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ABSTRACT
This manual provides test procedures which may be used to evaluate
those properties of a solid waste which determine whether the waste is
a hazardous waste within the definition of Section 3001 of the Resource
Conservation and Recovery Act (PL 94-580). These methods are approved
for obtaining data to satisfy the requirement of 40 CFR Part 261, Identi-
fication and Listing of Hazardous Waste. This manual encompasses methods
for collecting representative samples of solid wastes, and for determining
the reactivity, corrosivity, ignitability, and composition of the waste
and the mobility of toxic species present in the waste.
-------
United States Off ice of Solid Waste July 1982
Environmental Protection and Emergency Response SW-846
' Agency Washington, DC 20460 Second Edition
solid waste "~~~~"~~~~~ii~~~~i~~~ziiizz!zz!^!^z^^zzii^i^zzizz^
oEPA Test Methods
for Evaluating Solid Waste
Physical/Chemical Methods
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
OFFICE OF
SOLID WASTE AND EMERGENCY RESPONSE
Subject: Distibution of Test Methods for Solid Waste;
Physical/ Chemical Methods (SW-846)
From: Debra Villari; Office of Solid Waste
To: Addressees
Enclosed you will find a copy of the new edition of
SW-846- "Test Methods for Evaluating Solid Waste". We are
able to provide a very limited number of copies to EPA
personnel for their official use.
The general public can obtain this document from the
Government Printing Office ( GPO Stock Number 055-002-81001-2)
at a price of $55.00. The Federal Register Notice announcing the
availability or this document is attached for your referral.
If I can be of further assistance please feel free to
contact me at FTS-382-4487
-------
, 41.562 Federal Register / Vol. 47. No. 183 / Tuesday, September 21. 1982 / Rules and Regulations
Boston. Massachusetts 02203. (617) 723-
6486.
SUPPLEMENTAL INFORMATION: Part C of
the Safe Drinking Water Act (SDWA)
provides for an Underground Injection
Control (U1C) Program. Section 1421 of
the SDWA requires the Administrator to
promulgate minimum requirements for
effective State programs to prevent
underground injection which endangers
drinking water sources. The
Administrator is also to list in the
Federal Register each State for which in
his judgment a State UIC Program may
be necessary. Each State listed shall
submit to the Administrator an
application which contains a showing
satisfactory to the Administrator that
the State: (i) Has adopted after
reasonable notice and public hearings, a
UIC Program which meets the
requirements of regulations in effect
under Section 1421 of the SDWA; and
(ii) will keep such records and make
such reports with respect to its activities
under its UIC program as the
Administrator may require by
regulations. After reasonable
"opportunity for public comment, the
Administrator shall by rule approve,
disapprove or approve in part and
disapprove in part, the State's UIC
Program.
The State of New Hampshire was
listed as needing a UIC Program on
March 19,1980 (45 FR 17632). The State
of New Hampshire submitted an
application under Section 1422 on April
12.1982, for the approval of an UIC
Program governing Classes I, n, HI, IV,
and V injection wells to be administered
by the New Hampshire Water Supply
and Pollution Control Commission
(NHWSPCC). On May 7,1982, EPA
published notice of its receipt of the
application, requested public comments,
and scheduled a public hearing on the
New Hampshire UIC Program submitted
by the NHWSPCC (47 FR 19726). Neither
requests for public hearing nor requests
to offer testimony at such hearing were
received by EPA. Therefore, pursuant to
the provisions of 40 CFR 123.54(c), the
public hearing was cancelled on June 1,
1932 because of expressed lack of
sufficient public interest
After careful review of the application
I have determined that the New
Hampshire UIC Program submitted by
the NHWSPCC meets the requirements
established by Federal regulations
pursuant to Section 1422 of the SDWA.
and hereby approve it
List of Subjects in 40 CFR Part 123
Hazardous materials, Indians—lands,
Reporting and recordkeeping
requirements. Waste treatment and
disposal. Water pollution control, Water
supply, Intergovernmental relations.
Penalties, Confidential business
information.
OMB Review
The Office of Management and Budget
has exempted this rule from the
requirements of Section 3 of Executive
Order 12291.
Certification Under the Regulatory
Flexibility Act
Pursuant to the provisions of 5 U.S.C.
605(b), I certify that approval by EPA -
under Section 1422 of the Safe Drinking
Water Act of the application by the New
Hampshire Water Supply and Pollution
Control Commission will not have a
significant economic impact on a
substantial number of small entities,
since this rule only approves State
'actions. It imposes no new requirements
on small entities.
Dated: September 9.1982.
Anne M. Gonuch,
Administrator.
[FR Doc. U-2SM2 PU«d 9-20-82: K48 am)
BIUJNO COOC «6«0 80 M
40 CFR Parts 122 and 260
[SWH-FRL 2209-1J
EPA Administered Permtt Programs:
The Hazardous Waste Permtt Program;
and Hazardous Waste Management
System: General
AGENCY: Environmental Protection
Agency.
ACTION: Notice of availability of
document; Amendment to final rule.
SUMMARY: The Environmental Protection
' Agency (EPA) is today announcing the
availability of a second edition of the
EPA manual Test Methods for
Evaluating Solid Waste, Physical/
Chemical Methods," EPA Publication
SW-846. This notice provides
information on when and where the
manual is available and how it differs
from the first edition. This notice also
amends the sections of EPA's
'consolidated permit regulations and
hazardous waste regulations that
incorporate the manual by reference, to
reflect the availability of a second
edition of the manual
EFFECTIVE DATE: September 21,1982.
FOR FURTHER INFORMATION CONTACT:
The RCRA Hotline at (800) 424-9346 (toll
free), or (202) 382-3000. For technical
information contact David Friedman,'
Office of Solid Waste fWH-565), U.S.
Environmental Protection Agency, 401 M
Street, S.W., Washington, D.C. 20460,
(202) 755-9187.
• SUPPLEMENTARY INFORMATION:
/. Second Edition of Manual
The EPA manual 'Test Methods for
Evaluating Solid Waste, Physical/
Chemical Methods," (1980HEPA
Publication No. SW-846). is
incorporated by reference hi several
sections of EPA's regulations. EPA first
published the manual in May, 1980 when
the Agency promulgated Phase I of the
hazardous waste regulations in the
Federal Register (45 FR 33065-33588).
Three revisions to the manual—Revision
A (August 1980), Revision B (July 1981],
and Revision C (February 1982)—have
been published since that date. EPA is
today announcing the publication of a
second edition of the manual which
incorporates all three revisions.
Although the second edition is
significantly reorganized and contains
additional explanatory information, EPA
views this edition as equivalent to the
first edition (with revisions), for
regulatory compliance purposes.
II. Availability of Manual and Revisions
In the past, the manual and revisions
to the manual have been made available
to the public free of charge on request
from the EPA Solid Waste Information
Office in Cincinnati, Ohio. The Agency
is no longer able to distribute these
publications on this basis. From now on,
these materials will be available to the
public as follows:
• A limited number of Revisions A
and B are available free of charge from
the EPA RCRA Hotline (see telephone
number above).
• Revision C is available for $7.50
from the National Technical Information
Service (NTIS) at 5285 Port Royal Road
in Springfield. Virginia 22161. The order
number is PB 82-172-156.
• The second edition of the manual is
available from the Superintendent of
Documents, U.S. Government Printing
Office, Washington, D.C. 20402, on a
subscription basis. The subscription
includes both the second edition of the
manual and a number of future updates
(approximately six mailings). Because
the updates will be available only
through this subscription, EPA
recommends that persons interested in
future updates to the manual subscribe
to the second edition. The cost is $55.00
per subscription for domestic mailing
($68.75 if mailed to a foreign address).
m. Amendments to 40 CFR 12Z2Q and
260.11
Sections 122^0 and 260.11 of Title 40
of the Code of Federal Regulations set
-------
NO. l«3 / Tuesday, September 21, 1982 / Rules and Regulations 41563
„; . . -'C:'~i.ii;o-, about publications
.,. - — irriicc: i'V reference in EPA's
--<, ...:.iicd permit regulations and
-• .-.::-.:o::s wasie regulations,
• I : o.-.!> to the 1980 edition, and
—:ca:e (hat (he 1980 edition is
.-viable from the EPA Solid Waste
:-:'rrmauon Office in Cincinnati. As
j ^cussed above, this is no longer
.:tc'j.-ate since (1) the first edition is no
.j.-rcr available at all, (2) revisions to
:~f first edition are not available from
:ne Solid Waste Information Office, and
(C) persons may use the second edition-
o.f the manual in lieu of the first edition.
Accordingly, EPA is amending §§ 122.20
and 260.11 to reflect these changes.
EPA has determined under Section
553 of the Administrative Procedure Act,
5 U.S.C. 553. that there is good cause for
promulgating these amendments without
prior notice and opportunity for
comment. These amendments are
entirely technical in nature and do not
change any substantive requirements.
Furthermore, in light of the current
inaccuracies in §§ 122.20 and 260.11,
delaying promulgation of these
amendments would be contrary to the
public interest.
IV. Lilt cf Subjects
40 CFR Part 122
Administrative practice and
procedure. Air pollution control.
Hazardous materials. Reporting
requirements. Waste treatment and
disposal. Water pollution control,
Confidential business information.
•iO CFR Part 260
Administrative, practice and
procedure. Hazardous materials, Waste
treatment and disposal.
Da led: September 9,1982.
Rita M. Laveue,
Associate Administrator for Solid Waste and
Emergency Response.
For the reasons set out in the
preamble, Title 40 of the Code of Federal
Regulations is amended as follows:
PART 260—HAZARDOUS WASTE
MANAGEMENT SYSTEM: GENERAL
1. The authority citation for Part 260
reads as follows:
Authority: Sees. 1006, 2002(a), 3001-3007
and 3010 of the Solid Waste Disposal Act, as
amended (42 U.S.C. 6905, 6912(a), 6921-6927
and 6930).
2. Section 260.11 is amended by
revising the fourth reference in
paragraph (a} to read as follows:
§260.11 References.
(a) * * *
','Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods,"
EPA Publication SW-846 (First Edition,
1980, as updated by Revisions A
(August, 1980), B (July, 1981), and C
(February, 1982)) or (Second Edition,
1982). The first edition of SW-846 is no
longer in print. Revisions A and B are
available from EPA, Office of Solid
Waste, (WH-565B), 401 M Street. S.W.,
Washington, D.C. 20460. Revision C is
available from NTIS, 5285 Port Royal
Road, Springfield, Virginia 22161. The
second edition of SW-846 includes
material from the first edition and
Revisions A, B, and C in a reorganized
format. It is available from the
Superintendent of Documents, U.S.
Government Printing Office,
Washington, D.C. 20402. (202) 783-3238,
on a subscription basis, and future
updates will automatically be mailed to
the subscriber.
PART 122—EPA ADMWISTERED
PERMIT PROGRAMS: THE NATIONAL
POLLUTANT DISCHARGE
ELIMINATION SYSTEM; THE
HAZARDOUS WASTE PERMIT
PROGRAM; AND THE UNDERGROUND
INJECTION CONTROL PROGRAM
3. The authority citation for Part 122
reads as follows:
Authority: Resource Conservation and
Recovery Act, 42 U.S.C. 6901 et seq.; Safe
Drinking Water Act, 42 U.S.C. 300(f) et seq.:
and Clean Water Act. 33 U.S.C. 1251 et seq.
4. Section 122.20 is amended by
revising the first reference in paragraph
(a) to read as follows:
§ 122.20 References.
(a) ' • •
"Test Methods for Evaluating Solid
Waste. Physical/Chemical Methods,"
EPA Publication SW-646 (First Edition,
1980, as updated by Revisions A
(August. 1980), B (July, 1981), and C
(February, 1982)) or (Second Edition.
1982). The first edition of SW-846 is no
longer in print. Revisions A and B are
available from EPA, Office of Solid
Waste, (WH-565B), 401 M Street, SW.,
Washington. D.C. 20460. Revision C is
available from NTIS, 5285 Port Royal
Road, Springfield, Virginia 22161. The
second edition of SW-846 includes
material from the first edition and
Revisions A, B, and C in a reorganized
format. It is available from the
Superintendent of Documents, U.S.
Government Printing Office,
Washington, D.C. 20402, (202) 783-3238,
on a subscription basis, and future
updates will automatically be mailed to
be the subscriber.
*****
[PR Doc. 82-25843 FU«f 9-ZO-8Z; 8:45 «mj
BILLING CODE 6MO-50-U
DEPARTMENT OF HEALTH AND
HUMAN SERVICES
Health Care Financing Administration
42 CFR Part 433
Equipment Acquired Under Public
Assistance Programs
AGENCY: Health Care Financing
Administration, HHS.
ACTION: Final rule.
SUMMARY: This Final Rule revises and
consolidates current regulations
concerning Federal financial
participation in the cost of equipment
under the Medicaid Program (Title XIX
of the Social Security Act). The rule also
revises and consolidates current
regulations on the management and
disposition of equipment under the
Program.
The rule would permit State public
assistance agencies to claim the cost of
most of their equipment at the time of
purchase rather than depreciating the
equipment over its useful life as required
by the current regulations. This change
would allow these agencies to claim
Federal financial participation in the
cost of the equipment at an earlier date
than under the current regulations and
would simplify the accounting'
requirements associated with the
equipment.
EFFECTIVE DATE: October 21. 1982.
FOR FURTHER INFORMATION CONTACT:
Edward M.-Tracy, (202) 245-7411.
SUPPLEMENTARY INFORMATION: A Notice
of proposed rulemaking was published
in the Federal Register on July 24,1981
at 46 FR 38280 inviting public comments
on a proposed revision to the
Departments' current regulations
concerning Federal financial
participation in the cost of equipment
acquired under HHS supported public
assistance programs. The regulation,
Subpart G of 45 CFR Part 95, allows for
the claiming of the cost of equipment
costing $25,000 or less in the period the
equipment was acquired. Public
comments were invited for 60 days
ending September 22,1981. Comments
were received from eleven State or local
agencies and two medical care
-------
-------
TEST METHODS FOR EVALUATING SOLID WASTE
—Physical/Chemical Methods—
SW-846
Second Edition
Revised
U.S. ENVIRONMENTAL PROTECTION AGENCY
APRIL 1984
Protection Agency
-------
TABLE OF CONTENTS*
TABLE OF CONTENTS
CONVERSION TABLE
ABSTRACT
ACKNOWLEDGMENT
SECTION/METHOD2
TABLE OF CONTENTS
CONVERSION
ABSTRACT
ACKNOWLEDGMENT
SECTION ONE SAMPLING OF SOLID WASTES [Section 1]
1.1 Development"of Appropriate Sampling Plans
1.1.1 Regulatory and Scientific Objectives
1.1.2 Fundamental Statistical Concepts
1.1.3 Basic Sampling Strategies
1.1.3.1 Simple Random Sampling
1.1.3.2 Stratified Random Sampling
1.1.3.3 Systematic Random Sampling
1.1.4 Special Considerations
1.1.4.1 Composite Sampling
1.1.4.2 Subsampling
1.1.4.3 Cost and Loss Functions
1.2 Implementation of Sampling Plan
1.2.1 Selection of Sampling Equipment
1.2.1.1 Composite Liquid Waste Sampler
(Coliwasa)
SAMPLING
Development
Objectives
Statistics
Strategies
Considerations
Implementation
Equipment
^Section and method numbers from the first edition of this manual are
given in brackets, and are also listed in the Conversion Table following this
Table of Contents.
2To ensure that future additions and deletions of material can be made
without disruption, the manual's pages are not numbered sequentially.
Section numbers are given with the page number. Actual methods are numbered
sequentially within themselves. Revised pages are noted as such in the bottom
corner of the page.
