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

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8.0  QUALITY CONTROL

      8.1    All  quality control  data should be  maintained  and available for
easy reference or inspection.

      8.2    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

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                    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

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    FIGURE 4.
COMPACTION TESTER
                                   Combined Weight
                                   0.33 kg (0.73 Ib)
                               Sample
                                   Elastomeric
                                   Sample Holder
    1310A - 15
Revision 1
July  1992

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                           ,   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

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1311

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                                  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. .
                                     1311-  1                       Revision  0
                                                             ,     July  1992

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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.
                                    1311-  2                       Revision 0
                                                                 July 1992

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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.

                                  .  1311- 3                      Revision 0
                                                                 July 1992

-------
      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
                                                                 July 1992

-------
      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.


                                    1311-  5                      Revision 0
                                                        ,         July 1992

-------
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
                                    1311- 6       .               Revision 0
                                                                 July 1992

-------
      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


                                    1311-7                       Revision 0
                                                                 July  1992

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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
                         '.••'•             '                     July 1992

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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
                                   ....  •          •-.       •'     July 1992

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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
                                                                 July 1992

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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
                                                                 July  1992

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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
                                                    Revision 0
                                                    July 1992

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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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.July  1992

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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
                                                                 July .1992

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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
                                                                 July 1992

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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
                                 Revision 0
                                 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
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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

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              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

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              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

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        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

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                  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

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                          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

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1312

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                                  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

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      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

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      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

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              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


                                   1312 - 6                       Revision  0
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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.
                      1312 - 7                       Revision 0
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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)
                             1312 - 9                       Revision 0
                                                            September 1994

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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

                             1312 - 11                       Revision 0
                                                            September 1994,

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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

                                   1312 - 12                       Revision 0
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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.
                                   1312  -  13                       Revision 0
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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.
                                   1312  -  14                       Revision 0
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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.
                             1312  -  15                       Revision 0
                                                            September 1994

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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

                                   1312 -  16                       Revision 0
                                                                  September 1994

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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

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      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

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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

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                         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

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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
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

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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
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

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                      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

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       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

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                    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
                            July 1992

-------
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

-------
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

-------
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

-------
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
July  1992

-------
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
                                                                  July 1992

-------
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

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                                  METHOD 3015

                 MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS
                             SAMPLES AND EXTRACTS
 1.0  SCOPE AND APPLICATION

         1.1   This digestion procedure  is  used  for the preparation of aqueous
 samples, mobility-procedure extracts, and wastes that contain suspended solids
 for analysis, by flame atomic absorption spectroscopy (FLAA), graphite furnace
 absorption spectroscopy  (GFAA),  inductively coupled argon plasma  spectroscopy
 (ICP),  or  inductively coupled argon  plasma mass  spectrometry  (ICP-MS).   The
 procedure is a hot acid leach for determining available metals.  Due to the rapid
 advances  in  microwave   technology,  consult  your  manufacturer's  recommended
 instructions  for guidance on their microwave digestion system and  refer to the
 SW-846  "DISCLAIMER" when conducting analyses using Method 3015.

         1.2   Samples  prepared by Method 3015 using nitric acid digestion may be
 analyzed by FLAA, GFAA,  ICP-AES, or ICP-MS  for the following:

                          Aluminum             Lead
                          Antimony             Magnesium
                          Arsenic*             Manganese
                          Barium               Molybdenum
                          Beryllium            Nickel
                          Cadmium              Potassium
                          Calcium              Selenium*
                          Chromium             Silver
                          Cobalt               Sodium
                          Copper               Thallium
                          Iron                 Vanadium
                                               Zinc
                          *Cannot be analyzed by FLAA

2.0  SUMMARY OF METHOD

         2.1   A  representative 45 ml  aqueous  sample  is  digested in  5  mL of
concentrated nitric acid in a fluorocarbon (PFA or  TFM) digestion  vessel for 20
minutes  using microwave  heating.   After the digestion process,  the sample is
cooled, and then filtered, centrifuged, or allowed to settle in a clean sample
bottle prior to analysis.

3.0  INTERFERENCES

         3.1   Many samples that contain organics,  such as TCLP extracts, will
result in higher vessel pressures which have the potential to cause venting of
the vessels.   Venting  can result in either loss  of analytes and/or  sample, which
must be avoided.  A smaller sample size can be used but the final water volume

                                   3015 - 1                       Revision 0
                                                                  September 1994

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prior to nitric acid addition must remain  at 45 mL.  This is required to retain
the heat characteristics of the calibration procedure.  Limits of quantitation
will change with sample quantity (dilution) as with instrumentation."

4.0  APPARATUS AND MATERIALS

        4.1  Microwave  apparatus  requirements

               4.1.1   The  microwave  unit  provides  programmable power  with a
        minimum  of 574 W,  which  can be  programmed to within  + 10 W  of the
        required  power.   Typical  units provide  a  nominal  600 W to  1200  W of
        power.   Temperature monitoring  and control of  the  microwave unit are
        desirable.

               4.1.2   The  microwave unit  cavity  is  corrosion  resistant  and
        well ventilated.

               4.1.3   All electronics  are  protected against  corrosion for safe
        operation.

               4.1.4   The system requires  fluorocarbon  (PFA or  TFM)  digestion
        vessels  (120  mL capacity)  capable  of  withstanding  pressures  up to 7.5
        ± 0.7  atm  (110 ± 10 psig) and capable of controlled pressure relief at
        pressures  exceeding  7.5 ± 0.7 atm  (110 ± 10 psig).

