 7000
Section 7.3.
Stop
,7951 - 4
Revision 0
July 1992
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