Revised 4/84
-------
SECTION/METHOD
SECTION ONE SAMPLING OF SOLID WASTES (Continued)
1.2.1.2 Weighted Bottle
1.2.1.3 Dipper
1.2.1.4 Thief
1.2.1.5 Trier
1.2.1.6 Auger
1.2.1.7 Scoop and Shovel
1.2.2 Selection of Sample Containers
1.2.3 Processing and Storage of Samples
1.3 Documentation of Chain of Custody [Section 2]
Sample Labels
Sample Seals
Field Log Book
Chain-of-Custody Record
Sample Analysis Request Sheet
Sample Delivery to the Laboratory
i.o./ Shipping of Samples
1.3.8 Receipt and Logging of Sample
1.3.9 Assignment of Sample for Analysis
1.3.1
1.3.2
1.3.3
1.3.4
1.3.5
1.3.6
1.3.7
1
1.4 Sampling Methodology [Section 3]
1.4.1 Containers
1.4.2 Tanks
1.4.3 Waste Piles
1.4.4 Landfills and Lagoons
Containers
Processing
Chain of Custody
Labels
Seals
Log Book
Record
,Request
Delivery
Shipping
Receipt
Assignment
Methodology
Containers
Tanks
Waste Piles
Landfills
SECTION TWO WASTE EVALUATION PROCEDURES
2.1 Characteristics of Hazardous Waste
2.1.1 Ignitability [Section 4]
Introduction
Regulatory Definition
Pensky-Martens Closed-Cup Method
Setaflash Closed-Cup Method
2.1.2 Corrosivity [Section 5]
Introduction
Regulatory Definition
Corrosivity Toward Steel
EVALUATION
Characteristics
Ignitability
Introduction
Regulatory Definition
1010
1020
Corrosivity
Introduction
Regulatory Definition
1110
-------
SECTION TWO WASTE EVALUATION PROCEDURES (Continued)
2.1 Characteristics of Hazardous Waste (Continued)
2.1.3 Reactivity [Section 6]
Introduction
Regulatory Definition
Introduction
Regulatory Definition
Extraction Procedure (EP) Toxicity Test Method
and Structural Integrity Test
2.2 Mobility Procedures
Multiple Extraction Procedure (reserved)
T of C / 3
SECTION/METHOD
Reactivity
Introduction
Regulatory Definition
2.1.4 Extraction Procedure Toxicity [Section 7] EP Toxicity
Introduction
Regulatory Definition
1310
MOBILITY
1410
SECTION THREE MONITORING (reserved)
3.1 Groundwater
3.1.1 Background
3.1.2 Regulatory Definition
3.1.3 Sampling
3.1.3.1 Introduction
3.1.3.2 Sample Collection
3.1.4 Analysis
3.2 Land Treatment Monitoring
3.2.1 Background
3.2.2 Regulatory Definition
3.2.3 Sampling
3.2.4 Analysis
3.2.5 References
3.3 Incineration
3.3.1 Background
3.3.2 Regulatory Definition
3.3.3 Analysis
MONITORING
Groundwater
Background
Regulatory Definition
Sampling
Analysis
Land Treatment
Background
Definition
Sampling
Analysis
References
Incineration
Background
Definition
Analysis
-------
4 / TABLE OF CONTENTS
SECTION/METHOD
SECTION FOUR SAMPLE WORKUP TECHNIQUES [Section 8]
4.1 Inorganic Techniques
Acid Digestion Procedure for Flame Atomic
Absorption Spectroscopy [8.49]
Acid Digestion Procedure for Furnace Atomic
Absorption Spectroscopy [8.49]
Acid Digestion of Oils, Greases, or Waxes [8.49]
Dissolution Procedure for Oils, Greases, or
Waxes [8.49]
Acid Digestion of Sludges (reserved)
Alkaline Digestion [8.548]
4.2 Organic Techniques
Separatory Funnel Liquid-Liquid Extraction [8.84]
Continuous Liquid-Liquid Extraction [9.01]
Acid-Base Cleanup Extraction [8.25]
Soxhlet Extraction [8.86]
Sonication Extraction [8.85]
WORKUP TECHNIQUES
Inorganic
3010
3020
3030
3040
3050
3060
Organic
3510
3520
3530
3540
3550
SECTION FIVE SAMPLE INTRODUCTION TECHNIQUES [Section 8] INTRODUCTION TECHNIQUES
Headspace [8.82]
Purge-and-Trap [8.83]
5020
5030
SECTION SIX MULTIELEMENT INORGANIC ANALYTICAL METHOD
(reserved)
Inductively Coupled Plasma Method
MULTIELEMENT
6010
SECTION SEVEN INORGANIC ANALYTICAL METHODS [Section 8]
Antimony [8.50]
Atomic Absorption, Direct Aspiration Method
Atomic Absorption, Graphite Furnace Method
Arsenic [8.51]
Atomic Absorption, Furnace Method
Atomic Absorption, Gaseous Hydride Method
Barium [8.52]
Atomic Absorption, Direct Aspiration Method
Atomic Absorption, Furnace Method
INORGANIC ANALYTICAL
7040
7041
7060
7061
7080
7081
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T OF C / 5
SECTION/METHOD
SECTION SEVEN INORGANIC ANALYTICAL METHODS (Continued)
Beryllium (reserved)
Atomic Absorption, Direct Aspiration Method
Atomic Absorption, Furnace Method
Cadmium [8.53]
Atomic Absorption, Direct Aspiration Method
Atomic Absorption, Furnace Method
Chromium [8.54]
Atomic Absorption, Direct Aspiration Method
Atomic Absorption, Furnace Method
Hexavalent Chromium: Coprecipitation [8.545]
Hexavalent Chromium: Colorimetric [8.546]
Hexavalent Chromium: Chelat ion-Extraction [8.547]
Copper (reserved)
Direct Aspiration Method
Furnace Method
Direct Aspiration Method
Furnace Method
Atomic Absorption
Atomic Absorption
Lead [8.56]
Atomic Absorption
Atomic Absorption
Mercury [8.57]
Mercury in Liquid Waste (Manual Cold-Vapor
Technique)
Mercury in Solid or Semisolid Waste (Manual
Cold-Vapor Technique) (reserved)
Nickel [8.58]
Direct Aspiration Method
Furnace Method
Atomic Absorption
Atomic Absorption
Osmium (reserved)
Atomic Absorption
Atomic Absorption
Selenium [8.59]
Atomic Absorption
Atomic Absorption
Silver [8.60]
Atomic Absorption
Atomic Absorption
Thallium (reserved)
Atomic Absorption
Atomic Absorption
Vanadium (reserved)
Atomic Absorption
Atomic Absorption
Zinc (reserved)
Atomic Absorption
Direct Aspiration Method
Furnace Method
Furnace Method
Gaseous Hydride Method
Direct Aspiration Method
Furnace Method
Direct Absorption Method
Furnace Method
Direct Aspiration Method
Furnace Method
Direct Aspiration Method
Atomic Absorption, Furnace Method
7090
7091
7130
7131
7190
7191
7195
7196
7197
7210
7211
7420
7421
7470
7471
7520
7521
7550
7551
7740
7741
7760
7761
7840
7841
7910
7911
7950
7951
-------
6 / TABLE OF CONTENTS
SECTION/METHOD
SECTION EIGHT ORGANIC ANALYTICAL METHODS
8.1 Gas Chromatographic Methods
Halogenated Volatile Organics [8.01]
Nonhalogenated Volatile Organics [8.01]
Aromatic Volatile Organics [8.01]
Acrolein, Acrylonitrile, Acetonitrile [8.03]
Phenols [8.04]
Phthalate Esters [8.06]
Organochlorine Pesticides and PCB's [8.08]
Nitroaromatics and Cyclic Ketones [8.09]
Polynuclear Aromatic Hydrocarbons [8.10]
Chlorinated Hydrocarbons [8.12]
Organophosphorus Pesticides [8.22]
Chlorinated Herbicides [8.40]
8.2 Gas Chromatographic/Mass Spectroscopy Methods
GC/MS Method for Volatile Organics [8.24]
GC/MS Method for Semivolatile Organics:
Packed Column Technique [8.25]
GC/MS Method for Semivolatile Organics:
Capillary Column Technique [8.27]
8.3 High Performance Liquid Chromatographic Methods
Polynuclear Aromatic Hydrocarbons [8.10]
ORGANIC ANALYTICAL
GC
8010
8015
8020
8030
8040
8060
8080
8090
8100
8120
8140
8150
GC/MS
8240
8250
8270
HPLC
8310
i
SECTION NINE MISCELLANEOUS ANALYTICAL METHODS
Total and Amenable Cyanide [8.55]
Total Organic Hal ides (TOX) [8.56]
Sulfides [8.57]
pH Measurement [5.2]
pH Paper Method (reserved)
Soil pH (reserved)
Specific Conductance (reserved)
Total Organic Carbon (reserved)
Cation-Exchange Capacity (Ammonium Acetate)
(reserved)
Cation-Exchange Capacity (Sodium Acetate)
(reserved)
MISCELLANEOUS ANALYTICAL
9010
9020
9030
9040
9041
9045
9050
9060
9080
9081
-------
APPENDIX A SAMPLING AND ANALYSIS METHODS FOR
HAZARDOUS WASTE INCINERATION
T OF C / 7
SECTION/METHOD
SECTION TEN QUALITY CONTROL/QUALITY ASSURANCE QC/QA
[Section 10]
10.1 Introduction Introduction
10.2 Program Design Design
10.3 Sampling Sampling
10.4 Analysis Analysis
10.5 Data Handling Data Handling
-------
CONVERSION TABLE
The sections and methods of the first edition of this manual are given
on the lefthand side of the page, and the location of their replacements is
given on the righthand side.
First Edition
1.0 Evaluation Plan Design
2.0 Chain of Custody Procedures
3.0 Sampling Methodology
3.1 Sampling Plan Design
3.2 Sampling Equipment
3.3 Sample Containers
3.4 Sampling Handling & Preservation
4.0 Ignitability
5.0 Corrosivity
5.2 pH Measurement
6.0 Reactivity
7.0 Extraction Procedure Toxicity
8.0 Analytical Methodology
Gas Chromatographic Methods
8.01 Volatile organics, general
8.02 Volatile aromatics, selected
ketones and ethers
8.03 Acrolein, Acrylonitrile and
Acetonitrile
8.04 Phenols
8.06 Semi-volatile organics
8.08 Organochlorine pesticides and PCBs
8.09 Nitroarornatics
8.10 Polynuclear Aromatic Hydrocarbons
8.12 Semi-volatile chlorinated hydro-
carbons
8.22 Organophosphorus pesticides
8.40 Chlorophenoxy acid pesticides
Current (Second) Edition
Section 1.0
Section 1.3
Section 1.4
Section 1.1
Section 1.2.1
Section 1.4.1
Section 1.3; also see
individual method
Section 2.1.1
Section 2.1.2
Methods 9040, 9041, 9045
Section 2.1.3
Section 2.1.4
8000 series of methods
8000, 8100 series of methods
Methods 8010, 8015, 8020
Method 8090
Method 8030
Method 8040
Method 8060
Method 8080
Method 8090
Methods 8100, 8310
Method 8120
Method 8140
Method 8150
-------
2 / CONVERSION
i
First Edition
Gas Chromatographic/Mass Spectroscopy
Methods
8.24 Volatile organics
8.25 Semi-volatile organics
8.27 Capillary Column GC/MS Method for
the Analysis of Wastes
High Performance Liquid Chromatographic
Methods
8.30 Polynuclear Aromatic Hydrocarbons
(see method 8.10)
Atomic Absorption Spectrographic Methods
8.49 General Requirements
8.50 Antimony
8.51 Arsenic
8.52 Barium
8.53 Cadmium
8.54 Chromium
8.545 Hexavalent chromium: Coprecipi-
tation
8.546 Hexavalent chromium:
8.547 Hexavalent chromium:
Extraction
8.548 Alkaline Digestate
8.55 Cyanide
8.56 Lead
8.57 Mercury
8.58 Nickel
8.59 Selenium
8.60 Silver
Colorimetric
Chelation-
Other Measurement Methods
8.55 Titrimetric Method for Cyanide
8.56 Microcoulometric Method
for Total Organic Halide
8.57 Titrimetric Method for Sulfides
Sample Preparation/Introduction Techniques
8.82 Headspace
8.83 Purge and Trap
8.84 Shake Out
8.85 Sonication
8.86 Soxhlet Extraction
Current (Second) Edition
8200 series of methods
Method 8240
Method 8250
Method 8270
8300 series of methods
Method 8310
7000 series of methods
Methods 7040, 7041
Methods 7060, 7061
Methods 7080, 7081
Methods 7090, 7091
Methods 7190, 7191
Method 7195
Method 7196
Method 7197
Method 3060
Method 9010
Methods 7420, 7421
Methods 7470, 7471
Methods 7520, 7521
Methods 7740, 7741
Methods 7760, 7761
9000 series of methods
Method 9010
Method 9020
Method 9030
Sections 4 and 5
Method 5020
Method 5030
Method 3510
Method 3550
Method 3540
-------
CONVERSION / 3
First Edition Current (Second) Edition
9.0 Interference Removal Procedures See individual method
9.01 Liquid-Liquid Extraction Method 3520
10.0 Quality Control/Quality Assurance Section 10
11.0 Suppliers See individual method
-------
PREFACE
This second edition of "Test Methods for Evaluating Solid Waste"
contains the procedures that may be used by the regulated community or
others in order to determine whether a waste is a hazardous waste as
defined by regulations promulated under Section 3001 of the Resource
Conservation and Recovery Act (RCRA, PL 94-580 (40 CFR Part 261). The
manual provides methodology for collecting representative samples of the
waste, and for determining the ignitability, corrosivity, reactivity,
Extraction Procedure (EP) Toxicity and composition of the waste.
This document has been developed to:
a. provide methods which will be acceptable to the Agency when used
by the regulated community to support waste evaluations and
listing and deli sting petitions, and
b. describe the methods that will be used by the Agency in conducting
investigations under Section 3001, 3007, and 3008.
The practice of evaluating solid wastes for environmental and human
health hazards is new. Experience has only recently accumulated in
analyzing wastes for inorganic and organic species, and for intrinsic
properties such as pH, flash point, reactivity and Teachability. This
manual will serve as a compilation of state-of-the-art methodology for
conducting such tests. It is meant to be a dynamic document. The
methodology descriptions will be frequently updated and expanded in order
to keep pace with the developments being achieved by EPA, the regulated
community, and others.
Standardized approved methods must be available so that the regulated
community can be certain that the data it provides will be acceptable to
the Agency. This manual thus makes available to the regulated community
and others, those methods that the Agency considers suitable.
Many of the methods presented in this manual have not been fully
evaluated by the Agency using materials characteristic of the wastes
regulated under RCRA. Such evaluations are underway. However, until
such time as the methods in this manual are superseded, the Agency will
accept data obtained by the test methods presented in this manual. Only
those data that are obtained when Quality Control and Quality Assurance
procedures are followed by the testing organization will be accepted by
the Agency.
This manual will eventually include a second part comprised of
biological methods for determining toxic properties of RCRA wastes. Such
toxic properties may include carcinogenicity, mutagenicity, teratogenicity,
aquatic toxicity, phytotoxicity, and mammalian toxicity.
Methods will be provided in this present volume for the following
specific areas:
a. design of sampling and evaluation plans;
-------
b. collection of samples from various types of environments (e.g.,
pipes, drums, pits, ponds, piles, tanks);
c. transportation and storage of samples;
d. chain-of custody considerations to insure defensibility of data;
e. determination of the pH, corrosivity to steel, flash point, and
explosivity;
f. conduct of the Extraction Procedure;
g. analysis of wastes and extracts for organic and inorganic constituents;
h. safety in solid waste sampling and testing, and
i. quality control and quality assurance.
The analytical and sampling methods presented in this manual have
been derived from a number of published sources, chiefly:
a. "Methods for the Evaluation of Water and Wastewater,"
EPA-600/4-79-020, U.S. EPA, Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268,
b. "Methods for Benzidine, Chlorinated Organic Compounds,
Pentachlorophenol and Pesticides in Water an Wastewater," U.S.
EPA, Environmental Monitoring and Support Laboratory, Cincinnati,
OH 45268, September 1978,
c. Guidelines Establishing Test Procedures for the Analysis of
Pollutants; Proposed Regulations; 44 FR 69464-69575, and
d. "Samplers and Sampling Procedures for Hazardous Waste Streams,"
EPA-600/2-80-018, U.S. EPA, Municipal Environmental Research
Laboratory, Cincinnati, OH 45268.
In addition, work conducted by and the assistance of scientists of
the Environmental Monitoring Systems Laboratory at Las Vegas, NV, the
Environmental Research Laboratory at Athens, GA, and the National
Enforcement Investigations Center at Denver, CO, is gratefully acknowledged
and appreciated.
Although a sincere effort has been made to select methods that are
applicable to the widest range of expected wastes, significant interferences,
or other problems, may be encountered with certain samples. In these
situations, the analyst is advised to contact the Manager, Waste Analysis
Program (WH-565), Waste Characterization Branch, Office of Solid Waste,
Washington, D.C. 20460 (202-755-9187) for assistance. The manual is
intended to serve all those with a need to evaluate solid waste. Your
comments, corrections, suggestions, and questions concerning any material
contained in, or omitted from, this manual will be gratefully appreciated.
Please direct your comments to the above address.
-------
ACKNOWLEDGMENT
The Office of Solid Waste would like especially to thank the
following individuals and groups for the help and advice they gave
us during the preparation of this manual:
U.S. Environmental Protection Agency, Inductively Coupled
Plasma Users Group
Dr. Theodore Martin and Dr. Gerald McKey, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio
Dr. John Warren, U.S. Environmental Protection Agency,
Regulations and Standards Division, Washington, D.C.
Dr. John Maney, Dr. Curt Rose, Ann Soule, Jan Connery,
Ann Gordon, Dr. Dallas Wait, Dr. Tyrone Smith, Scott Drew,
and George Perry of Energy Resources Company, Inc., Cambridge,
Massachusetts.
We would also like to thank the Environmental Protection Agency's
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio,
for providing the basic methodology used in this manual.