               4.1.5   A rotating  turntable is employed to  insure  homogeneous
        distribution  of microwave radiation within the unit.  The speed of the
        turntable  should be  a minimum of 3 rpm.

               CAUTION: Those laboratories now  using or contemplating the use of
               kitchen type microwave ovens for this method  should  be aware of
               several significant  safety  issues. First, when an acid  such as
               nitric  is used  to assist  sample digestion in  microwave units in
               open vessels,  or  sealed vessels equipped  with venting  features,
               there is the potential  for the acid gases  released to corrode the
               safety devices that prevent  the  microwave magnetron from shutting
               off when the door is opened.  This can result in operator exposure
               to microwave energy.  Use of a unit with corrosion resistant safety
               devices prevents this from occurring.

               CAUTION: The  second  safety  concern relates to the use  of sealed
               containers without pressure relief valves in the unit.   Tempera-
               ture is the important variable controlling the  reaction.  Pressure
               is needed to attain  elevated temperatures  but must be safely con-
               tained.  However,  many digestion vessels constructed from certain
               fluorocarbons  may crack,  burst,  or  explode  in  the oven  under
               certain  pressures.     Only  unlined   fluorocarbon  (PFA or  TFM)
               containers with pressure relief mechanisms  or containers  with
               fluorocarbon  (PFA or TFM) liners and pressure relief mechanisms
               are  considered acceptable at present.


                                   3015  -  2                       Revision 0
                                                                  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

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7.0  PROCEDURE

        7.1  Calibration of Microwave Equipment

              NOTE;  If the microwave unit uses temperature  feedback control
              capable  of replicating the performance  specifications of  the
              method,  then the calibration procedure may be omitted.

              7.1.1  Measurement  of  the  available   power   for  heating   is
        evaluated so that absolute  power  in  watts  may  be  transferred from  one
        microwave unit to another.   For cavity  type microwave equipment, this
        is  accomplished  by measuring the  temperature  rise  in  1 kg  of  water
        exposed to microwave radiation for a  fixed  period of time.  The analyst
        can relate power in watts to the partial  power setting of the unit.  The
        calibration format required  for laboratory microwave units  depends on
        the  type  of electronic  system used by .the manufacturer to provide
        partial microwave power.   Few units have an  accurate and precise linear
        relationship between percent power settings and absorbed power.  Where
        linear circuits have been  utilized, the calibration curve can be deter-
        mined  by  a  three-point  calibration method (7.1.3),   otherwise,  the
        analyst must use the multiple point  calibration method  (7.1.2).

              7.1.2  The multiple  point  calibration involves the  measurement
        of absorbed power over a large range  of power settings.  Typically,  for
        a 600 W unit, the following power  settings  are  measured; 100,99,98,97,
        95,90,80,70,60,50, and .40% using  the  procedure described in section
        7.1.4.  This data is clustered about the customary working power ranges.
        Nonlinearity has  been commonly encountered at the  upper  end of  the
        calibration.    If the unit's  electronics are known to  have  nonlinear
        deviations in  any region  of proportional   power  control,  it  will  be
        necessary to make a  set  of measurements that bracket the power  to be
        used.   The final  calibration point  should be at  the  partial  power
        setting that will be used in the test.   This setting  should  be checked
        periodically to  evaluate  the integrity  of the  calibration.   If  a
        significant change  is  detected  (±10 W), then  the entire  calibration
        should be reevaluated.

              7.1.3  The three-point  calibration  involves the  measurement of
        absorbed power at three different power settings.  Measure the power at
        100%  and  50%  using  the  procedure  described  in  section  7.1.4,  and
        calculate the power setting corresponding to the required power in watts
        specified  in   the  procedure  from  the  (2-point)  line.    Measure  the
        absorbed power at that partial power  setting.  If the  measured absorbed
        power does not correspond to the specified  power within  ±10  W, use  the
        multiple point calibration in 7.1.2.   This  point should  also be used to
        periodically verify the integrity of the calibration.

              7.1.4  Equilibrate a  large  volume  of water to  room temperature
        (23 ±2 °C).   One  kg  of  reagent water is weighed (1,000.0 g  ± 0.1 g)
        into a fluorocarbon (PFA or TFM)  beaker  or  a beaker made of  some  other
        material that  does  not significantly absorb microwave energy  (glass

                                   3015  -  4                        Revision  0
                                                                  September  1994

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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
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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

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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

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                  7.3.8.2   Settling:   Allow  the sample  to stand  until  the
               supernatant  is  clear.  Allowing  a sample to  stand overnight will
               usually accomplish this.  If it does not, centrifuge or filter the
               sample.

                  7.3.8.3  Filtering: The filtering apparatus must be
               thoroughly cleaned  and prerinsed with dilute  (approximately 10%
               V/V)  nitric  acid.  Filter the sample through   qualitative filter
               paper into a second  acid-cleaned container.

               7.3.9  The concentration values obtained  from analysis must be
         corrected for the dilution factor  from  the acid addition.  If the sample
         will  be  analyzed  by  ICP-MS  additional  dilution  will  generally  be
         necessary.   For example,  the sample may  be diluted by  a factor of 20
         with  reagent water and the acid strength  adjusted  back  to 10% prior to
         analysis.   The  dilutions used should be recorded and the measured con-
         centrations adjusted  accordingly  (e.g., for a 45 ml  sample and 5 ml of
         acid  the correction factor is  1.11).

8.0  QUALITY CONTROL

         8.1   All  quality  control  measures described  in Chapter  One,  of this
Manual, should be followed.

         8.2  For each analytical  batch  of  samples  processed,  analytical reagent
blanks (also field blanks if they were taken) should be carried throughout the
entire sample preparation and analytical process.   These blanks will be useful
in determining if samples are being contaminated.

         8.3   Duplicate  samples  should be  processed  on a routine  basis.   A
duplicate sample is a real  sample brought through the whole  sample preparation
and  analytical  process.   A duplicate  sample  should  be processed  with  each
analytical batch or every 20 samples, whichever is the greater number.

         8.4  Spiked  samples or standard reference materials  should be employed
to determine accuracy.  A  spiked sample should be included with each group of
samples processed and whenever a new sample matrix is  being analyzed.

9.0  METHOD PERFORMANCE

         9.1    Refer to  Table  1 for a summary of performance  data.
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                                                                  September 1994

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10.0  REFERENCES

1.       Introduction  to  Microwave Sample  Preparation:  Theory  and Practice.
         Kingston,  H.  M.;  Jassie,  L.  B., Eds.; ACS Professional Reference Book
         Series: American  Chemical  Society,  Washington, DC,  1988;  Ch 6  & 11.

2.       1985 Annual Book of ASTM Standards.  Vol.  11.01; "Standard  Specification
         for Reagent Water";  ASTM:  Philadelphia,  PA,  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

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                      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

-------
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

-------
                         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

-------
3051

-------
                                  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).
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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

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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

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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


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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.
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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.


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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.


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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.
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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
                                   3051 - 12                       Revision 0
                                                                   September 1994

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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
                                                   Revision 0
                                                   September 1994

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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
       September 1994

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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.


                                  , 3500A  - 1                        Revision 1
                                   ,  .    .       , .                    July 1992

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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.

                                   3500A - 2                         Revision  1
                                                                   .  July 1992

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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)
                                   3500A - 3                  '.   .  Revision  1
                                                                     July  1992

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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
                                   3500A -  4                       ' Revision 1
                                                                     July 1992

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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

                                  3500A - 5                        Revision 1
                                                                     July 1992

-------
      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.

                                   3500A -  6                        Revision  1
                                                                     July 1992

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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.

                                   3500A  - 7                        Revision 1
                                                                     July 1992

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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;

                       3500A  - 8                         Revision  1
                               •     ..           .        July 1992

-------
            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.
                                   3500A - 9                         Revision  1
                                         .                             July  1992

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                METHOD 3500A
ORGANIC  EXTRACTION AND  SAMPLE PREPARATION
                           Jrr i vc i a i. 11 e
Yes
) 	 '
I

7 1 5 Mat hod
• . 3580


'
7 1 1 Method
3S50

\,



                                                         722 Method
                                                            5030  -'
                                                           Ciract
                                                          In jeclion
                  3500A -' 10
Revision  1
 July  1992

-------
3510A

-------
                                 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.  ^

                                   3510A - 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   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.

                                  3510A :-x 2                  •    Revision 1
                                                    •.••'• July  1992

-------
            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

                                   3510A -  3                       Revision 1
                                                             -     July 1992

-------
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

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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

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      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

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      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

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            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

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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

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                            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

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                             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

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3540A

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                                 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

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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   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

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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

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      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

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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

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                                                  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

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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

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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).
            4.3.5 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

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      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.
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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.
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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.


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                                                                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.
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                                                                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

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                                 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

-------
      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

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     reaches  an apparent volume of  approximately  0.5  ml,  remove  the  apparatus
     from the water bath and  allow  to  drain  and cool  for  at  least  10 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

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     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

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            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

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      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

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            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

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      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

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                                                  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

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                                                  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

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                                 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

-------
      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

-------
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

-------
      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

-------
      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

-------
            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

-------
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

-------
            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

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                                   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

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                          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

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3630B

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                                 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

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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

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      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

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      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

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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

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                                    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

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                              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

-------
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

-------
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

-------
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.


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      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


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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.
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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
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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.

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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

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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

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      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,


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      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
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            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

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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

-------
                                    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

-------
                                          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
                                    July 1992

-------
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

-------
      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

-------
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

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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

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                                 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

-------
      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

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                                 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

-------
      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

-------
       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

-------
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

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                        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

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                                   TABLE  2
            QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
                      HIGH-CONCENTRATION SOILS/SEDIMENTS

                Approximate                         Volume of
            Concentration Range                  Methanol  Extract8
              500-10,000 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

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5040A

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                                 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

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      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

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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

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            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

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      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

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                  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

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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
                                                            -   September 1994

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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
                                                                   September 1994

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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
                                                        September  1994

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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
                 Revision 0
             September  1994

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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
                                                                September 1994

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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
                                                                September 1994

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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


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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


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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.
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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
    Revision 0
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
    Revision 0
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
                                   5041  -  28                        Revision 0
                                                                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

-------
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
                    Revision 0
               September  1994

-------
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
    Revision 0
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
     Revision 0
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
                                               Revision  0
                                          September  1994

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5050

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                                  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

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                                   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

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                                   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

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              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

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                                 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

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concentrated HN03 and dilute to volume in a 1,000 ml volumetric flask with
water.

      5.3.11   Iron solution,  stock,  1  mL = 1000 ug Fe:  Dissolve 1.40 g
Fe203  (mole fraction Fe  =  0.6994),  weighed accurately  to  at least four
significant figures,  in  a  warm mixture  of 20 ml  (1:1) HC1  and  2 ml of
concentrated HN03. Cool,  add an additional 5.0  ml of concentrated HN03, and
dilute to volume  in a 1,000 ml volumetric  flask with water.