-------
SECTION ONE
SAMPLING OF SOLID WASTES
The initial and perhaps most critical element in a program designed to
evaluate the physical and chemical properties of a solid waste is the plan
for sampling the waste. It is understandable that analytical studies, with
their sophisticated instrumentation and high cost, are often perceived as
the dominant element in a waste characterization program. Yet, despite that
sophistication and high cost, analytical data generated by a scientifically
defective sampling plan have limited utility, particularly in the case of
regulatory proceedings.
This section of the manual addresses the development and implementation
of a scientifically credible sampling plan for a solid waste and the documen-
tation of the chain of custody for such a plan. The information presented in
this section is relevant to the sampling of any solid waste, which has been
defined by the EPA in its regulations for the identification and listing of
hazardous wastes to include solid, semisolid, liquid, and contained gaseous
materials. However, the physical and chemical diversity of those materials,
as well as the dissimilar storage facilities (lagoons, open piles, tanks,
drums, etc.) and sampling equipment associated with them, preclude a detailed
consideration of any specific sampling plan. Consequently, since the burden
of responsibility for developing a technically sound sampling plan rests with
the waste producer, it is advisable that he seek competent advice before
designing a plan. This is particularly true in the early developmental
stages of a sampling plan, which require at least a basic understanding of
applied statistics. Applied statistics is the science of employing techniques
that allow the uncertainty of inductive inferences (general conclusions
based on partial knowledge) to be evaluated.
1.1 Development of Appropriate Sampling Plans
An appropriate sampling plan for a solid waste must be responsive to
both regulatory and scientific objectives. Once those objectives have been
clearly identified, a suitable sampling strategy, predicated upon fundamental
statistical concepts, can be developed. The statistical terminology associated
with those concepts is reviewed in Table 1.
1.1.1 Regulatory and Scientific Objectives
The EPA, in its hazardous waste management system, has required that
certain solid wastes be analyzed for physical and chemical properties. It is
mostly chemical properties that are of concern, and, in the case of a number
of chemical contaminants, the EPA has promulgated levels (regulatory thresholds)
that cannot be equaled or exceeded. The regulations pertaining to the
-------
2 / SAMPLING - Development
TABLE 1. BASIC STATISTICAL TERMINOLOGY APPLICABLE TO SAMPLING PLANS FOR SOLID WASTES
Terminology
Symbol
Mathematical equation
(Equation)
• Variable (e.g., barium
or endrln)
• Individual measurement
of variable
• Mean of all possible
measurements of variable
(population mean)
• Mean of measurements
generated by sample
(sample mean)
• Variance of sample
N
I
I"!
with N = number of
possible measurements
Simple random sampling and
systematic random sampling
n
I Xi
J * *-l , with n = number of
n sample measurements
Stratified random sampling
W^x.
with x|< - stratum
mean and W|< * fraction
of population represented
by Stratum k (number of
strata [k] ranges from
1 to r)
Simple random sampling and
systematic random sampling
(1)
(2a)
(2b)
II
X? - (Z Xi)2/n
• Standard deviation of
sample
• Standard error
(also standard error
of mean and standard
deviation of mean)
of sample
• Confidence interval
for u3
• Regulatory threshold3
• Appropriate number of
samples to collect from
a solid waste (financial
constraints not considered)
CI
RT
n - 1
Stratified random sampling
r
s2 - S W. s? , with s£ = stratum variance
W * and Wk » fraction of
population represented by
Stratum k (number of strata
Ik] ranges from 1 to r)
CI » x + t 20 sx Wltn t.20 obtained
' from Table 2 in this
section for appropriate
degrees of freedom
Defined by EPA (e.g., 100 ppm for
barium in elutriate of EP toxicity test)
t2 s2
.20
with A = RT - x
(3a)
(3b)
(4)
(5)
(6)
(7)
(8)
-------
Objectives / 3
TABLE 1 (Continued)
Terminology
Symbol
Mathematical equation
(Equation)
• Degrees of freedom
• Square root transformation
• Arcsin transformation
df
df = n - 1 (9)
>/Xi + 1/2 (10)
Arcsin^p"; if necessary, refer to any (11)
text on basic statistics;
measurements must be con-
verted to percentages (p)
aThe upper limit of the CI for u is compared to the applicable regulatory threshold (RT) to determine
if a solid waste contains the variable (chemical contaminant) of concern at a hazardous level. The con-
taminant of concern is not considered to be present in the waste at a hazardous level if the upper limit
of the CI is less than the applicable RT. Otherwise, the opposite conclusion is reached.
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4 / SAMPLING - Development
TABLE 2. TABULATED VALUES OF STUDENT'S
SOLID WASTES
"t" FOR EVALUATING
Degrees of
freedom (n-l)a
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
40
60
120 .
oo
Tabulated
"t" valueb
3.078
1.886
1.638
1.533
1.476
1.440
1.415
1.397
1.383
1.372
1.363
1.356
1.350
1.345
1.341
1.337
1.333
1.330
1.328
1.325
1.323
1.321
1.319
1.318
1.316
1.315
1.314
1.313
1.311
1.310
1.303
1.296
1.289
1.282
aDegrees of freedom (df) are equal to the number of samples (n)
collected from a solid waste less one.
^Tabulated "t" values are for a two-tailed confidence interval
and a probability of 0.20 (the same values are applicable to a one-
tailed confidence interval and a probability of 0.10).
-------
Objectives / 5
management of hazardous wastes contain three references regarding the sampling
of solid wastes for analytical properties. The first reference, which occurs
throughout the regulations, requires that representative samples of waste be
collected and defines representative samples as exhibiting average properties
of the whole waste. The second reference, which pertains just to petitions
to exclude wastes from being listed as hazardous wastes, specifies that
enough samples (but in no case less than four samples) be collected over a
period of time sufficient to represent the variability of the wastes. The
third reference, which applies only to groundwater monitoring systems,
mandates that four replicates (subsamples) be taken from each groundwater
sample intended for chemical analysis and that the mean concentration and
variance for each chemical constituent be calculated from those four subsamples
and compared to background levels for groundwater. Even the statistical
test to be employed in that comparison is specified (Student's t-test).
The first of the above-described references addresses the issue of
sampling accuracy, while the second and third references focus on sampling
variability or, conversely, sampling precision (actually the third reference
relates to analytical variability, which, in many statistical tests, cannot
be distinguished from true sampling variability). Sampling accuracy (the
closeness of a sample value to its true value) and sampling precision (the
closeness of repeated sample values) are also the issues of overriding
importance in any scientific assessment of sampling practices. Thus,
from both regulatory and scientific perspectives, the primary objectives of a
sampling plan for a solid waste are twofold - namely, to collect samples that
will allow sufficiently accurate and precise measurements of the chemical
properties of the waste. If the chemical measurements are sufficiently
accurate and precise, they will be considered reliable estimates of the
chemical properties of the waste.
It is now apparent that a judgment must be made as to the degree of
sampling accuracy and precision that is required to reliably estimate the
chemical characteristics of a solid waste for the purpose of comparing those
characteristics to applicable regulatory thresholds. Generally, high accuracy
and high precision are required if one or more chemical contaminants of a
solid waste is present at a concentration that is close to the applicable
regulatory threshold. Alternatively, relatively low accuracy and low pre-
cision can be tolerated if the contaminants of concern occur at levels far
below or far above their applicable thresholds. However, a word of caution
is in order. Low sampling precision is often associated with considerable
savings in analytical, as well as sampling, costs and is clearly recognizable
even in the simplest of statistical tests. On the other hand, low sampling
accuracy may not entail cost savings and is always obscured (cannot be
evaluated) in statistical tests. Therefore, while it is desirable to design
sampling plans for solid wastes to achieve only the minimally required
precision (at least two samples of a material are required for any estimate
of precision), it is prudent to design the plans to attain the greatest
possible accuracy.
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6 / SAMPLING - Development
The roles that inaccurate and imprecise sampling can play in causing
a solid waste to be inappropriately judged hazardous are illustrated in
Figure 1. When evaluating Figure 1, several points are worthy of consid-
eration. Although a sampling plan for a solid waste generates a mean con-
centration (x) and standard deviation (s, a measure of the extent to which
individual sample concentrations are dispersed around x) for each chemical
contaminant of concern, it is not the variation of individual sample con-
centrations that is of ultimate concern, but rather, the variation that
characterizes x itself. That measure of dispersion is termed the standard
deviation of the mean (also, the standard error of the mean or standard
error) and is designated as s£. Those two samples values, x and Sx, are
used to estimate the interval (range) within which the true mean (u.) of
the chemical concentration probably occurs, assuming that the individual
concentrations exhibit a normal (bell-shaped) distribution. For the purposes
of evaluating solid wastes, the probability level (confidence interval) of
80% has been selected. That is, for each chemical contaminant of concern,
a confidence interval (CI) is described within which u, occurs if the sample is
representative, which is expected of about 80 out of 100 samples. The upper
limit of the 80% CI is then compared to the appropriate regulatory threshold.
If the upper limit is less than the threshold, the chemical contaminant is
not considered to be present in the waste at a hazardous level; otherwise,
the opposite conclusion is drawn. One last point merits explanation. Even
if the upper limit of an estimated 80% CI is only slightly less than the
regulatory threshold (the worst case of chemical contamination that would be
judged acceptable), there is only a 10% (not 20%) chance that the threshold
is equaled or exceeded. That is because values of a normally distributed
contaminant that are outside the limits of an 80% CI are equally distributed
between the left (lower) and right (upper) tails of the normal curve.
Consequently, the CI employed to evaluate solid wastes is, for all practical
purposes, a 90% interval.
1.1.2 Fundamental Statistical Concepts
The concepts of sampling accuracy and precision have already been intro-
duced along with some measurements of central tendency (x) and dispersion
(standard deviation [ s ] and s^) for concentrations of a chemical contaminant
of a solid waste. The utility of x and s^ in estimating a confidence inter-
val that probably contains the true mean (u.) concentration of a contaminant
has also been described. However, it was noted that the validity of that
estimate is predicated upon the assumption that individual concentrations of
the contaminant exhibit a normal distribution.
Statistical techniques for obtaining accurate and precise samples are
relatively simple and easy to implement. Sampling accuracy is usually
achieved by some form of random sampling. In random sampling, every unit in
the population (e.g., every location in a lagoon used to store a solid waste)
has a theoretically equal chance of being sampled and measured. Consequently,
-------
Objectives / 7
ACCURATE AND PRECISE SAMPLE
(Waste Appropriately Judged Nonhazardous)
ACCURATE AND IMPRECISE SAMPLE
(Waste Inappropriately Judged Hazardous)
0.4-
True Mean (|i) and Sample Mean (x)
CO
LLJ
D
<
>
0.3-
Standard Error (s;) = 7
\
LLJ
O
01
a:
0.2-
0.1-
0.4-
M and x
Sx-11
, Regulatory
{Threshold (RT)
85 90 95 100 105 110
CONCENTRATION OF BARIUM (ppm)
INACCURATE AND PRECISE SAMPLE
(Waste Inappropriately Judged Hazardous)
65
I
100
I
105
85 90 95
CONCENTRATION OF BARIUM (ppm)
T
110
INACCURATE AND IMPRECISE SAMPLE
(Waste Inappropriately Judged Hazardous)
0.4-
$5-11
65 70 75 80 85 90 95 100 105 110
CONCENTRATION OF BARIUM (ppm)
65 70 75 80 85 90 95 100 105
CONCENTRATION OF BARIUM (ppm)
T
110
NOTE: In All Cases, Confidence Interval for M - x ± t 20 sx-
Figure 1.—Important theoretical relationships between sampling accuracy and precision and
regulatory objectives for a chemical contaminant of a solid waste that occurs at a concentration
marginally less than its regulatory threshold. In this example, barium is the chemical contaminant.
The true mean concentration of barium in the elutriate of the EP toxicity test is 85 ppm, as compared
to a regulatory threshold of 100 ppm. The upper limit of the confidence interval for the true
mean concentration, which is estimated from the sample mean and standard error, must be less than
the regulatory threshold if barium is judged to be present in the waste at a nonhazardous level.
-------
8 / SAMPLING - Development
statistics generated by the sample (e.g., x, and, to a lesser degree, s£}
are unbiased (accurate) estimators of true population parameters (e.g., the
CI for u.). In other words, the sample is representative of the population.
One of the commonest methods of selecting a random sample is to divide the
population by an imaginary grid, assign a series of consecutive numbers to
the units of the grid, and select the numbers (units) to be sampled through
the use of a random numbers table (such a table can be found in any text on
basic statistics). It is important to emphasize that a haphazardly selected
sample is not a suitable substitute for a randomly selected sample. That is
because there is no assurance that a person performing undisciplined sampling
will not consciously or subconsciously favor the selection of certain units
of the population, thus causing the sample to be unrepresentative of the
population.
Sampling precision is most commonly achieved by taking an appropriate
number of samples from the population. As can be observed from the equation
for calculating s£, precision increases (s£ and the CI for \n decrease)
as the number of samples (n) increases, although not in a 1:1 ratio. For
example, a 100% increase in the number of samples from two to four causes the
CI to decrease by approximately 62% (about 31% of that decrease is associated
with the critical upper tail of the normal curve). However, another 100%
increase in sampling effort from four to eight samples results in only an
additional 39% decrease in the CI. Another technique for increasing sampling
precision is to maximize the physicaTsize (weight or volume) of the samples
that are collected. That has the effect of minimizing between-sample variation
and, consequently, decreasing s£. Increasing the number or size of samples
taken from a population, in addition to increasing sampling precision, has the
secondary effect of increasing sampling accuracy.
In summary, reliable information concerning the chemical properties of a
solid waste is needed for the purpose of comparing those properties to
applicable regulatory thresholds. If chemical information is to be considered
reliable, it must be accurate and sufficiently precise. Accuracy is usually
achieved by incorporating some form of randomness into the selection process
for the samples that generate the chemical information. Sufficient precision
is most often obtained by selecting an appropriate number of samples.
There are a few ramifications of the above-described concepts that merit
elaboration. If, for example, as in the case of semiconductor etching
solutions, each batch of a waste is completely homogeneous with regard to the
chemical properties of concern and that chemical homogeneity is constant
(uniform) over time (from batch to batch), a single sample collected from the
waste at an arbitrary location and time would theoretically generate an
accurate and precise estimate of the chemical properties. However, most
wastes are heterogeneous in terms of their chemical properties. If a batch
of waste is randomly heterogeneous with regard to its chemical charac-
teristics and that random chemical heterogeneity remains constant from batch
to batch, accuracy and appropriate precision can usually be achieved by
simple random sampling. In that type of sampling, all units in the population
-------
Statistics / 9
(essentially all locations or points in all batches of waste from which a
sample could be collected) are identified, and a suitable number of samples
is randomly selected from the population. More complex stratified random
sampling is appropriate if a batch of waste is known to be nonrandomly
heterogeneous in terms of its chemical properties and/or nonrandom chemical
heterogeneity is known to exist from batch to batch. In such cases, the
population is stratified to isolate the known sources of nonrandom chemical
heterogeneity. After stratification, which may occur over space (locations
or points in a batch of waste) and/or time (each batch of waste), the units
in each stratum are numerically identified, and a simple random sample is
taken from each stratum. As previously intimated, both simple and stratified
random sampling generate accurate estimates of the chemical properties of a
solid waste. The advantage of stratified random sampling over simple random
sampling is that, for a given number of samples and a given sample size, the
former technique often results in a more precise estimate of chemical properties
of a waste (a lower value of s£) than the latter technique. However, greater
precision is likely to be realized only if a waste exhibits substantial
nonrandom chemical heterogeneity and stratification efficiently "divides"
the waste into strata that exhibit maximum between-strata variability and
minimum within-strata variability. If that does not occur, stratified
random sampling can produce results that are less precise than in the case of
simple random sampling. Therefore, it is reasonable to select stratified
random sampling over simple random sampling only if the distribution of
chemical contaminants in a waste is sufficiently known to allow an intelligent
identification of strata and at least two or three samples can be collected
in each stratum. If a strategy employing stratified random sampling is
selected, a decision must be made regarding the allocation of sampling effort
among strata. When chemical variation within each stratum can be estimated
with a great degree of detail, samples should be optimally allocated among
strata, i.e., the number of samples collected from each stratum should be
directly proportional to the chemical variation encountered in the stratum.
When detailed information concerning chemical variability within strata is
not available, samples should be proportionally allocated among strata, i.e.,
sampling effort in each stratum should be directly proportional to the size
of the stratum.
Simple random sampling and stratified random sampling are types of
probability sampling, which, because of a reliance upon mathematical and
statistical theories, allows an evaluation of the effectiveness of sampling
procedures. Another type of probability sampling is systematic random
sampling, in which the first unit to be collected from a population is
randomly selected, but all subsequent units are taken at fixed space or time
intervals." An example of systematic random sampling is the sampling of a
wastg lagoon along a transect in which the first sampling point on the
transect is 1 m from a randomly selected location on the shore and subsequent
sampling points are located at 2-m intervals along the transect. The
advantages of systematic random sampling over simple random sampling and
stratified random sampling are the ease in which samples are identified and
collected (the selection of the first sampling unit determines the remainder
-------
10 / SAMPLING - Development
of the units) and, sometimes, an increase in precision. In certain cases,
for example, systematic random sampling might be expected to be a little more
precise than stratified random sampling with one unit per stratum because
samples are distributed more evenly over the population. As will be demon-
strated shortly, disadvantages of systematic random sampling are the poor
accuracy and precision that can occur when unrecognized trends or cycles
occur in the population. For those reasons, systematic random sampling is
recommended only when a population is essentially random or contains at most
a modest stratification. In such cases, systematic random sampling would be
employed for the sake of convenience, with little expectation of an increase
in precision over other random sampling techniques.
Probability sampling is contrasted with authoritative sampling, in which
an individual who is well acquainted with the solid waste to be sampled
selects a sample without regard to randomization. The validity of data
gathered in that manner is totally dependent on the knowledge of the sampler
and, although valid data can sometimes be obtained, authoritative sampling is
not recommended for the chemical characterization of most wastes.
It may now be useful to offer a generalization regarding the four
sampling strategies that have been identified for solid wastes. If little or
no information is available concerning the distribution of chemical contami-
nants of a waste, simple random sampling is the most appropriate sampling
strategy. As more information is accumulated for the contaminants of concern,
greater consideration can be given (in order of the additional information
required) to stratified random sampling, systematic random sampling, and,
perhaps, authoritative sampling.
The validity of a CI for the true mean (u.) concentration of a chemical
contaminant of a solid waste is, as previously noted, based on the assumption
that individual concentrations of the contaminant exhibit a normal distribu-
te' on. This is true regardless of the strategy that is employed to sample the
waste. Although there are computational procedures for evaluating the
correctness of the assumption of normality, those procedures are meaningful
only if a large number of samples are collected from a waste. Since sampling
plans for most solid wastes entail just a few samples, one can do little more
than superficially examine resulting data for obvious departures from normality
(this can be done by simple graphical methods), keeping in mind that even if
individual measurements of a chemical contaminant of a waste exhibit a consid-
erably abnormal distribution, such abnormality is not likely to be the case for
sample meansi which are our primary concern. One can also compare the mean of
the sample (x) to the variance of the sample (s^). In a normally distributed
population, x would be expected to be greater than s^ (assuming that the number
of samples [n] is reasonably large). If that is not the case, the chemical
contaminant of concern may be characterized by a Poisson distribution (x is
approximately equal to s^) or a negative binomial distribution (S is less than
s'-). In the former circumstance, normality can often be achieved by trans-
forming data according to the square root transformation. In the latter cir-
cumstance, normality may be realized through use of the arcsine transformation.
-------
Statistics; Strategies / 11
If either transformation is required, all subsequent statistical evaluations
must be performed on the transformed scale.
Finally, it is necessary to address the appropriate number of samples to
be employed in the chemical characterization of a solid waste. As has
already been emphasized, the appropriate number of samples is the least
number of samples required to generate a sufficiently precise estimate of the
true mean (u.) concentration of a chemical contaminant of a waste. From the
perspective of most waste producers, that means the minimal number of samples
needed to demonstrate that the upper limit of the CI for \i is less than the
applicable regulatory threshold (RT). The formula for estimating appropriate
sampling effort (Table 1, Equation 8) indicates that increased sampling
effort is generally justified as s^ or the "t.2o" value (probable error rate)
increases and as A (RT - x) decreases. In a well-designed sampling
plan for a solid waste, an effort is made to estimate the values of x
and s^ before sampling is initiated. Such preliminary estimates,whTch
may be derived from information pertaining to similar wastes, process
engineering data, or limited analytical studies, are used to identify the
approximate number of samples that must be collected from the waste. It is
always prudent to collect a somewhat greater number of samples than indicated
by preliminary estimates of x and s2 since poor preliminary estimates
of those statistics can result in an underestimate of the appropriate number
of samples to collect. It is usually possible to appropriately process and
store the extra samples until analysis of the initially identified samples is
completed and it can be determined if analysis of the additional samples is
warranted.
1.1.3 Basic Sampling Strategies
It is now appropriate to present general procedures for implementing the
three previously introduced sampling strategies (simple random sampling,
stratified random sampling, and systematic random sampling) and a hypothetical
example of each sampling strategy. The hypothetical examples illustrate the
statistical calculations that must be performed in most situations likely to
be encountered by a waste producer and, also, provide some insight into the
efficiency of the three sampling strategies in meeting regulatory objectives.
The following hypothetical conditions are assumed to exist for all three
sampling strategies. First, barium, which has a RT of 100 ppm as measured in
the EP elutriate test, is the only chemical contaminant of concern. Second,
barium is discharged in particulate form to a waste lagoon and accumulates
in the lagoon in the form of a sludge, which has built up to approximately
the same thickness throughout the lagoon. Third, concentrations of barium
are relatively homogeneous along the vertical gradient (from the water-sludge
interface to the sludge-lagoon interface), suggesting a highly controlled
manufacturing process (little between-batch variation in barium concentrations),
-------
12 / SAMPLING - Development
Fourth, the physical size of sludge samples collected from the lagoon is as
large as practical, and barium concentrations derived from those samples are
normally distributed (note that we do not refer to~ barfum levels j_n the
samples of sludge since barium measurements are actually made on the elutriate
from EP toxicity tests performed with the samples). Last, a preliminary
study of barium levels in the elutriate of four EP toxicity tests conducted
with sludge collected from the lagoon several years ago identified values of
86 and 90 ppm for material collected near the outfall (in the upper third) of
the lagoon and values of 98 and 104 ppm for material obtained from the
far end (the lower two-thirds) of the lagoon.
For all sampling strategies, it is important to remember that barium
will be determined to be present in the sludge at a hazardous level if the
upper limit of the CI for u. is equal to or greater than the RT of 100 pprn
(Table 1, Equations 6 and 7).
1.1.3.1 Simple Random Sampling
Simple random sampling (Box 1) is performed by general procedures in
which preliminary estimates of x and s2, as well as a knowledge of the RT,
for each chemical contaminant of a solid waste that is of concern are employed
to estimate the appropriate number of samples (n) to be collected from the
waste. That number of samples is subsequently analyzed for each chemical
contaminant of concern. The resulting analytical data are then used to
definitively conclude that each contaminant is or is not present in the
waste at a hazardous concentration or, alternatively, to suggest a reiterative
process, involving increased sampling effort, through which the presence or
absence of hazard can be definitively determined.
In the hypothetical example for simple random sampling (Box 1), prelimi-
nary estimates of x and s2 indicated a sampling effort consisting of six
samples. That number of samples was collected and initially analyzed,
generating analytical data somewhat different from the preliminary data (s2
was substantially greater than was preliminarily estimated). Consequently,
the upper limit of the CI was unexpectedly greater than the applicable RT,
resulting in a tentative conclusion of hazard. However, a reestimation of
appropriate sampling effort, based on statistics derived from the six samples,
suggested that such a conclusion might be reversed through the collection and
analysis of just one more sample. Fortunately, a resampling effort was not
required because of the foresight of the waste producer in obtaining three
extra samples during the initial sampling effort, which, because of their
influence in decreasing the final values of x, sjj, t420» anc'> conse-
quently, the upper limit of the CI - values obtainedfrom all nine samples -
resulted in a definitive conclusion of nonhazard.
-------
Strategies / 13
BOX 1. STRATEGY FOR DETERMINING IF CHEMICAL CONTAMINANTS OF SOLID WASTES
ARE PRESENT AT HAZARDOUS LEVELS - SIMPLE RANDOM SAMPLING OF WASTES
Step
1. Obtain preliminary estimates of x and s2 for each chemical con-
taminant of a solid waste that is of concern. The two above-identified
statistics are calculated by, respectiveTy, Equations 2a and 3a (Table 1),
2. Estimate the appropriate number of samples (ni) to be collected from
the waste through use of Equation 8 (Table 1) and Table 2. Derive
individual values of r\i for each chemical contaminant of concern.
The appropriate number of samples to be taken from the waste is the
greatest of the individual nj values.
3. Randomly collect at least nj samples (or t\2 ~ nl» n3 ~ n2» e^c> samples,
as will be indicated later in this box) from the waste (collection of a
few extra sampjes will provide protection against poor preliminary
estimates of x and s2). Maximize the physical size (weight or
volume) of all samples that are collected.
4. Analyze the nj (or r\2 - n]_, n3 - n2, etc.) samples for each chemical con-
taminant of concern. Superficially (graphically) examine each set of
analytical data for obvious departures from normality.
5. Calculate x, s2, the standard deviation (s), and s% for eacn set of
analytical data by, respectively, Equations 2a, 3a, 4, and 5 (Table 1).
6. If x for a chemical contaminant is equal to or greater than the
applicable RT (Equation 7; Table 1)) and is believed to be an accurate
estimator of u,, the contaminant is considered to be present in the
waste at a hazardous concentration and the study is completed. Otherwise,
continue the study. In the case of a set of analytical data that does
not exhibit obvious abnormality and for which x is greater than s2,
perform the following calculations with nontransformed data. Otherwise,
consider transforming the data by the square root transformation (if
x is about equal to s2) or the arcsine transformation (if x is less
than s2) and performing all subsequent calculations with transformed
data. Square root and arcsine transformations are defined by, respect-
ively, Equations 10 and 11 (Table 1).
7. Determine the CI for each chemical contaminant of concern by Equation 6
(Table 1) and Table 2. If the upper limit of the CI is less than the
applicable RT (Equations 6 and 7; Table 1), the chemical contaminant is
not considered to be present in the waste at a hazardous concentration
and the study is completed. Otherwise, the opposite conclusion is
tentatively reached.
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14 / SAMPLING - Development
8. If a tentative conclusion of hazard is reached, reestimate the total
number of samples (n2) to be collected from the waste by use of
Equation 8 (Table 1) and Table 2. When deriving n2, employ the newly
calculated (not preliminary) values of x and s2. If an additional n£ -
samples of waste cannot reasonably be collected, the study is completed
and a definitive conclusion of hazard is reached. Otherwise, collect
an extra r\2 - nj samples of waste.
9. Repeat the basic operations described in Steps 3-8 until the waste is
judged to be nonhazardous or, if the opposite conclusion continues to
be reached, increased sampling effort is impractical.
Hypothetical Example
Step
1. The preliminary study of barium levels in the elutriate of four EP
toxicity tests conducted with sludge collected from the lagoon several
years ago generated values of 86 and 90 ppm for sludge obtained from
the upper third of the lagoon and values of 98 and 104 ppm for sludge
from the lower two-thirds of the lagoon. Those two sets of values are
not judged to be indicative of nonrandom chemical heterogeneity (strati
fication) within the lagoon. Therefore, preliminary estimates of
x and s2 are calculated as:
- = il_ = 86 + 90 + 98 + 104 = 94>5Q>
n y n 7
z ^ - (z X^Vn
s2 = — - ~^± - (Equation 3a)
= 35.916.00 - 35.721.00 = 65 QQ
w
2. Based on the preliminary estimates of x and s2, as well as
the knowledge that the RT for barium is 100 ppm,
= 120L_ = (1.6382)(65 00)
1 '** 5.50^
-------
Strategies / 15
3. As indicated above, the appropriate number of sludge samples (r\i) to
be collected from the lagoon is six. That number of samples (plus
three extra samples for protection against poor preliminary estimates
of x and s2) is collected from the lagoon by a single randomization
process (Figure 2). All samples consist of the greatest volume of
sludge that can be practically collected. The three extra samples are
suitably processed and stored for possible later analysis.
The six samples of sludge (r\i) designated for immediate analysis
generate the following concentrations of barium in the EP toxicity
test: 89, 90, 87, 96, 93, and 113 ppm. Although the value of 113
appears unusual as compared to the other data, there is no obvious
indication that the data are not normally distributed.
New values for x and s2 and associated values for the standard
deviation (s) and s^ are calculated as:
ppm
x =
89 + 90 + 87 + 96 + 93 + 113
= 94.67,
(Equation 2a)
S2 =
n ? n p
I K - (I X.r/n
1
__
"n"- 1
= 54,224.00 - 53,770.67 = 9Q 67
s =
= 9.52, and
n~= 9.52/-y/lf = 3.89.
(Equation 3a)
(Equation 4)
(Equation 5)
6. The new value for x (94.67) is less than the RT (100). In
addition, x is greater (only slightly) than s2 (90.67) and, as
previously indicated, the raw data are not characterized by obvious
abnormality. Consequently, the study is continued, with the following
calculations performed with nontransformed data.
7. CI = x _+ t ?n s- = 94.67 +. (1.476)(3.89)
(Equation 6)
= 94.67 + 5.74.
Since the upper limit of the CI (100.41) is greater than the applicable
RT (100), it is tentatively concluded that barium is present in the
sludge at a hazardous concentration.
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16 / SAMPLING - Development
WASTE OUTFALL
1
18
35
52
69
86
103
—
_
239
409
»
113
~
_
^
_
—
—
87
—
'
—
—
*r/7.
>
r
90
iSKl^ai
_
93
1 93
~~
_
—
—
__
91
—
N
—
-H-~
—
_
89
V
—
\
&'
***•
~
—
~
^
*
?
'A
\>^*v
rt
—
90
'
WASTE LAGOON I I
OVERFLOW PIPE
__
—
—
—
—
—
'X
96
^
—
17
34
— ~"
255
_
425
^
U
O
\
L(
0
'PER THIRD
: LAGOON
DWER TWO-THIRDS
= LAGOON
V
IMAGINARY SAMPLING GRID
LEGEND
1-425 Units in Sampling Grid
0 Barium Concentrations (ppm)
Associated with Nine Samples of Sludge
Figure 2.—Hypothetical sampling conditions in waste lagoon containing sludge contaminated with barium.
Barium concentrations associated with samples of sludge refer to levels measured in the elutriate of EP toxicity
tests conducted with the samples.
-------
Strategies / 17
8. n is now reestimated as:
_ ><
• JT 5.33^
The value for n£ (^7) indicates that an additional (n2 - n^ = 1)
sludge sample should be collected from the lagoon.
9. The additional sampling effort is not necessary because of the three
extra samples that were initially collected from the lagoon. All extra
samples are analyzed, generating the following levels of barium for the
EP toxicity test: 93, 90, and 91 ppm. Consequently, x, s2, the stan-
dard deviation (s), and Sx are recalculated as:
n
1 Xi
_ 1=1 1 89 + 90 + . . . + 91
x = = = 93.56, (Equation 2a)
n 9
n 9 n 9
Z XJ - ( £X T/n
2 i=l i=l
s = (Equation 3a)
n - 1
79,254.00 - 78,773.78
= —! ' = 60.03,
8
s =\/s2 = 7.75, and (Equation 4)
sx = s//"~ = 7.75/JT= 2.58. (Equation 5)
The value for x (93.56) is again less than the RT (100), and there is no
indication that the nine data points, considered collectively, are abnor-
mally distributed (in particular, x is now substantially greater than s2).
Consequently, CI, calculated with nontransformed data, is determined to be:
CI = x + t 9ns- = 93.56 ± (1.397)(2.58) (Equation 6)
""~ • fL U X
= 93.56 + 3.60.
The upper limit of the CI (97.16) is now less than the RT of 100.
Consequently, it is definitively concluded that barium is not present
in the sludge at a hazardous level.
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18 / SAMPLING - Development
1.1.3.2 Stratified _R.an^qm_Samp_l i_n_g_
Stratified random sampling (Box 2) is conducted by general procedures
that are similar to the procedures described for simple random sampling. The
only difference is that, in stratified random sampling, values of x and s^
are calculated for each stratum in the population and then integrated into
overall estimates of those statistics, the standard deviation (s), s^,
and the appropriate number of samples (n) for all strata.
The hypothetical example for stratified random sampling (Box 2) is based
on the same nine sludge samples previously identified in the example of
simple random sampling (Box 1) so that the relative efficiencies of the two
sampling strategies can be fully compared. The efficiency generated through
the process of stratification is first evident in the preliminary estimate of
n (Step 2 in Boxes 1 and 2), which is six for simple random sampling and four
for stratified random sampling. (The lesser value for stratified sampling
is the consequence of a dramatic decrease in s2, which more than compen-
sated for a modest increase in A.) The most relevant indication of sampling
efficiency is the value of Sx, which is directly employed to calculate
the CI. In the case of simple random sampling, s% is calculated as 2.58 (Step 9
in Box 1), while, for stratified random sampling, s^ is determined to be 2.35
(Steps and 5 and 7 in Box 2). Consequently, the gain in efficiency attributable
to stratification is approximately 9% (0.23/2.58).
1.1.3.3 Systematic Random SampJ_in_g
Systematic random sampling (Box 3) is implemented by general procedures
that are identical to the procedures identified for simple random sampling.
The hypothetical example for systematic random sampling (Box 3) demonstrates
the bias and imprecision that are associated with that type of sampling when
unrecognized trends or cycles exist in the population.
1.1.4 Special Considerations
The preceding discussion has addressed the major issues that are critical
to the development of a reliable sampling strategy for a solid waste. The
remaining discussion focuses on several "secondary" issues that should be
considered when designing an appropriate sampling strategy. These secondary
issues are applicable to all three of the basic sampling strategies that have
been identified.