      5.3.;12   Lead solution,  stock,  1  mL = 1000 ug Pb:  Dissolve 1.60 g
Pb(NO,)2  (mole  fraction Pb  » 0.6256), weighed  accurately to  at least four
significant figures, in  a  minimum amount of  (1:1) HN03. Add 10 ml (1:1)
HN03 and  dilute to volume in a 1,000 ml volumetric flask with water.

      5.3.13  Lithium solution,  stock,  1  ml = 1000 ug Li: Dissolve  5.324 g
lithium carbonate (mole  fraction  Li  =  0.1878), weighed accurately to at
least  four significant  figures,  in  a minimum amount  of  (1:1)  HC1  and
dilute to volume  in a 1,000 mL volumetric-flask with water.

      5.3.14   Magnesium solution,  stock,  1'  mL  =  1000 ug  Mg:  Dissolve
1.7.0 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

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     at least four  significant figures, in water  and  dilute to volume  in  a
   .  1,000 mL volumetric flask with water.

           5.3.21  Silver solution, stock,  1 ml = 1000  ug Ag:  Dissolve
     1.60 g AgNO? (mole fraction Ag = 0.6350),  weighed  accurately to at least
     four significant figures,  in water  and  10  ml concentrated HN03. Dilute to
     volume in a 1,000 ml volumetric flask with water.

           5.3.22  Sodium solution, stock,  1 ml = 1000 ug Na:  Dissolve 2.50 g
     NaCl  (mole  fraction  Na =  0.3934),  weighed  accurately to  at  least  four
     significant figures,  in water. Add  10.0 ml concentrated HN03 and dilute to
     volume in a 1,000 ml volumetric flask with water.

           5.3.23   Strontium  solution,   stock,  1  ml =  1000 ug  Sr:  Dissolve
     2.415 g of  strontium  nitrate (Sr(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

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      NOTE:  If the  addition  of  silver  to  the  recommended  acid  combination
            results in  an initial precipitation, add 15 ml  of water and warm the
            flask until the solution clears.  Cool 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
                                                                  July 1992

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 8.0   QUALITY  CONTROL

       8.1  All quality control data should be maintained and available for easy
 reference  or  inspection.'  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
                           July 1992

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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

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                                  METHOD 6020

                INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
1.0  SCOPE AND APPLICATION

      1.1  Inductively coupled plasma-mass spectrometry  (ICP-MS) is applicable
to the determination of sub-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).


                                    6020-1                         Revision 0
                                                                  September 1994

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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]).


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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


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deposition on the sampler and skimmer cones,  spray chamber design,  and  the type
of nebulizer affect the extent of the memory interferences which are observed.
The rinse period  between  samples  must be long enough to eliminate significant
memory interference.

4.0  APPARATUS AND MATERIALS

      4.1  Inductively coupled plasma-mass spectrometer:

            4.1.1   A system capable  of providing resolution,  better  than or
      equal to amu at 10% peak height is required. The  system must have  a mass
      range from at least  6  to 240 amu and a data system  that  allows corrections
      for isobaric  interferences  and  the application of the  internal  standard
      technique.  Use of  a  mass-flow controller for  the nebulizer argon and a
      peristaltic pump for the sample solution are recommended.

            4.1.2  Argon gas supply:  high-purity grade (99.99%).

5.0  REAGENTS

      5.1  Acids used in  the preparation of standards and  for sample processing
must be of high purity.  Redistilled acids are recommended because of  the high
sensitivity of ICP-MS.  Nitric acid at less than  2  per cent (v/v)  is  required for
ICP-MS to minimize damage to the  interface and to minimize(isobaric molecular-ion
interferences with  the analytes.   Many more molecular-ion  interferences are
observed on the analytes  when hydrochloric and  sulfuric acids are used  [3,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.


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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.
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      5.5  Blanks:  Three  types of blanks are required  for  the analysis.   The
calibration  blank  is  used  in  establishing   the  calibration  curve.    The
preparation blank is used to monitor for possible contamination resulting from
the sample preparation procedure.  The rinse blank is used to flush the system
between all samples and standards.

            5.5.1  The calibration blank consists of the same concentration(s)
      of the same acid(s)  used to prepare the final dilution of the calibrating
      solutions of  the  analytes [often  1 percent HN03  (v/v)  in reagent water]
      along with  the  selected concentrations of  internal  standards  such that
      there  is  an  appropriate  internal  standard  element  for  each  of  the
      analytes.  Use of HC1 for antimony and silver is cited in Section 5.1

            5.5.2   The  preparation  (or  reagent) blank  must be carried through
      the  complete  preparation procedure  and   contain  the  same volumes  of
      reagents as the sample solutions.

            5.5.3   The  rinse blank consists of 1 to 2  percent  HN03  (v/v)  in
      reagent water.  Prepare a sufficient quantity to flush the system between
      standards and samples.

            NOTE;  The  ICS  solutions  in .Table  2  are  intended  to  evaluate
            corrections for known interferences  on only the analytes in Table 1.
            If Method 6020 is used to determine an element not listed in Table
            1,  it  is  the responsibility  of the  analyst to  modify the  ICS
            solutions, or  prepare an alternative ICS solution,  to allow adequate
            verification of correction of interferences  on the unlisted element
            (see section 8.4).

      5.6  The  interference check solution  (ICS)  is  prepared  to contain known
concentrations of interfering  elements  that  will  demonstrate  the magnitude of
interferences and provide  an adequate  test of any  corrections.  Chloride in the
ICS provides  a means  to  evaluate  software  corrections  for  chloride-related
interferences such  as 35C11V  on 5V and  40Ar35Cl+  on  75As+.   Iron  is used to
demonstrate adequate  resolution of  the  spectrometer for  the  determination  of
manganese. Molybdenum serves to indicate oxide effects on cadmium isotopes.  The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion isobaric interferences. The  ICS is  used to
verify that  the interference levels  are  corrected  by the data  system  within
quality control limits.

            5.6.1   These  solutions  must be  prepared  from ultra-pure  reagents.
      They can be obtained commercially  or prepared by the following procedure.

                  5.6.1.1    Mixed ICS  solution  I  may  be  prepared by  adding
            13.903 g A1(N03)3-9H20,  2.498 g CaC03  (dried at 180 C  for 1 h before
            weighing), 1.000 g Fe, 1.658  g MgO,  2.305 g  Na2C03,  and 1.767  g K2C03
            to 25 ml of reagent water.  Slowly  add 40 ml of (1+1) HN03.   After
            dissolution is  complete,  warm  the  solution to degas.    Cool  and
            dilute to 1,000 ml with  reagent water.


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                  5.6.1.2   Mixed  ICS solution  II  may be  prepared by  slowly
            adding 7.444 g 85 %  H3P04, 6.373 g 96% H2S04,  40.024  g  37%  HC1,  and
            10.664 g  citric  acid C607H8 to 100 ml of reagent water.  Dilute to
            1,000 mL  with reagent water.

                  5.6.1.3   Mixed ICS  solution  III may be  prepared by  adding
            1.00 mL   each  of  100-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

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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

                                   6020-11                        Revision  0
                                                                  September 1994

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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
                                                                  September 1994

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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).
                                    6020-13                        Revision  0
                                                                  September 1994

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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
                                    6020-14                        Revision  0
                                                                   September 1994

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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
                                    6020-15                        Revision 0
                                                                   September 1994

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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.
                                    6020-16                        Revision  0
                                                                  September 1994

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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.
                                    6020-17
                                                      Revision  0
                                                      September 1994

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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
                                                Revision  0
                                                September 1994

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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
Revision 0
September 1994

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7000A

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                                 METHOD 7000A

                           ATOMIC  ABSORPTION  METHODS
1.0   SCOPE AND APPLICATION

      1.1   Metals in solution may  be  readily  determined  by atomic absorption
spectroscopy. The method is simple,  rapid, and applicable to a large number of
metals  in  drinking,  surface,  and saline waters  and domestic  and industrial
wastes. While drinking water free of  particulate matter may  be analyzed directly,
ground  water,  other  aqueous  samples,  EP extracts,  industrial  wastes,  soils,
sludges, sediments, and other solid wastes require digestion prior to analysis
for both total and acid  Teachable metals.  Analysis for dissolved elements does
not require digestion if the sample has been filtered and acidified.

      1.2   Detection limits,  sensitivity, and optimum ranges of the metals will
vary with the matrices and models of atomic absorption spectrophotometers. The
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
                                                                  July  1992

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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

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interferences.  It  is particularly  useful  when analyzing  for  As in the
presence of Al and when analyzing for Se in the presence of Fe.

      7.3.3    Memory effects  occur  when   the analyte  is  not  totally
volatilized during atomization.  This condition depends on several  factors:
volatility  of  the  element  and  its  chemical  form,  whether  pyrolytic
graphite  is  used,  the rate  of atomization,  and  furnace  design.  This
situation is  detected through blank burns. The tube  should be  cleaned by
operating  the furnace  at  full  power for  the required  time  period,  as
needed, at  regular intervals during the series of determinations.

      7.3.4   Inject  a  measured  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.

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                               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

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                                  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

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7.0  PROCEDURE                                                         '

      7.1   Place a 50-mL aliquot of digested sample  (or, in the case of analysis
of EP extracts, 50 mL) of the material to be analyzed in a 100-mL beaker.  Add
10 ml concentrated HNO, and 12 ml 18N H2S04.  Evaporate the sample in the hood
on an electric hot plate until white SO, fumes are observed (a volume of about
20 ml),.  Do not let the sample char.  If charring occurs, immediately turn off
the heat, cool, and add an additional  3  ml  of HN03.  Continue to add additional
HN03 in' order  to  maintain an excess  (as  evidenced  by the .formation  of brown
fumes).  Do not let the solution  darken,  because arsenic may be  reduced and lost.
When the sample remains colorless or straw yellow during evolution of S03 fumes,
the digestion is complete.  Cool the  sample,  add about 25 ml water, and again
evaporate  until S03 fumes  are produced  in  order to expel  oxides of nitrogen.
Cool.  Transfer the digested sample  to a 100-mL volumetric flask.   Add 40 mL of
concentrated HC1 and bring to volume with water.

      7.2   Prepare  working  standards  from  the standard  arsenic  solution.
Transfer 0,  0.5,  1.0,  1.5, 2.0, and  2.5 ml of  standard  to  100-mL volumetric
flasks and bring to volume  with diluent.  These concentrations will be 0, 5, 10,
15, 20, and 25 ug As/liter.

      7.3   If EP  extracts are  being analyzed or if  a matrix interference is
encountered,  take  the 15-, 20-, and  25-mg/liter standards  and quantitatively
transfer 25 mL of each of these standards into separate 50-mL volumetric flasks.
Add  10  mL  of the prepared  sample to  each   flask.   Bring  to  volume with water
containing  1.5 mL HCl/liter.