-------
Strategies / 19
BOX 2. STRATEGY FOR DETERMINING IF CHEMICAL CONTAMINANTS OF SOLID WASTES ARE
PRESENT AT HAZARDOUS LEVELS - STRATIFIED RANDOM SAMPLING OF WASTES
Step GengraJ .Procedures
1. Obtain preliminary estimates of x and s^ for each chemical
contaminant of a solid waste that is of concern. The two above-
identified statistics are calculated by, respectively, Equations 2b
and 3b (Table 1).
2. Estimate the appropriate number of samples (r\i) to be collected
from the waste through use of Equation 8 (Table 1) and Table 2.
Derive individual values of nj for each chemical contaminant of
concern. The appropriate number of samples to be taken from the
waste is the greatest of the individual ni values.
3. Randomly collect at least nj samples (or ng - ni, n3 - r\2>
samples, as will be indicated later in this box) from the waste
(collection of a few extra samples will provide protection against
poor preliminary estimates of x and s^). if S|< for each stratum
(see Equation 3b) is believed to be an accurate estimate, optimally
allocate samples among strata (i.e., allocate samples among strata
so that the number of samples collected from each stratum is directly
proportional to S|< for that stratum). Otherwise, proportionally
allocate samples among strata according to size of the strata.
Maximize the physical size (weight or volume) of all samples that
are collected from the strata.
4. Analyze the nj (or ng - HJ, 113 - r\2, etc.) samples for each chemical
contaminant of concern. Superficially (graphically) examine each
set of analytical data from each stratum for obvious departures from
normality.
5. Calculate x, s^, the standard deviation (s), and sjj for each set
of analytical data by, respectively, Equations 2b, 3b, 4, and 5
(Table 1).
6. If x for a chemical contaminant is equal to or greater than
the applicable RT (Equation 7; Table 1) and is believed to be an
accurate estimator of u, the contaminant is considered to be present
in the waste at a hazardous concentration and the study is completed.
Otherwise, continue the study. In the case of a set of analytical
data that does not exhibit obvious abnormality and for which x
is greater than s^, perform the following calculations with
nontransformed data. Otherwise, consider transforming the data by
the square root transformation (if x is about equal to s^)
or the arcsine transformation (if x is less than s^) and
performing all subsequent calculations with transformed data.
Square root and arcsine transformations are defined by, respectively,
Equations 10 and 11 (Table 1).
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20 / SAMPLING - Development
9.
Step
2.
Determine the CI for each
6 (Table 1) and Table 2.
the applicable RT (Equations 6
is not considered to be present in
tration and the study is completed.
is tentatively reached.
chemical contaminant of concern by Equation
If the upper limit of the CI is less than
and
7; Table 1),
the waste at
the chemical contaminant
a hazardous concen-
Otherwise, the opposite conclusion
If a tentative conclusion of hazard is reached, reestimate the total
number of samples (n£) to be collected from the waste by use of
Equation 8 (Table 1) and Table 2. When deriving r\2, employ the
newly calculated (not preliminary) values of x and s2. if an
additional r\2 - n\ samples of waste cannot reasonably be collected,
the study is completed and a definitive conclusion of hazard is
reached. Otherwise, collect an extra r\2 - nj samples of waste.
Repeat the basic operations described in Steps 3-8 until the waste is
judged to be nonhazardous or, if the opposite conclusion continues to
be reached, increased sampling effort is impractical.
Hypothetical Example
The preliminary study of barium levels in the elutriate of four EP
toxicity tests conducted with sludge collected from the lagoon several
years ago generated values of 86 and 90 ppm for sludge obtained from
the upper third of the lagoon and values of 98 and 104 ppm for sludge
from the lower two-thirds of the lagoon. Those two sets of values are
judged to be indicative of nonrandom chemical heterogeneity (two_
strata) within the lagoon. Therefore, preliminary estimates of x
and s^ are calculated as:
wkxk =
.(2)001.00)
>67} and (Equation 2b)
s2 =
k=l
r
k=l
W
k'k
+ (2)08.00) = 14 67
3 + ^3 14'b/'
(Equation 3b)
Based on the preliminary estimates of x and s2, as well as the
knowledge that the RT for barium is 100 ppm,
<
_ \20S _ (1.368^)04.67) , ,,
p — Q — . .. -_ —— — o, 0 0 .
1 3.33^
(Equation 8)
-------
Strategies / 21
3.
6.
7.
As indicated above, the appropriate number of sludge samples (n^) to
be collected from the lagoon is four. However, for purposes of
comparison to simple random sampling (Box 1), six samples (plus
three extra samples for protection against poor preliminary estimates
of x and s2) are collected from the lagoon by a two-stage random-
ization process (Figure 2). Because S|< for the upper (2.12 ppm) and
lower (5.66 ppm) strata are not believed to be very accurate estimates,
the nine samples to be collected from the lagoon are not optimally
allocated between the two strata (optimum allocation would require two
and seven samples to be collected from the upper and lower strata,
respectively). Alternatively, proportional allocation is employed -
three samples are collected from the upper stratum (which represents
one-third of the lagoon), and six samples are taken from the lower
stratum (two-thirds of the lagoon). All samples consist of the
greatest volume of sludge that can be practically collected.
The nine samples of sludge generate the following concentrations
of barium in the EP toxicity test: upper stratum - 89, 90, and 87 ppm;
lower stratum - 96, 93, 113, 93, 90, and 91 ppm. Although the value
of 113 ppm appears unusual as compared to other data for the lower
stratum, there is no obvious indication that the data are not normally
distributed.
New values for x and s2 and associated values for the standard
deviation (s) and s^ are calculated as:
k=l
k
-m + J2K.73.6PJ.
33
s = 2 = 7.06, and
s- = s//n~ = 7.06/79 = 2.35.
(Equation 2b)
(Equation 3b)
(Equation 4)
(Equation 5)
The new value for x (93.56) is less than the RT (100). In addition,
x is greater than s2 (49.84) and, as previously indicated, the raw
data are not characterized by obvious abnormality. Consequently, the
study is continued, with the following calculation performed with
nontransformed data.
CI = x + t 9ns- = 93.56 + (1.397)(2.35)
~" • t U X
= 93.56 + 3.28.
(Equation 6)
The upper limit of the CI (96.84) is less than the applicable RT (100).
Therefore, it is concluded that barium is not present in the sludge at
a hazardous concentration.
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22 / SAMPLING - Development
BOX 3. STRATEGY FOR DETERMINING IF CHEMICAL CONTAMINANTS OF SOLID WASTES
ARE PRESENT AT HAZARDOUS LEVELS - SYSTEMATIC RANDOM SAMPLING
Step General Procedure
1. Follow general procedures presented for simple random
sampling of solid wastes (Box 1).
>tep Hypothetical Example
1. The example presented in Box 1 is applicable to systematic random
sampling with the understanding that the nine sludge samples obtainec
from the lagoon would be collected at equal intervals along a tran-
sect running from a randomly selected location on one bank of the
lagoon to the opposite bank. If that randomly selected transect
were established between Units 1 and 409 of the sampling grid
(Figure 2) and sampling were performed at Unit 1 and, thereafter,
at three-unit intervals along the transect (i.e., Unit 1, Unit 52,
Unit 103, . . . , and Unit 409), it is apparent that only two
samples would be collected in the upper third of the lagoon, while
seven samples would be obtained from the lower two-thirds of the
lagoon. If, as suggested by the barium concentrations illustrated
in Figure 2, the lower part of the lagoon is characterized by
greater and more variable barium contamination than the upper part
of the lagoon, systematic random sampling along the above-identified
transect, by placing undue (disproportionate) emphasis on the lower
part of the lagoon, might be expected to result in an inaccurate
(overestimation) and imprecise characterization of barium levels in
the whole lagoon, as compared to either simple random sampling
or stratified random sampling. Such inaccuracy and imprecision,
which is typical of systematic random sampling when unrecognized
trends or cycles occur in the population, would be magnified if, for
example, the randomly selected transect were established solely in
the lower part of the lagoon, e.g., between Units 239 and 255 of the
sampling grid.
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Strategies / 23
1.1.4.1 Composite Sampling
In composite sampling, a number of random samples are initially collected
from a waste and combined into a single sample, which is then analyzed for
the chemical contaminants of concern. The major disadvantage of composite
sampling as compared to noncomposite sampling is that information concerning
the chemical contaminants is lost, i.e., each initial set of samples generates
only a single estimate of the concentration of each contaminant. Consequently,
since the number of analytical measurements (n) is small, s£ and t.20 are
large, thus decreasing the likelihood that a contaminant will be judged to
occur in the waste at a nonhazardous level (refer to appropriate equations in
Table 1 and to Table 2). A remedy to that situation is to collect and
analyze a relatively large number of composite samples, thereby offsetting
the savings in analytical costs that are often associated with composite
sampling, but achieving better representation of the waste than would occur
with noncomposite sampling.
The appropriate number of composite samples to be collected from a solid
waste is estimated by use of Equation 8 (Table 1) as previously described for
the three basic sampling strategies. In comparison to noncomposite sampling,
composite sampling may have the effect of minimizing between-sample variation
(the same phenomenon that occurs when the physical size of a sample is
maximized), thereby reducing somewhat the number of samples that must be
collected from the waste.
1.1.4.2 Subsampling
The variance (s2) associated with a chemical contaminant of a
waste consists of two components in that:
p
2 = 2 +.fa., (Equation 12)
s m
with s2 = a component attributable to sampling (sample) variation, s| =
a component attributable to analytical (subsample) variation, and m = number
of subsamples. In general, s^ should not be allowed to exceed one-ninth
of s2. if a preliminary study indicates that s2 exceeds that threshold,
a sampling strategy involving subsampling shoula be considered. In such a
strategy, a number of replicate measurements are randomly made on a relatively
limited number of randomly collected samples. Consequently, analytical
effort is allocated as a function of analytical variability. The efficiency
of that general strategy in meeting regulatory objectives has already been
demonstrated in the previous discussions of sampling effort.
-------
24 / SAMPLING - Development
The appropriate number of samples (n) to be collected from a solid waste
for which subsarnpling will be employed is again estimated by Equation 8
(Table 1). In the case of simple random sampling or systematic random
sampling with an equal number of subsamples analyzed per sample:
n
x = £ x-j/n, (Equation 13)
i=l
with x-j = sample mean (calculated from values for subsamples) and n = number of
samples. Also,
n n
E x2 - (E x.)2/n
S2 _ i=l i_=_l^ . (Equation 14)
"n""-"l
The optimum number of subsamples to be taken from each sample (m Op^4 ) is
estimated as:
_fa (Equation 15)
m(opt.) - Ss
when cost factors are not considered. The value for sa is calculated from
available data as:
n m ,, ,,
E E X?. - (E X. -r/m
_ . i=l J=l , (Equation 16)
a / n (m - 1)
and ss, which can have a negative characteristic, is defined as:
rp—r-
f ~ _a_ , (Equation 17)
ss ' J m
with s^ calculated as indicated in Equation 14.
In the case of stratified random sampling with subsampling, critical
formulas for estimating sample size (n) by Equation 8 (Table 1) are:
- _ z u ' (Equation 2b)
k=l k k'
-------
Special Considerations / 25
with Xk = stratum mean and W^ = fraction of population represented by Stratum K
(number of strata, k, ranges from 1 to r). In Equation 2b, x^ for each stratum
is calculated as the average of all sample means in the stratum (sample means
are calculated from values for subsamples). In addition:
S2 = Z w s2 (Equation 3b)
2
with Sk for each stratum calculated from all sample means in the stratum.
The optimum subsampling effort when cost factors are not considered and all
replication is symmetrical is again estimated as:
sa
m(opt.) = 7~ » with (Equation 15)
n m 9 -J
Z .Z .E Xkij ' ( EXkij} /m
j^L-LlLjilL » anc' (Equation 18)
rn (m - 1)
, (Equation 17)
m
with s2 derived as shown in Equation 3b.
1.1.4.3 Cost and Lo_ss F_unc_tj_ons
The cost of chemically characterizing a waste is dependent on the
specific strategy that is employed to sample the waste. For example, in the
case of simple random sampling without subsampling, a reasonable cost function
might be:
C(n) = Co + Cln ' (Equation 19)
with C(n\ = cost of employing a sample size of n, C0 = an overhead cost
(which is independent of the number of samples that are collected and analyzed),
and Ci = a sample-dependent cost. A consideration of C(n) mandates an
evaluation of L(n), which is the sample-size-dependent expected financial
loss related to the erroneous conclusion that a waste is hazardous. A simple
loss function is:
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26 / SAMPLING - Development
2
, , . as , (Equation 20)
L(n) - —
with ot = a constant related to the cost of a waste management program if the
waste is judged to be hazardous, s2 = sample variance, and n = number of
samples. A primary objective of any sampling strategy is to minimize C(n)
+ L(n)- Differentiation of Equations 19 and 20 indicates that the number of
samples (n) which minimize C(n) + L(n) is:
(Equation 21)
As is evident from Equation 21, a comparatively large number of samples (n)
is justified if the value of a or s2 is large, whereas a relatively small
number of samples is appropriate if the value of Cj is large. These
general conclusions are valid for any sampling strategy for a solid waste.
-------
1.2 Implementation of Sampling Plan
This section describes EPA-approved equipment and procedures for obtaining
representative samples of a solid waste. The information in this section is
general in nature. Since each specific sampling situation is unique, the
equipment and procedures described must be modified appropriately in an
actual use situation to ensure that representative samples are collected. It
is the responsibility of those persons conducting sampling programs to make
the appropriate modifications.
1.2.1 Selection of Sampling Equipment
Sampling the diverse types of RCRA-regulated wastes requires a variety
of different types of samplers. Several sampling devices are described in
this section. Some of these samplers are commercially available. Others
will have to be fabricated by the user. Table 1 is a general guide to the
types of waste that can be sampled by each of the samplers described.
1.2.1.1 Composite Liquid Waste Sampler (Coliwasa)
Scope and Purpose
The Coliwasa is a device employed to sample free-flowing liquids and
slurries contained in drums, shallow open-top tanks, pits, and similar
containers. It is especially useful for sampling wastes that consist of
several immiscible liquid phases.
The Coliwasa consists of a glass, plastic, or metal tube equipped with
an end closure which can be opened and closed while the tube is submerged in
the material to be sampled.
The Coliwasa was developed by the California Department of Health under
a grant from the U.S. EPA. A more detailed discussion of the Coliwasa can
be found in the Department of Health's report "Samplers and Sampling Proce-
dures for Hazardous Waste Streams," Grant No. R804692010, MERL, USEPA,
Cincinnati, Ohio. A modification of the device is described in "Evaluation
of the Procedures for Identification of Hazardous Wastes," by L.R. Williams
et al. (EPA/EMSC, Las Vegas, Nevada).
It should be mentioned that some experienced sampling personnel find
the Coliwasa cumbersome and difficult to clean or dispose of following use.
General Comments and Precautions
1. Do not use a plastic Coliwasa, unless it is constructed of fluoro-
carbons (e.g., Teflon), to sample wastes containing organic
materials.
-------
2 / SAMPLING - Implementation
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Equipment / 3
2. Do not use a glass Coliwasa to sample liquids that contain
hydrofluoric acid.
3. If significant amounts of solid material are present within
2 inches of the bottom of the container to be sampled, special
procedures will be necessary to obtain a representative sample of
this solid phase.
Apparatus
Coliwasas are available commercially (NASCO) or can be fabricated to
conform to the specifications detailed in Figure 1. Table 2 lists the parts
required to fabricate a plastic or glass Coliwasa.
Assembly
Assemble Coliwasa sampler as follows:
1. Attach swivel to the T-handle with the 3.12-cm-long bolt and secure
with the 3/16-in. NC washer and lock nut.
2. Shape stopper into a cone by boring a 0.95-cm hole through the
center of the stopper. Insert a short piece of 0.95-cm-O.D. handle
through the hole until the end of the handle is flush against the
bottom (smaller diameter) surface of the stopper. Carefully and
uniformly turn the stopper into a cone against a grinding wheel.
This is done by turning the stopper with the handle and grinding it
down conically from about 0.5 cm of the top (larger diameter)
surface to the edge of the 0.95-cm-hole on the bottom surface.
Attach neoprene stopper to one end of the stopper rod and secure
with the 3.8-in. NC washer and lock nut.
3. Install the stopper and stopper rod assembly in the sampling
tube.
4. Secure locking block sleeve on the block with glue or screws.
5. Position the locking block on top of the sampling tube so that the
sleeveless portion of the block fits inside the tube, the sleeve
sits against the top end of the tube, and the upper end of the
stopper rod slips through the center hold of the block.
6. Attach the upper end of the stopper to the swivel of the T-handle.
7. Place the sampler in the closed position and adjust the tension on
the stopper by screwing the T-handle in or out.
8. Test the tension by filling the Coliwasa with water to ensure that
it is leak free.