      7.4   Add 10 mL of prepared sample to a 50-mL  volumetric  flask.  Bring to
volume  with water  containing 1.5  mL HCl/liter.   This  is the  zero addition
aliquot.                ,   '                         -        .

NOTE:       The absorbance from the .zero addition aliquot will  be  one-fifth that
            produced  by the prepared sample.  The  absorbance from the spiked
            "samples will  be one-half that  produced by  the  standards plus the
            contribution from one-fifth of  the prepared sample.   Keeping these
            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

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                                      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

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7062

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                                 METHOD 7062

       ANTIMONY AND ARSENIC (ATOMIC ABSORPTION.  BOROHYDRIDE REDUCTION)


1.0  SCOPE AND APPLICATION

      1.1  Method 7062 is an atomic absorption  procedure  for determining  1/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

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      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

-------
      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

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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

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      7.4   Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of  mercury.   Determine  the peak height of the unknown
from the chart and read the  mercury value  from the  standard curve.  Duplicates,
spiked samples, and check standards should be routinely analyzed.

      7.5   Calculate  metal  concentrations  (1)  by  the method  of  standard
additions,  or  (2) from a  calibration curve.   All dilution  or concentration
factors must be taken into account. Concentrations  reported for multiphased or
wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).

8.0   QUALITY CONTROL

      8.1  Refer to section 8.0 of Method 7000.

9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method 245.1 of Methods
for Chemical Analysis of Water and Wastes.

10.0  REFERENCES

1.    Methods  for Chemical   Analysis  of  Water  and Wastes,  EPA-600/4-82-055,
December 1982, Method 245.1.
                                   7470A  -  5                       Revision 1
                                                                  September 1994

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                            METHOD 7470A
MERCURY  IN LIQUID  WASTE  (MANUAL COLD-VAPOR  TECHNIQUE)
              Sample Preparation
                   Standard Preparation'
  7.1 Transfer aliquot
  to bottle, add 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

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7471

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                                 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

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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

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                                                    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

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     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

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     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

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     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

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                      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

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   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

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                               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

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7471A

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                                 METHOD 7471A

       MERCURY  IN  SOLID OR SEMISOLID  WASTE  (MANUAL  COLD-VAPOR  TECHNIQUE)


1.0   SCOPE AND APPLICATION

      1.1   Method 7471  is approved  for measuring total  mercury  (organic and
inorganic) in soils,  sediments,  bottom  deposits, and sludge-type materials. All
samples must be subjected to an  appropriate dissolution step prior to analysis.
If this dissolution procedure is  not sufficient to dissolve  a specific matrix
type or sample, then this method is not applicable for that matrix.

2.0   SUMMARY OF METHOD

      2.1   Prior to analysis, the solid or semi-solid samples must be prepared
according to the procedures discussed in this method.

      2.2   Method 7471, a cold-vapor atomic  absorption method, is based on the
absorption of radiation at the 253.7-nm  wavelength by mercury vapor.  The mercury
is reduced to the  elemental state  and aerated from  solution in a closed system.
The mercury vapor  passes through a cell  positioned in the light  path  of an atomic
absorption spectrophotometer.  Absorbance (peak  height) is measured as a function
of mercury concentration.

      2.3   The typical  instrument detection  limit  (IDL)  for this method  is
0.0002 mg/L.

3.0   INTERFERENCES

      3.1   Potassium permanganate is added to  eliminate possible  interference
from sulfide.  Concentrations as high as 20 mg/Kg of sulfide, as sodium sulfide,
do not interfere with  the recovery of added inorganic mercury in reagent water.

      3.2   Copper has also been reported to  interfere; however, copper concen-
trations as high  as 10  mg/Kg had  no  effect on  recovery  of mercury  from spiked
samples.

      3.3   Samples high in chlorides require additional  permanganate  (as much
as 25 ml) because, during  the oxidation step,  chlorides  are  converted  to free
chlorine, which also absorbs radiation  of 253 nm.   Care must therefore be taken
to ensure that free chlorine is  absent  before the  mercury is  reduced and swept
into the cell.  This  may be accomplished by using an excess  of  hydroxylamine
sulfate reagent (25 ml).   In addition, the dead  air space  in the BOD bottle must
be purged before adding stannous sulfate.

      3.4   Certain volatile organic materials that  absorb at this wavelength may
also cause interference.  A preliminary run  without  reagents should determine if
this type of interference is present.

4.0   APPARATUS AND MATERIALS

      4.1   Atomic  absorption  spectrophotometer  or  equivalent:    Any  atomic
absorption unit with  an open sample presentation  area  in which to mount the

                                   7471A -  1                       Revision 1
                                                                  September 1994

-------
absorption cell is suitable.   Instrument  settings recommended by .the particular
manufacturer  should  be followed.   Instruments designed  specifically  for the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.

      4.2   Mercury hollow cathode lamp or electrodeless discharge lamp.

      4.3   Recorder:  Any multirange variable-speed recorder that  is compatible
with the UV detection system is suitable.

      4.4   Absorption cell:  Standard spectrophotometer cells 10 cm long with
quartz end windows may be used.  Suitable cells may be constructed from Plexiglas
tubing,  1  in.  O.D.   x  4.5  in.    The  ends  are ground  perpendicular  to the
longitudinal axis, and quartz windows  (1  in.  diameter x 1/16 in. thickness) are
cemented in place.  The cell  is strapped  to a burner  for support and aligned in
the light beam by  use of two 2-in.  x 2-in. cards.  One-in.-diameter  holes  are cut
in the middle of each  card.  The cards are then placed over each  end of the cell.
The cell  is then positioned and adjusted vertically and horizontally to give the
maximum transmittance.