-------
4 / SAMPLING - Implementation
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Stopper Rod, PVC
0.95cm (3/8") 0. D.
Pipe, PVC, 4.13cm (1 5/8") I. D.
4.26cm (1 7/8") O. D.
Stopper, Neoprene, No. 9 with
3/8" S. S. or PVC Nut and Washer
SAMPLING POSITION
CLOSE POSITION
Figure 1. Composite liquid waste sampler (Coliwasa).
-------
Equipment / 5
TABLE 2. PARTS FOR CONSTRUCTING A COLIWASA
Quantity Item
1 Sample tube, translucent PVC
plastic, 4.13 cm I.D. x 1.52 m
long x 0.4 cm wall thickness
1 Sample tube, borosilicate glass,
4.13 cm I.D. x 1.52 m long
1 Stopper, neoprene rubber #9
1 Stopper rod, PVC, 0.95 cm
O.D. x 1.67 m long
1 Stopper rod, teflon, 0.95 cm
O.D. x 1.67 m long
1 Locking block, PVC, 3.8 cm
O.D. x 10.2 cm long with
0.56-cm hole in center
1 Locking block sleeve, PVC,
4.13 cm I.D. x 6.35 cm long
Comments
Plastic
Coliwasa
only
Glass
Coliwasa
only
Plastic
Coliwasa
only
Glass or
Plastic
Coliwasa
Fabricate by
drilling
0.56-cm hole
through center
Fabricate from
stock 4.13-cm
PVC pipe
Supplier
Plastic
supply
houses
Corning
Glass Works
#72-1602
Laboratory
supply house
Plastic
supply
houses
Plastic
supply
houses
Plastic
supply
houses
Plastic
supply
houses
T-handle, aluminum, 18 cm long
x 2.86 cm wide with 1.27-cm-wide
channel
Swivel, aluminum bar 1.27 cm
square x 5.08 cm long with
3/8-in. NC inside thread to
attach stopper rod
Fabricate from
aluminum bar
stock
Fabricate from
aluminum bar
stock
Hardware stores
Hardware stores
-------
6 / SAMPLING - Implementation
TABLE 2 (CONT.)
Quantity
1
1
1
1
1
1
1
Item
Comments
Nut, PVC, 3/8 in. NC
Washer, PVC, 3/8 in. NC
Nut, stainless steel, 3/8 in. NC
Washer, stainless steel, 3/8 in.
Bolt, 3.12 cm long x 3.16 in. NC
Nut, 3/16 in. NC
Washer, lock 3/16 in.
Supplier
Plastic supplier
Plastic supplier
Hardware stores
Hardware stores
Hardware stores
Hardware stores
Hardware stores
-------
Equipment / 7
Procedure
1. Clean Coliwasa.
2. Adjust sampler's locking mechanism to ensure that the stopper
provides a tight closure. Open sampler by placing stopper rod
handle in the T-position and pushing the rod down until the handle
sits against the sampler's locking block.
3. Slowly lower the sampler into the waste at a rate that permits the
level of liquid inside and outside the sampler to remain the same.
If the level of waste in the sampler tube is lower inside than
outside, the sampling rate is too fast and will produce a nonrepre-
sentative sample.
4. When the sampler hits the bottom of the waste container, push
sampler tube down to close and lock the stopper by turning the
T-handle until it is upright and one end rests on the locking
block.
5. Withdraw Coliwasa from waste and wipe the outside with a disposable
cloth or rag.
1.2.1.2 Weighted Bottle
Scope and Application
This sampler consists of a glass or plastic bottle, sinker, stopper, and
a line which is used to lower, raise, and open the bottle. The weighted
bottle samples liquids and free-flowing slurries.
General Comments and Precautions
1. Do not use a nonfluorocarbon plastic bottle to sample wastes con-
taining organic materials.
2. Do not use a glass bottle to sample wastes that contain hydrofluoric
acid.
3. Before sampling, ensure that the waste will not corrode the sinker,
bottle holder, or line.
Apparatus
A weighted bottle with line is built to the specifications in ASTM
Methods D 270 and E 300. Figure 2 shows the configuration of a weighted
bottle sampler.
-------
8 / SAMPLING - Implementation
Washer
Pin
Nut
Figure 2. Weighted bottle sampler.
-------
Equipment / 9
Procedure
1. Clean bottle.
2. Assemble weighted bottle sampler.
3. Lower the sampler to directed depth and pull out the bottle stopper
by jerking the line.
4. Allow bottle to fill completely as evidenced by cessation of air
bubbles.
5. Raise sampler, cap, and wipe off with a disposable cloth. The
bottle can serve as a sample container.
1.2.1.3 Dipper
Scope and Application
The dipper consists of a glass or plastic beaker clamped to the end of a
2- or 3-piece telescoping aluminum or fiberglass pole which serves as the
handle. A dipper samples liquids and free-flowing slurries.
General Comments and Precautions
1. Do not use a nonfluorocarbon plastic beaker to sample wastes
containing organic materials.
2. Do not use a glass beaker to sample wastes of high pH or wastes
that contain hydrofluoric acid.
3. Paint aluminum pole and clamp with a 2-part epoxy or other chemical-
resistant paint when sampling either alkaline or acidic wastes.
Apparatus
Dippers are not available commercially and must be fabricated to conform
to the specifications detailed in Figure 3. Table 3 lists the parts required
to fabricate a dipper.
Procedure
1. Clean beaker, clamp, and handle.
2. Assemble dipper by bolting adjustable clamp to the pole. Place
beaker in clamp and fasten shut.
3. Turn dipper so the mouth of the beaker faces down and insert into
waste material. Turn beaker right side up when dipper is at
desired depth. Allow beaker to fill completely as shown by the
cessation of air bubbles.
4. Raise dipper and transfer sample to container.
-------
10 / SAMPLING - Implementation
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-------
Equipment / 11
TABLE 3. PARTS FOR CONSTRUCTING A DIPPER
Quantity
Item
4
4
Adjustable clamp, 6.4 to 8.9 cm
(2-1/2 to 3-1/2 in.) for 250- to
600-ml beakers. Heavy-duty
aluminum
Tube 2.5 to 4.5 m long with
joint cam locking mechanism.
Diameter 2.54 cm I.D. and
3.18 cm I.D.
Polypropylene or glass beaker,
250 ml to 600 ml
Bolts 2-1/4 in. x 1/4 in., NC
Nuts, 1/4 in., NC
Supplier
Laboratory
supply houses
Swimming pool
supply houses
Laboratory
supply houses
Hardware stores
Hardware stores
-------
12 / SAMPLING - Implementation
1.2.1.4 Thief
Scope and Application
A thief consists of two slotted concentric tubes usually made of stainless
steel or brass. The outer tube has a conical pointed tip which permits the
sampler to penetrate the material being sampled. The inner tube is rotated
to open and close the sampler. A thief is used to sample dry granules or
powdered wastes whose particle diameter is less than one-third the width of
the slots.
Apparatus
A thief is available at laboratory supply stores (Figure 4).
Procedure
1. Clean sampler.
2. Insert closed thief into waste material. Rotate inner tube to open
thief. Wiggle the unit to encourage material to flow into thief.
Close thief and withdraw. Place sampler thief in a horizontal
position with the slots facing upward. Remove inner tube from
thief and transfer sample to a container.
1.2.1.5 Trier
Scope and Application
A trier consists of a tube cut in half lengthwise with a sharpened tip
that allows the sampler to cut into sticky solids and loosen soil. A trier
samples moist or sticky solids with a particle diameter less than one-half
the diameter of the trier.
Apparatus
1.
Triers 61 to 100 cm long and 1.27 to 2.54 cm in diameter are
available at laboratory supply stores.
A large trier can be fabricated to conform to the specifications in
Figure 5. A metal or polyvinyl chloride pipe, 1.52 m (5 ft) long x
3.2 cm (1.4 in.) I.D., with a 0.32-cm (1-1/8 in.) wall thickness, is
needed. The pipe should be sawed lengthwise, about 60-40 split, to
form a trough stretching from one end to 10 cm away from the other
end. The edges of the slot and the tip of the pipe are sharpened
to permit the sampler to cut into the waste material being sampled.
The unsplit length of the pipe serves as the handle.
-------
Equipment / 13
60-100 cm
1.27-2.54 cm
Figure 4. Thief sampler.
-------
14 / SAMPLING - Implementation
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r
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, 122-1 83 cm
(48-72")
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60-100 cm
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FigureB. Sampling triers.
-------
Equipment /15
Procedure
1. Clean trier.
2. Insert trier into waste material 0 to 45" from horizontal. Rotate
trier to cut a core of the waste. Remove trier with concave side
up and transfer sample to container.
1.2.1.6 Auger
Scope and Application
An auger consists of sharpened spiral blades attached to a hard metal
central shaft. An auger samples hard or packed solid wastes or soil.
Apparatus
Augers are available at hardware and laboratory supply stores.
Procedure
1. Clean sampler.
2. Bore a hole through the middle of an aluminum pie pan large enough
to allow the blade of the auger to pass through. The pan will be
used to catch the sample brought to the surface by the auger.
3. Place pan against the sampling point. Auger through the hole in
the pan until the desired sampling depth is reached. Back off the
auger and transfer the sample in the pan and adhering to the auger
to a container. Spoon out the rest of the loosened sample with a
sample trier.
1.2.1.7 Scoop and Shovel
Scope an_d_App1_ication
Scoops and shovels are used to sample granular or powdered material in
bins, shallow containers ana conveyor belts.
Apparatus
Scoops are available at laboratory supply houses. Flat-nosed shovels
are available at hardware stores.
-------
16 / SAMPLING - Implementation
Procedure
1. Clean sampler.
2. Obtain a full cross section of the waste material using a scoop or
shovel that is large enough to contain the waste collected in one
cross section sweep.
1.2.2 Selection of Sample Containers
The most important factors to consider when choosing containers for
hazardous waste samples are compatibility with the waste, cost, resistance to
breakage, and volume. Containers must not distort, rupture, or leak as a
result of chemical reactions with constituents of waste samples. Thus, it is
important to have some idea of the properties and composition of the waste.
The containers must have adequate wall thickness to withstand handling during
sample collection and transport to the laboratory. Containers with wide
mouths are desirable to facilitate transfer of samples from samplers to
containers. Also, the containers must be large enough to contain the optimum
sample volume.
Containers for collecting and storing hazardous waste samples are
usually made of plastic or glass. Plastics that are commonly used to make
the containers include high-density or linear polyethylene (LPE), conventional
polyethylene, polypropylene, polycarbonate, teflon FEP (fluorinated ethylene
propylene), polyvinyl chloride (PVC), or polymethylpentene. Teflon FEP is
almost universally usable due to its chemical inertness and resistance to
breakage. However, its high cost severely limits its use. LPE, on the other
hand, usually offers the best combination of chemical resistance and low cost
when samples are to be analyzed for inorganic parameters.
Glass containers are relatively inert to most chemicals and can be used
to collect and store almost all hazardous waste samples except those that
contain strong alkali and hydrofluoric acid. Soda glass bottles are suggested
due to their low cost and ready availability. Borosilicate glass containers,
such as Pyrex and Corex, are more inert and more resistant to breakage than
soda glass but are expensive and not always readily available. Glass con-
tainers are generally more fragile and much heavier than plastic containers.
Glass or FEP containers must be used for waste samples that will be analyzed for
organic compounds.
The containers must have tight, screw-type lids. Plastic bottles are
usually provided with screw caps made of the same material as the bottles.
Buttress threads are recommended. Cap liners are not usually required for
plastic containers. Teflon cap liners should be used with glass containers
supplied with rigid plastic screw caps. Teflon liners may be purchased from
plastic specialty supply houses (e.g., Scientific Specialties Service, Inc.,
P.O. Box 352, Randallstown, Maryland 21133). These caps are usually provided
with waxed paper liners. Other liners that may be suitable are polyethylene,
polypropylene, and neoprene plastics.
-------
Processing / 17
1.2.3 Processing and Storage of Samples
Once a sample has been collected, steps must be taken to preserve the
chemical and physical integrity of the sample during transport and storage
prior to analysis. The type of sample preservation required will vary
according to the sample type and the parameter to be measured.
Preservation and storage requirements are described in the individual
analytical methods in this manual. Since these requirements vary with the
analytical method to be employed, it may be necessary to prepare more than
one container of the same waste if more than one type of analysis is to be
conducted. The chemical makeup of the samples can alter the effectiveness of
preservation, therefore all sample analyses should be performed as soon as
possible after sampling.
Section 1.3 of this manual describes specifications for packaging and
shipping samples.
-------
SAMPLING - Implementation; Chain of Custody
1.3 Documentation of Chain of Custody
An essential part of any sampling/analytical scheme is ensuring the
integrity of the sample from collection to data reporting. This includes the
ability to trace the possession and handling of samples from the time of
collection through analysis and final disposition. This documentation of the
history of the sample is referred to as Chain of Custody.
Chain of custody is necessary if there is any possibility that the
analytical data or conclusions based upon analytical data will be used in
litigation. In cases where litigation is not involved, many of the chain-of-
custody procedures are still useful for routine control of sample flow. The
components of chain of custody - sample seals, a field log book, chain-of-
custody record, and sample analysis request sheet - and the procedures for
their use are described in the following sections.
A sample is considered to be under a person's custody if (1) it is in a
person's physical possession, (2) in view of the person after he has taken
possession, (3) secured by that person so that no one can tamper with the
sample, or (4) secured by that person in an area which is restricted to
authorized personnel. A person who has samples under his custody must comply
with the procedures described in the following sections.
The material presented here briefly summarizes the major aspects of chain
of custody. The reader is referred to NEIC Policies and Procedures,
EPA-330/9/78/001-R (as revised 1/82), or other manual as appropriate, for
more information.
1.3.1 Sample Labels
Sample labels (Figure 1) are necessary to prevent misidentification of
samples. Gummed paper labels or tags are adequate and should include
at least the following information:
Sample number
Name of collector
Date and time of collection
Place of collection
Labels should be affixed to sample containers prior to or at the time of
sampling. The labels should be filled out at the time of collection.
1.3.2 Sample Seals
Sample seals are used to detect unauthorized tampering of samples
following sample collection up to the time of analysis. Gummed paper
seals may be used for this purpose. The paper seal should include, at least,
the following information:
-------
2 / SAMPLING - Chain of Custody
Collector
Place of Collection
Sample No.
Date Sampled
Field Information
Time Sampled
Figure 1. Example of Sample Label
-------
Seals; Log Book / 3
Sample number (This number must be identical with the number on
the sample label)
Collector's name
Date and time of sampling
The seal must be attached in such a way that it is necessary to break it
in order to open the sample container. An example of a sample seal is shown
in Figure 2. Seals must be affixed to containers before the samples leave
the custody of sampling personnel.
1.3.3 Field Log Book
All information pertinent to a field survey or sampling must be
recorded in a log book. This should be bound, preferably with consecu-
tively numbered pages that are 21.6 by 27.9 cm (8-1/2 by 11 in.). As a
minimum, entries in the log book must include the following:
Purpose of sampling (e.g., surveillance, contract number)
Location of sampling point
Name and address of field contact
Producer of waste and address, if different than location
Type of process (if known) producing waste
Type of waste (e.g., sludge, wastewater)
Suspected waste composition, including concentrations
Number and volume of sample taken
Description of sampling point and sampling methodology
Date and time of collection
Collector's sample identification number(s)
Sample distribution and how transported (e.g., name of laboratory,
UPS, Federal Express)
References such as maps or photographs of the sampling site
Field observations
Any field measurements made (e.g., pH, flammability, explosivity)
Signatures of personnel responsible for observations
-------
4 / SAMPLING - Chain of Custody
NAME AND ADDRESS OF ORGANIZATION COLLECTING SAMPLES
Person Collecting Sample Sample No.
(signature)
Date Collected Time Collected
Place Collected
Figure 2. Example of Official Sample Seal
-------
Log Book; Record; Request / 5
Sampling situations vary widely. No general rule can be given as to the
extent of information that must be entered in the log book. A good rule,
however, is to record sufficient information so that someone can reconstruct
the sampling without reliance on the collector's memory.
The log book must be protected and kept in a safe place.
1.3.4 Chain-of-Custody Record
To establish the documentation necessary to trace sample possession from
the time of collection, a chain-of-custody record should be filled out and
accompany every sample. This record becomes especially important if the
sample is to be introduced as evidence in a court litigation. A chain-of-
custody record is illustrated in Figure 3.
The record should contain the following minimum information.