      4.5   Air pump:  Any peristaltic pump capable of 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

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      4.10  Hot plate  or  equivalent  -  Adjustable and capable of maintaining a
temperature of 90-95°C.

      4.11  Graduated cylinder or equivalent.

5.0   REAGENTS

      5.1   Reagent  Water:    Reagent water  will  be  interference  free.   All
references  to  water in this  method refer  to  reagent water  unless  otherwise
specified.

      5.2   Aqua regia: Prepare immediately before use by carefully  adding three
volumes.of concentrated HC1 to one volume of concentrated HN03.

      5.3   Sulfuric acid, 0.5 N:   Dilute  14.0 ml of  concentrated sulfuric acid
to 1 liter.

      5.4   Stannous sulfate:   Add 25 g  stannous  sulfate to 250  ml  of 0.5 N
sulfuric acid.   This mixture is a  suspension  and should be stirred continuously
during use. A  10% solution of stannous chloride  can be substituted  for stannous
sulfate.

      5.5   Sodium chloride-hydroxylamine sulfate solution:   Dissolve 12 g of
sodium chloride and  12  g of hydroxylamine sulfate in reagent water and dilute to
100 ml.   Hydroxylamine hydrochloride  may be used  in place  of hydroxylamine
sulfate.

      5.6   Potassium permanganate,  mercury-free,  5% solution (w/v):  Dissolve
5 g of potassium permanganate in 100 ml of reagent water.

      5.7   Mercury stock solution:  Dissolve 0.1354 g of mercuric chloride in
75 mL of reagent water.   Add  10 ml of  concentrated  nitric acid and adjust the
volume to 100.0 mL (1.0 ml = 1.0 mg Hg).

      5.8   Mercury working standard:   Make  successive  dilutions  of  the stock
mercury solution to obtain a working standard  containing 0.1 ug/mL.   This working
standard and the dilution of the stock mercury solutions should be prepared fresh
daily.  Acidity of  the working standard should be maintained at  0.15% nitric
acid.    This acid  should be added  to the  flask, as  needed,  before adding the
aliquot.

6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   All samples must  have been collected  using a sampling  plan that
addresses the  considerations discussed in Chapter Nine of this manual.

      6.2   All sample containers  must  be  prewashed with detergents, acids, and
reagent water.   Plastic and glass containers are both suitable.

      6.3   Non-aqueous  samples  shall  be  refrigerated, when  possible,  and
analyzed as soon as possible."
                                   7471A  -  3                       Revision 1
                                                                  September 1994

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7.0   PROCEDURE

      7.1   Sample preparation:   Weigh  triplicate 0.2-g portions of untreated
sample and place in the bottom of a BOD bottle.  Add 5 ml of reagent water and
5 ml of aqua regia.  Heat 2 min in a water bath at  95°C.  Cool; then add 50 ml
reagent water and 15 ml potassium permanganate solution to each sample bottle.
Mix thoroughly and place in the water bath for 30 min at 95°C.  Cool and add 6
ml of sodium chloride-hydroxylamine sulfate to reduce the excess permanganate.

            CAUTION: Do this addition  under  a hood,  as 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

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                      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

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                                 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

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                                 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

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                          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

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4.0  APPARATUS AND MATERIALS

      4.1  Electric hot  plate:   Large enough to hold at  least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride  generator  or  a  generator
constructed similarly  to that shown in  Figure 1 (P. S. Analytical or equivalent).

            4.2.1  Peristaltic Pump: A four-channel, variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).   Pump  speed and tubing diameters should  be  adjusted to
      provide  the  following  flow rates:    sample/blank  flow  = 4.2  mL/min;
      borohydride flow =  2.1 mL/min.

            4.2.2  Sampling Valve (optional):    A sampling valve (found in the
      P. S.  Analytical  Hydride Generation System  or equivalent)  that  allows
      switching between samples and blanks (rinse solution) without introduction
      of air into the  system will provide more signal  stability.

            4.2.3  Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
      mixing T's, and  connectors are made of  fluorocarbon  (PFA or TFM)  and are
      of compatible  sizes  to form  tight,  leak-proof  connections  (Latchat,
      Technicon, etc.  flow injection  apparatus accessories or equivalent).

            4.2.4  Mixing Coil:  A 20-turn coil made by wrapping transfer tubing
      around a 1-cm diameter by 5-cm  long plastic or  glass rod (see Figure 1).

            4.2.5  Mixing  Coil  Heater,  if appropriate:   A  250-mL  Erlenmeyer
      flask containing 100 mL  of water heated to boiling on  a  dedicated  one-
      beaker hotplate  (Corning PC-35 or equivalent).   The  mixing coil  in 4.2.4
      is immersed in the  boiling water  to speed kinetics of the hydride  forming
      reactions  and   increase  solubility   of  interfering   reduced   metal
      precipitates.

            4.2.6  Gas-Liquid Separator:  A glass apparatus  for  collecting and
      separating liquid  and  gaseous  products (P.  S.  Analytical accessory or
      equivalent) which allows the liquid fraction to drain to waste and  gaseous
      products above the  liquid to be  swept by a regulated carrier  gas  (argon)
      out of the cell  for analysis.  To  avoid undue carrier  gas dilution, the
      gas volume above the  liquid  should not exceed 20 mL.   See Figure 1 for an
      acceptable separator shape.