Sample number
Signature of collector
Date and time of collection
Place and address of collection
Waste type
Signature of persons involved in the chain of possession
Inclusive dates of possession
1.3.5 Sample Analysis Request Sheet
The sample analysis request sheet (Figure 4) is intended to accompany the
sample on delivery to the laboratory. The field portion of this form is
completed by the person collecting the sample and should include most of the
pertinent information noted in the log book. The laboratory portion of this
form is intended to be completed by laboratory personnel and to include at a
minimum:
Name of person receiving the sample
Laboratory sample number
Date of sample receipt
Sample allocation
Analyses to be performed
-------
6 / SAMPLING - Chain of Custody
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Request / 7
SAMPLING ANALYSIS REQUEST
PART I: Field Section
Collector
Date Sampled
Time
hours
Affiliation of Sampler
Address
number street city state
Telephone ( ) Company Contact
LABORATORY
SAMPLE COLLECTOR'S TYPE OF
NUMBER SAMPLE NO. SAMPLE*
zip
FIELD INFORMATION**
Analysis Requested
Special Handling and/or Storage
PART II: LABORATORY SECTION**
Received by
Analysis Required
Title
Date
* Indicate whether sample is soil, sludge, etc.
**Use back of page for additional information relative to sample location.
Figure 4. Example of hazardous waste sample analysis request sheet.
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8 / SAMPLING - Chain of Custody
1.3.6 Sample Delivery to the Laboratory
The sample should be delivered to the laboratory for analysis as soon as
practicable - usually within 1 or 2 days after sampling. The sample must be
accompanied by the chain-of-custody record (Figure 3) and by a sample analysis
request sheet (Figure 4). The sample must be delivered to the person in the
laboratory authorized to receive samples (often referred to as the sample
custodian).
1.3.7 Shipping of Samples
Any material that is identified in the DOT Hazardous Material Table
(49 CFR 172.101) must be transported as prescribed in the table. All other
hazardous waste samples must be transported as follows:
1. Collect sample in a 16-ounce or smaller glass or polyethylene
container with nonmetallic teflon-lined screw cap. Allow sufficient
air space (approximately 10% by volume) so container is not liquid
full at 54* C (130* F). If collecting a solid material, the container
plus contents should not exceed 1 pound net weight. If sampling for
volatile organic analysis, fill VOA container to septum but place the
VOA container inside a 16-ounce or smaller container so the required
air space may be provided. Large quantities, up to 3.785 liters
(1 gallon), may be collected if the sample's flash point is 23° C
(75° F) or higher. In this case, the flash point must be marked
on the outside container (e.g., carton, cooler), and shipping papers
should state that "Flash point is 73° F or higher."
2. Seal sample and place in a 4-mil-thick polyethylene bag, one sample
per bag.
3. Place sealed bag inside a metal can with noncombustible, absorbent
cushioning material (e.g., vermiculite or earth) to prevent breakage,
one bag per can. Pressure-close the can and use clips, tape or
other positive means to hold the lid securely.
4. Mark the can with:
Name and address of originator
"Flammable Liquid N.O.S. UN 1993"
(or "Flammable Solid N.O.S. UN 1325")
NOTE: UN numbers are now required in proper shipping names.
5. Place one or more metal cans in a strong outside container such as a
picnic cooler or fiberboard box. Preservatives are not used for
hazardous waste site samples.
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Shipping; Receipt / 9
6. Prepare for shipping:
"Flammable Liquid, N.O.S. UN 1993" or "Flammable Solid, N.O.S. UN 1325";
"Cargo Aircraft Only" (if more than 1 quart net per outside package);
"Limited Quantity" or "Ltd. Qty."; "Laboratory Samples"; "Net Weight "
or "Net Volume " (of hazardous contents) should be indicated on ship-
ping papers and on outside of outside shipping container. "This Side Up"
or "This End Up" should also be on container. Sign shipper certification.
7. Stand by for possible carrier requests to open outside containers for
inspection or modify packaging. It is wise to contact carrier before
packing to ascertain local packaging requirements and not to leave area
before the carrier vehicle (aircraft, truck, etc.) is on its way.
1.3.8 Receipt and Logging of Sample
In the laboratory, a sample custodian should be assigned to receive the
samples. Upon receipt of a sample, the custodian should inspect the condition
of the sample and the sample seal, reconcile the information on the sample
label and seal against that on the chain-of-custody record, assign a laboratory
number, log in the sample in the laboratory log book, and store the sample in
a secured sample storage room or cabinet until assigned to an analyst for
analysis.
The sample custodian should inspect the sample for any leakage from the
container. A leaky container containing multiphase sample should not be
accepted for analysis. This sample will no longer be a representative
sample. If the sample is contained in a plastic bottle and the container
walls show that the sample is under pressure or releasing gases, the sample
should be treated with caution since it may be explosive or release extremely
poisonous gases. The custodian should examine whether the sample seal is
intact or broken, since a broken seal may mean sample tampering and would
make analysis results inadmissible in court as evidence. Any discrepancies
between the information on the sample label and seal and the information that
is on the chain-of-custody record and the sample analysis request sheet
should be resolved before the sample is assigned for analysis. This effort
might require communication with the sample collector. Results of the
inspection should be noted on the sample analysis request sheet and on the
laboratory sample log book.
Incoming samples usually carry the inspector's or collector's identifi-
cation numbers. To further identify these samples, the laboratory should
assign its own identification numbers, which normally are given consecutively.
Each sample should be marked with the assigned laboratory number. This
number is correspondingly recorded on a laboratory sample log book along with
the information describing the sample. The sample information is copied from
the sample analysis request sheet and cross-checked against that on the
sample label.
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10 / SAMPLING - Chain of Custody; Methodology
1.3.9 Assignment of Sample for Analysis
In most cases, the laboratory supervisor assigns the sample for analysis.
The supervisor should review the information on the sample analysis request
sheet, which now includes inspection notes recorded by the laboratory sample
custodian. The technician assigned to analysis should record in the laboratory
notebook the identifying information about the sample, the date of receipt,
and other pertinent information. This record should also include the subsequent
testing data and calculations. The sample may have to be split with other
laboratories in order to obtain all the necessary analytical information. In
this case, the same type of chain-of-custody procedures must be employed at
the other laboratory and while the sample is being transported to the other
laboratory.
Once the sample has been received in the laboratory, the supervisor or
his assignee is responsible for its care and custody. He should be prepared
to testify that the sample was in his possession or secured in the laboratory
at all times from the moment it was received from the custodian until the
analyses were performed.
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1.4 Sampling Methodology
The sampling methodology will be determined in part by the sampling
strategy to be employed. Four different types of sampling strategies (simple
random, stratified random, systematic random, and authoritative sampling)
were discussed in Section 1.1. The latter three strategies require more
information than the simple random approach. This additional information
must either be acquired through sampling or must be estimated. The informa-
tion requirements of the sampling strategy to be used should be kept in mind
when designing a sampling plan.
The methods and equipment used for sampling waste materials will vary
with the form and consistency of the waste materials to be sampled. Samples
collected using the sampling protocols listed below, for sampling waste with
properties similar to the indicated materials, will be considered by the
Agency to be representative of the waste.
Extremely viscous liquid ASTM Standard D140-701
Crushed or powdered material ASTM Standard D346-75
Soil or rock-like material ASTM Standard D420-69
Soil-like material ASTM Standard D1452-65
Fly-ash-like material ASTM Standard D2234-76
1.4.1 Containers
The term container as used here refers to receptacles that are designed
for transporting materials, e.g., drums and other smaller receptacles as
opposed to stationary tanks. (Stationary tanks are discussed in
Section 1.4.2.) Weighted bottles, Coliwasas, drum thiefs, or triers are
the sampling devices which are chosen for the sampling of containers.
The sampling strategy for containers varies according to (1) the
number of containers to be sampled, and (2) access to the containers.
Ideally, if the waste is contained in several containers, every container
will be sampled. If this is not possible due to the large number of containers
or cost factors, a subset of individual containers must be randomly selected
for sampling. This can be done by assigning each container a number and then
randomly choosing a set of numbers for sampling.
Access to a container will affect the number of samples that can
be taken from the container and the location within the container from
which samples can be taken. Ideally, several samples should be taken
from locations displaced both vertically and horizontally throughout the
waste. The number of samples required for reliable sampling will vary
depending on the distribution of the waste components in the container. As a
minimum with an unknown waste, a sufficient number and distribution of
samples should be taken to address any possible vertical anomalies in the
*ASTM Standards are available from ASTM, 1916 Race Street,
Philadelphia, PA 19103.
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2 / SAMPLING - Methodology
waste. This is because contained wastes have a much greater tendency to be
nonrandomly heterogeneous in a vertical rather than a horizontal direction
due to (1) settling of solids and the denser phases of liquids, and (2)
variation in the content of the waste as it entered the container. Bags,
paper drums, and open-headed steel drums (of which the entire top can be
removed) generally do not restrict access to the waste and therefore do not
limit sampling.
When access to a container is unlimited, a useful strategy for obtaining
a representative set of samples is a three-dimensional simple random sampling
strategy in which the container is divided by constructing an imaginary three-
dimensional grid (see Figure 1). This is done as follows. First, the top
surface of the waste is divided into a grid whose sections either approximate
the size of the sampling device or are larger than the sampling device if the
container is large. (Cylindrical containers can be divided into imaginary
concentric circles which are then further divided into grids of equal size.)
Each section is assigned a number. The height of the container is then
divided into imaginary levels that are at least as large as the vertical
space required by the chosen sampling device. These imaginary levels are
then assigned numbers. Specific levels and grid locations are then selected
for sampling using a random number table or random number generator.
Another appropriate sampling approach is the two-dimensional simple
random sampling strategy, which can usually yield a more precise sampling
when fewer samples are collected. This strategy involves (1) dividing
the top surface of the waste into an imaginary grid as in the three-
dimensional strategy, (2) selecting grid sections for sampling using random
number tables or number generators, and (3) sampling each selected grid point
in a vertical manner along the entire length from top to bottom using a
sampling device such as a drum thief, or Coliwasa.
Some containers such as drums with bung openings limit access to
the contained waste and restrict sampling to a single vertical plane.
Samples taken in this manner can be considered representative of the entire
container only if the waste is known to be homogeneous. Precautions must be
taken when sampling any type of steel drum since the drum may explode or
expel gases and/or pressurized liquids. An EPA/NEIC manual, "Safety Manual
for Hazardous Waste Site Investigation," addresses these safety precautions.
1.4.2 Tanks
Tanks are essentially large containers. The considerations involved in
sampling tanks are therefore similar to those for "sampling containers
(Section 1.4.1). As with containers, the goal of sampling tanks is to
acquire a sufficient number of samples from different locations within the
waste to provide analytical data that are representative of the entire tank
contents. The accessibility of the tank contents will affect the sampling
methodology.
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Tanks / 3
Figure 1. Container divided into an imaginary three-dimensional grid.
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4 / SAMPLING - Methodology
If the tank is an open one, allowing unrestricted access, then usually a
representative set of samples is best obtained using the three-dimensional
simple random sampling strategy described in Section 1.4.1. This strategy
involves dividing the tank contents into an imaginary three-dimensional grid.
As a first step, the top surface of the waste is divided into a grid whose
sections either approximate the size of the sampling device or are larger
than the sampling device if the tank is large. (Cylindrical tanks can be
divided into imaginary concentric circles which are then further divided into
grids of equal size.) Each section is assigned a number. The height of the
tank is then divided into imaginary levels that are at least as large as the
vertical space required by the chosen sampling device. These imaginary
levels are assigned numbers. Specific levels and grid locations are then
selected for sampling using a random number table or random number generator.
A less comprehensive sampling approach may be appropriate if information
regarding the distribution of waste components is known or assumed (e.g.,
vertical compositing will yield a representative sample). In such cases, a
two-dimensional simple random sampling strategy may be appropriate. In this
strategy, the top surface of the waste is divided into an imaginary grid;
grid sections are selected using random number tables or number generators;
and each selected grid point is then sampled in a vertical manner along the
entire length from top to bottom using a sampling device such as a weighted
bottle, a drum thief, or Coliwasa. If the waste is known to consist of two
or more discrete strata, a more precise representation of the tank contents
can be obtained by using a stratified random sampling strategy, i.e., sampling
each stratum separately using the two- or three-dimensional simple random
sampling strategy.
Some tanks permit only limited access to their contents, which restricts
the locations within the tank from which samples can be taken. If sampling
is restricted, the sampling strategy must, as a minimum, take sufficient
samples to address the potential vertical anomalies in the waste in order to
be considered representative. This is because contained wastes tend to
display vertical, rather than horizontal, nonrandom heterogeneity due to
settling of suspended solids or denser liquid phases. If access restricts
sampling to a portion of the tank contents (e.g., in an open tank, the size
of the tank may restrict sampling to the perimeter of the tank; in a closed
tank, the only access to the waste may be through inspection ports), then the
resulting analytical data will only be deemed representative of the accessed
area, not of the entire tank contents unless the tank contents are known to
be homogeneous.
\
If a limited access tank is to be sampled, and little is known about the
distribution of components within the waste, a set of samples that are
representative of the entire tank contents can be obtained by taking a series
of samples as the tank contents are being drained. This should be done in a
simple random manner by estimating how long it will take to drain the tank
and then randomly selecting times during drainage for sampling.
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Waste Piles; Landfills / 5
The most appropriate type of sampling device for tanks depends on
the tank parameters. In general, shallow tanks are sampled using subsurface
samplers (i.e., pond samplers), while weighted bottles are usually employed
for tanks deeper than 5 ft. Dippers are useful for sampling pipe effluents.
1.4.3 Waste Piles
Waste accessibility, which is frequently a function of pile size, is
a key factgor in the design of a sampling strategy for a waste pile.
Ideally, piles containing unknown wastes should be sampled using a three-
dimensional simple random sampling strategy. This strategy can be employed
only if all points within the pile can be accessed. In such cases, the
pile should be divided into a three-dimensional grid system, the grid sections
assigned numbers, and the sampling points then chosen using random number
talbes or number generators.
If sampling is limited to certain portions of the pile, then the
collected sample will be representative only of those portions unless
the waste is known to be homogeneous.
In cases where the size of a pile impedes access to the waste, a
set of samples that are representative of the entire pile can be obtained
with a minimum of effort by scheduling sampling to coincide with pile
removal. The number of truckloads needed to remove the pile should be
estimated, and the truckloads randomly chosen for sampling.
The sampling devices most commonly used for small piles are thiefs,
triers, and shovels. Excavation equipment such as backhoes can be useful for
sampling medium-sized piles.
1.4.4 Landfills and Lagoons
Landfills contain primarily solid waste, while lagooned waste may
range from liquids to dried sludge residues. Lagooned waste that is either
liquid or semisolid is often best sampled using the methods recommended for
large tanks (see Section 1.4.2). Usually solid wastes contained in a landfill
or lagoon are best sampled using the three-dimensional random sampling
strategy.
The three-dimensional random sampling strategy involves establishing an
imaginary three-dimensional grid of sampling points in the waste and then
using random number tables or generators to select points for sampling. In
the case of landfills and lagoons, the grid is established using a survey or
map of the area. The map is divided into 2 two-dimensional grids with
sections of equal size. These sections are then assigned numbers sequentially.
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6 / SAMPLING - Methodology
Next, the depth to which sampling will take place is determined and
subdidvided into equal levels which are also sequentially numbered. (The
lowest sampling depth will vary from landfill to landfill. Usually, sampling
extends to the interface of the fill and the natural soils. If soil contamin-
ation is suspected, sampling may extend into the natural soil.) The
horizontal and vertical sampling coordinates are then selected using random
number tables or generators. If some information is known about the nature
of the waste, then a modified three-dimensional strategy may be more appro-
priate. For example, if the landfill consists of several cells, a more
precise measurement may be obtained by considering each cell as a stratum and
employing a stratified three-dimensional random sampling strategy (see
Section 1.1).
Hollow stem augers combined with split-spoon samplers are frequently
appropriate for sampling landfills. Water-driven or water-rinsed coring
equipment should not be used for sampling since the water can rinse chemical
components from the sample. Excavation equipment such as backhoes may be
useful in obtaining samples at various depths; the resulting holes may be
useful for viewing and recording the contents of the landfill.
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SECTION TWO
WASTE EVALUATION PROCEDURES
2.1 Characteristics of Hazardous Waste
Section 262.11 of the Resource Conservation and Recovery Act regulations
requires that a generator of a "solid waste" - i.e., any garbage, refuse,
sludge or any other waste that is not excluded under Section 261.4(a) - must:
1. Determine if his waste is excluded.
2. If it is not excluded he must determine if his waste is listed as a
hazardous waste.
3. If the waste is not excluded and not listed, then he must evaluate
his waste in terms of the four Hazardous Characteristics: Ignita-
bility, Corrosivity, Reactivity, and EF* Toxicity, unless he can
properly evaluate the waste based upon his own knowledge of the
waste (e.g., corrosivity testing may not be required if the generator
has a long history of running the waste through steel pipes without
any evidence of corrosion).
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2.1.1 Ignitability
Introduction
This section discusses the hazardous characteristics of ignitability.
The regulatory background of this characteristic is summarized and the
regulatory definition of Ignitability is presented. Two testing methods are
described in Methods 1010 and 1020.
The objective of the ignitability characteristic is to identify wastes
that either present fire hazards under routine storage, disposal, and trans-
portation or are capable of severely exacerbating a fire once started.
Regulatory Definition
The following definitions have been taken verbatim from the RCRA
regulations (40 CFR 261.21).