            4.2.7  Condenser:  Moisture  picked  up  by the  carrier gas  must be
      removed before  encountering the  hot absorbance cell.   The moist  carrier
      gas with the  hydrides is dried by passing the gasses through a small (< 25
      mL) volume condenser  coil (Ace Glass Model 6020-02 or equivalent)  that is
      cooled to 5°C by  a water chiller (Neslab  RTE-110 or equivalent).  Cool  tap-
      water in place of a chiller is acceptable.
                                    7742-2                         Revision 0
                                                                  September 1994

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            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

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      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

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      7.2  Prepare samples for hydride analysis by adding 1.00 g urea,  and 20 ml
concentrated HC1 to a 5.00 ml aliquot of digested sample in a 50-mL volumetric
flask.  Heat in a water bath  to dissolve  salts and reduce selenium  (at least 30
minutes  is  suggested).    Bring flask  to  volume  with  reagent water  -before
analyzing.    A  ten-fold  dilution  correction   must   be  made   in  the  final
concentration calculations.

      7.3  Prepare working standards from the standard  stock selenium solution.
Transfer  0,  0.5,  1.0,  1.5,  2.0, and  2.5 ml of  standard to  100-mL volumetric
flasks and bring to volume with  diluent.  These concentrations will  be  0, 5, 10,
15, 20, and 25 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

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9.0  METHOD PERFORMANCE

      9.1  The relative standard deviation obtained by a single laboratory for
7 replicates of a contaminated soil was 18% for selenium at 8.2 ug/L in solution.
The average percent recovery of  the analysis of an 2 jjg/L  spike on  ten different
samples is 100.5% for selenium.

10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of  Water  and Wastes,   EPA-600/4-82-055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride Atomic Absorption  Methods  for Antimony, Arsenic,
      Selenium, and Tin",  an EMSL-LV internal report under Contract 68-03-3249,
      Job Order  70.16,  prepared for  T.  A. Hinners by D.  E.  Dobb,  and J.  D.
      Lindner of Lockheed Engineering and Sciences Co.,  and L. V. Beach of the
      Varian Corporation.
                                    7742-7                        Revision 0
                                                                  September 1994

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                                METHOD  7742
SELENIUM  (ATOMIC  ABSORPTION,   BOROHYDRIDE  REDUCTION)
    7.1 Use Method
    3050 (furnace AA
    option) to digest
     1.0 g sample.
       7.1 - 7.4
      Digest with
       H203as
     described in
     Method 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

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7760 A

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                                 METHOD 7760A

                 SILVER (ATOMIC  ABSORPTION.  DIRECT ASPIRATION)
1.0  SCOPE AND APPLICATION

      1.1 Method 7760 is an atomic absorption procedure approved for determining
the concentration of silver (CAS Registry Number, 7440-22-4) in wastes, mobility
procedure extracts, soils,  and ground water. All samples must  be subjected to an
appropriate dissolution step prior to analysis.


2.0  SUMMARY OF METHOD

      2.1   Prior to analysis by Method 7760,  samples must be prepared  for direct
aspiration.  The method of sample preparation will  vary according to the sample
matrix. Aqueous samples are subjected  to the  acid-digestion procedure described
in this method.                   .

      2.2   Following the appropriate dissolution of the sample, a representative
aliquot is aspirated  into  an  air/acetylene flame.  The resulting absorption of
hollow  cathode radiation  will  be proportional to  the  silver  concentration.
Background correction must be employed for all analyses.

      2.3   The typical detection limit for  this  method is 0.01 mg/L; typical
sensitivity is 0.06 mg/L.


3.0  INTERFERENCES

      3.1  Background correction is required  because nonspecific absorption and
light scattering may occur at the analytical wavelength.

      3.2  Silver nitrate solutions are light-sensitive and have the tendency to
plate out on container  walls. Thus silver  standards  should be  stored in brown
bottles.

      3.3  Silver chloride  is  insoluble; therefore, hydrochloric acid should be
avoided unless the silver  is already in solution as a chloride complex.

      3.4  Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.                         '


4.0  APPARATUS AND MATERIALS

      4.1 Atomic absorption 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

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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples must  have been collected  using a  sampling  plan  that
addresses the considerations discussed in Chapter Nine of this manual. .
                                    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

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                                 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

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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

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      6.2   Standards and samples should be stored In the dark,  In brown bottles,
and refrigerated. .


7.0  PROCEDURE

      7.1   Sample preparation - Aqueous samples should be prepared according to
Steps 7.2 and 7.3.  The applicability of a sample preparation technique to a new
matrix type  must  be  demonstrated by analyzing  spiked  samples and/or relevant
standard reference materials.

      7.2   Preparation of aqueous samples

            7.2.1  Transfer a representative aliquot of the well-mixed sample to
      a beaker and add 3  ml of concentrated HN03.  Cover the beaker with a watch
      glass.  Place the beaker on the hot plate and cautiously  evaporate to near
      dryness, making certain that the sample does not boil. 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

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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

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8.0  QUALITY CONTROL

      8.1   All quality control data should be maintained and available for easy
reference or inspection.         •'...'

      8.2   Calibration.curves must be composed  of  a  minimum  of a calibration
blank and three standards.  A calibration curve .must be prepared each day.

      8.3   Dilute  samples  if  they  are  more concentrated  than  the  highest
standard or if they fall on the plateau of a calibration curve.

      8.4   Employ a minimum of one reagent blank per sample batch or every 20
samples to determine if contamination or any memory effects are occurring.

      8.5   Verify calibration with an  independently  prepared quality control
reference sample every 10 samples.

      8.6   Run  one  spiked  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

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                                            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

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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

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                              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

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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

-------
                   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

-------