Characteristics of Ignitability Regulation
A solid waste exhibits the characteristic of ignitability if a represen-
tative sample of the waste has any of the following properties:
1. It is a liquid, other than an aqueous solution, containing less than
24% alcohol by volume, and has a flash point less than 60° C
(140° F), as determined by a Pensky-Martens Closed Cup Tester, using
the test method specified in ASTM Standard D-93-79 or D-93-80,1 or
a Setaflash Closed Cup Tester, using the test method specified in
ASTM standard D-3278-78,1 or as determined by an equivalent test
method approved by the Administrator under the procedures set forth
in §§260.20 and 260.21.
2. It is not a liquid and is capable, under standard temperature and
pressure, of causing fire through friction, absorption or moisture,
or spontaneous chemical changes and, when ignited, burns so vigorously
and persistently that it creates a hazard.
3. It is an ignitable compressed gas as defined in 49 CFR 173.300 and
as determined by the test methods described in that regulation or
equivalent test methods approved by the Administrator under §§260.20
and 260.21.
4. It is an oxidizer as defined in 49 CFR 173.151.
*ASTM Standards are available from ASTM, 1916 Race Street, Philadelphia,
PA 19103.
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2 / CHARACTERISTICS - Ignitability
A solid waste that exhibits the characteristic of ignitability, but is
not listed as a hazardous waste in Subpart D, has the EPA Hazardous Waste
Number of D001.
Ignitable Compressed Gas
For the purpose of this regulation the following terminology is defined:
1. Compressed gas. The term "compressed gas" shall designate any
material or mixture having in the container an absolute pressure
exceeding 40 psi at 21° C (70° F) or, regardless of the pressure at
21° C (70° F), having an absolute pressure exceeding 104 psi at 54° C
(130° F), or any liquid flammable material having a vapor pressure
exceeding 40 psi absolute at 38° C (100° F) as determined by ASTM
Test D-323.
2. Ignitable compressed gas. Any compressed gas as defined in
paragraph (a) of this section shall be classed as an "ignitable
compressed gas" if any one of the following occurs:
a. Either a mixture of 13% or less (by volume) with air forms a
flammable mixture or the flammable range with air is wider than
12% regardless of the lower limit. These limits shall be
determined at atmospheric temperature and pressure. The method
of sampling and test procedure shall be acceptable to the
Bureau of Explosives.
b. Using the Bureau of Explosives' Flame Projection Apparatus (see
Note 1), the flame projects more than 18 inches beyond the
ignition source with valve opened fully, or, the flame flashes
back and burns at the valve with any degree of valve opening.
c. Using the Bureau of Explosives' Open Drum Apparatus (see
Note 1), there is any significant propagation of flame away
from the ignition source.
d. Using the Bureau of Explosives' Closed Drum Apparatus (see
Note 1), there is any explosion of the vapor-air mixture in the
drum.
NOTE 1: A description of the Bureau of Explosives' Flame Projection
Apparatus, Open Drum Apparatus, Closed Drum Apparatus, and method
of tests may be procured from the Bureau of Explosives (Association
of American Railroads, Operations and Maintenance Dept., Bureau of
Explosives, American Railroad Building, Washington, D.C. 20036;
202-293-4048).
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Regulatory Definition / 3
Oxidizer
For the purpose of this regulation, an oxidizer is any material that
yields oxygen readily to stimulate the combustion of organic matter (e.g.,
chlorate, permanganate, inorganic peroxide, or a nitrate).
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METHOD 10101
PENSKY-MARTENS CLOSED-CUP METHOD
1.0 Scope and Application
1.1 Method 1010 uses the Pensky-Martens closed-cup tester to determine
the flash point of fuel oils, lube oils, suspensions of solids, liquids that
tend to form a surface film under test conditions, and other liquids.
2.0 Summary of Method
2.1 The sample is heated at a slow, constant rate with continual
stirring. A small flame is directed into the cup at regular intervals with
simultaneous interruption of stirring. The flash point is the lowest temper-
ature at which application of the test flame ignites the vapor above the
sample.
3.0 Interferences
3.1 Ambient pressure, sample homogeneity, drafts, and operator bias can
affect flash point values.
4.0 Apparatus
4.1 Pensky-Martens Closed Flash Tester, as described in Annex Al of ASTM
Method D93-77. (Automatic flash point testers are available and may be
advantageous since they save testing time, permit the use of smaller samples,
and exhibit other advantages. If automatic testers are used, the user must be
sure to follow all the manufacturer's instructions for calibrating, adjusting,
and operating the instrument. In any cases of dispute, the flash point as
determined manually shall be considered the referee test.)
4.2 Thermometers: Two standard thermometers shall be used with the
ASTM Pensky-Martens tester.
4.2.1 For tests in which the indicated reading falls within -7° to
+110° C (20* to 230" F), inclusive: either (1) an ASTM Pensky-Martens
Low Range or Tag Closed Tester Thermometer having a range from -7* to
+110° C (20° to 230° F) and conforming to the requirements for Thermometers
9C (9F) and as prescribed in ASTM Specification El, or (2) an IP Thermo-
meter 15C (15F) conforming to specifications given in Annex A3 of ASTM
093-77.
iThis method is based on ASTM Method D93-77. Refer to D93-77 or D93-80
for more information.
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2 / CHARACTERISTICS - Ignitability
4.2.2 For tests in which the indicated reading falls within 110°
to 370' C (230* to 700° F): either (1) an ASTM Pensky-Martens High
Range Thermometer having a range from 90° to 370° C (200° to 700° F) and
conforming to the requirements for Thermometers IOC (10F) as prescribed
in Specification El, or (2) IP Thermometer 16C (16F) conforming to
specifications given in Annex A3 of ASTM D93-77.
5.0 Reagents
5.1 Calcium chloride.
5.2 p-Xylene reference standard.
6.0 Sample Collection. Preservation, and Handling
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Section One of this manual.
6.2 Samples shall not be stored in plastic bottles since volatile
materials may diffuse through the walls of the bottle.
7.0 Procedure
7.1 Preparation of samples: Samples that do not contain volatile
contaminants shall be prepared in the following manner. NOTE: If the sample
is suspected of containing volatile contaminants, the treatment described in
7.1.1 and 7.1.2 should be omitted.
7.1.1 Samples of very viscous materials may be warmed until they
are reasonably fluid before they are tested. However, no sample should
be heated more than is absolutely necessary, and no sample should ever
be heated to a temperature that exceeds 17° C (30° F) below the sample's
expected flash point.
7.1.2 Samples containing dissolved or free water may be dehydrated
with calcium chloride or by filtering through a qualitative filter paper
or a loose plug or dry absorbent cotton. Warming the sample is permitted,
but it shall not be heated for prolonged periods or above a temperature
of 17° C (30° F) below the sample's expected flash point.
7.2 Routine procedure
7.2.1 Thoroughly clean and dry all parts of the cup and its
accessories before starting the test. Be sure to remove any solvent
that was used to clean the apparatus. Fill the cup with the sample to
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1010 / 3
be tested to the level indicated by the filling mark. Place the lid on
the cup and set the latter in the stove. Be sure to properly engage the
locating or locking device. Insert the thermometer. Light the test
flame and adjust it to a diameter of 5/32 in. (4 mm). Supply the heat
at such a rate that the temperature as indicated by the thermometer
increases 5° to 6" C (9* to 11° F)/min. Turn the stirrer 90 to 120 rpm,
stirring in a downward direction.
7.2.2 If the sample is expected to have a flash point of 110° C
(230° F) or below, apply the test flame when the temperature of the
sample is from 17° C (30° F) to 28° C (50° F) below the expected
flash point and thereafter at a temperature reading that is a multiple
of 1* C (2° F). Apply the test flame by operating the mechanism on the
cover which controls the shutter and test flame burner so that the flame
is lowered into the vapor space of the cup in 0.5 sec, left in its
lowered position for 1 sec, and quickly raised to its high position.
Do not stir the sample while applying the test flame.
7.2.3 If the sample is expected to have a flash point above 110° C
(230° F), apply the test flame in the manner just described at each
temperature that is a multiple of 2° C (5° F), beginning at a temperature
of 17° C (30° F) to 28° C (50° F) below the expected flash point.
NOTE: When testing materials to determine if volatile contaminants are
present, it is not necessary to adhere to the temperature limits for
initial flame application as stated in 7.2.2 and 7.2.3.
7.2.4 Record as the flash point the temperature read on the
thermometer at the time the test flame application causes a distinct
flash in the interior of the cup. Do not confuse the true flash point
with the bluish halo that sometimes surrounds the test flame at applica-
tions preceding the one that causes the actual flash. The actual flash
will have occurred when a large flame propagates itself over the surface
of the sample.
7.3 Determination of flash point of suspensions of solids and highly
viscous materials
7.3.1 Bring the material to be tested and the tester to a tempera-
ture of 15° _+ 5° C (60° +_ 10° F) or 11° C (20° F) lower than the estimated
flash point, whichever is lower. Turn the stirrer 250 +_ 10 rpm, stirring
in a downward direction. Raise the temperature throughout the duration
of the test at a rate of not less than 1° nor more than 1.5° F (2 to 3° F)/
min. With the exception of these requirements for rates of stirring
and heating, proceed as prescribed in Section 7.2.
7.4 Calculation and report
7.4.1 Observe and record the ambient barometric pressure at the
time of the test. When the pressure differs from 760 mm Hg (101.3 kPa),
correct the flash point as follows:
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4 / CHARACTERISTICS - Ignitability
(A) Corrected flash point = C + 0.25 (101.3 - p)
(B) Corrected flash point = F + 0.06 (760 - P)
(C) Corrected flash point = C + 0.033 (760 - P)
where:
F = observed flash point, °F
C = observed flash point, °C
P = ambient barometric pressure, mm Hg
p = ambient barometric pressure, kPa.
NOTE: The barometric pressure used in this calculation must be the
ambient pressure for the laboratory at the time of test. Many aneroid
barometers, such as those used at weather stations and airports, are
precorrected to give sea level readings. These must not be used.
7.4.2 Record the corrected flash point to the nearest
0.5° C (or 1° F).
7.4.3 Report the recorded flash point as the Pensky-Martens Closed
Cup Flash Point ASTM D93 - IP 34, of the sample tested.
7.5 Refer to Method ASTM D93 77 for more details and background
on the Pensky-Marten method.
8.0 Quality Control
8.1 All quality control data should be available for review.
8.2 Duplicates and standard reference materials should be routinely
analyzed.
8.3 The flash point of the p-xylene reference standard must be deter-
mined in duplicate at least once per sample batch. The average of the two
analyses should be 27° + 0.8° C (81* + 1.5° F).
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METHOD 10201
SETAFLASH CLOSED-CUP METHOD
1.0 Scope and Application
1.1 Method 1020 make use of the SetaflashUvdosed Tester to determine
the flash point of paints, enamels, lacquers, varnishes, and related products
and their components that have flash points between 0° and 110° C (32° and
230° F) and a viscosity lower than 150 stokes at 25° C (77° F). Tests
at higher or lower temperatures are possible.
1.2 The procedures may be used to determine whether a material will or
will not flash at a specified temperature or to determine the finite tempera-
ture at which a material will flash.
2.0 Summary of Method
2.1 By means of a syringe, 2 ml of sample is introduced through a
leakproof entry port into the tightly closed Setaflash Tester or directly
into the cup that has been brought to wit.hin 3* C (5° F) below the expected
flash point.
2.2 As a 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 expected flash
point by slight adjustment of the temperature dial. After 1 min, 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.
2.3 For a finite flash measurement, the temperature is sequentially
increased through the 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.
3.0 Interferences
3.1 Ambient pressure, sample homogeneity, drafts, and operator bias
can affect flash point values.
iThis method is based on ASTM Method D327-78.
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2 / CHARACTERISTICS - Ignitability
4.0 Apparatus and Materials
4.1 Setaflash Tester as described in Appendix XI of ASTM Method 3278-78.
4.2 Thermometers conforming to specifications given in ASTM Method
3278-78. Test to determine that the scale error does not exceed 0.25* C
(0.5° F). A magnifying lens significantly assists in making temperature
observations.
4.3 Glass syringe: 2 ± 0.1-ml capacity at 25° C (77° F), to provide a
means of taking a uniform sample. Check the capacity by discharging water
into a weighing bottle and weighing. Adjust plunger if necessary. A dispos-
able syringe of equal precision may be used.
4.4 Cooling block: Aluminum (described in Appendix X2 of ASTM D3278-78)
which fits snugly within the test cup for rapid cooling of the sample cup.
4.5 Barometer.
5.0 Reagents
5.1 p-Xylene: Reference standard for checking the Setaflash Tester.
5.2 Cooling mixture of ice water or dry ice (solid C02) and acetone.
5.3 Liquefied petroleum gas.
5.4 Heat transfer paste.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must be collected employing a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 The sample size for each test is 2 ml. Obtain at least a 25-ml
sample from the bulk source and store in a nearly full, tightly closed clean
glass container or in another container suitable for the type of liquid being
sampled.
6.3 Erroneously high flash points may be obtained if precautions
are not taken to avoid loss of volatile materials. Do not open sample
containers unnecessarily and do not transfer the sample to the cup unless its
temperature is at least 10° C (20° F) below the expected flash point.
Discard samples in leaky containers.
6.4 Do not use plastic bottles since certain volatile compounds can
diffuse through the walls of the bottle.
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1020 / 3
7.0 Procedure
7.1 Prior to initial use and after removal of the thermometer, insert
the thermometer into its pocket with a good heat transfer paste.
7.2 To help in making the necessary settings during a test, determine
the relationship between the temperature control dial and thermometer readings
at intervals not over 5° C (10° F) throughout the scale range of the heater
before the initial use.
7.3 Place the tester in a subdued light and in a position where it is
not exposed to disturbing drafts. Provide a black-coated shield, if necessary.
7.4 Read the manufacturer's operating and maintenance instructions on
the care and servicing of the tester. Observe the specific suggestions
regarding the operation of its various controls.
7.5 Check the accuracy of the tester by determining the flash point of
the p-xylene reference standard in duplicate (Appendix X3). The average of
the results should be 27.2° _+ 0.8° C (81° +_ 1.5° F). If not, remove the ther-
mometer and observe whether sufficient heat transfer paste surrounds the
thermometer to provide good heat transfer from the cup to the thermometer.
7.6 Ambient to 110° C (230° F).
7.6.1 Inspect the inside of the test cup, lid, and shutter mechanism
for cleanliness and freedom from contamination. Use an absorbent tissue
to wipe clean, if necessary. Lock the cover lid tightly in place.
7.6.2 Switch the tester on, if not already at stand-by. To
rapidly approach the specification flash temperature of the charged
sample, turn the heater dial fully clockwise causing the heater signal
(red) light to glow. When the thermometer indicates a temperature of
about 3° C (5° F) below the specification or target flash point tempera-
ture, reduce the heat input to the test cup by slowly turning the heater
control dial counter-clockwise until the signal light goes out.
NOTE: When the correct temperature is dialed on the temperature controller,
the elapsed time to reach it may be greater than when turned full on,
but less attention will be required in the intervening period.
NOTE: The test cup temperature is stable when the signal light slowly
cycles on and off.
7.6.3 Determine the barometric pressure to determine the corrected
specification temperature at that barometric pressure.
7.6.4 After the test cup temperature has stabilized at the specifi-
cation or target flash point, charge the syringe with the sample to be
tested and transfer the syringe to the filling orifice, taking care not
to lose any sample. Discharge the sample into the test cup by depressing
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4 / CHARACTERISTICS - Ignitability
the syringe plunger to its lowest position, then remove the syringe. If
the sample has a viscosity greater than 45 SUS at 37.8° C (100° F) or
equivalent of 9.5 cSt at 25' C (77* F), discharge the contents of the
syringe directly into the cup. Immediately close tightly the lid and
shutter assembly.
7.6.5 Set the 1-min timing device by rotating its knob clockwise
to the required setting. In the meantime, open the gas control valve
and light the pilot and the test flames. Adjust the test flame size
with the pinch valve so as to match the size of the 5/32-in. (4-mm)
diameter flame gauge.
7.6.6 After 1 min has elapsed, observe the temperature. If at the
specification temperature (accounting for the differences of the barometer
reading from 760 mm), apply the test flame by slowly and uniformly
opening the slide fully and closing completely over a period of approxi-
mately 2-1/2 sec. Watch for a flash. (NOTE: The sample is considered
to have flashed only if a comparatively large blue flame appears and
propagates itself over the surface of the liquid. Occasionally, particu-
larly near the actual flash point temperature, application of the test
flame may give rise to a halo; this should be ignored.)
7.6.7 Turn off the test and the pilot flame. Clean the apparatus
in preparation for the next test.
7.7 0° C (32° F) to ambient
7.7.1 If the specification or target flash point is at or below ambient
temperature, cool the sample to 5° to 10° C (10° to 20° F) below that point by
some convenient means.
7.7.2 Cool the tester to the approximate temperature of the sample
by inserting the cooling block filled with a cooling mixture into the
sample well. Dry the cup with a paper tissue to remove any collected
moisture prior to adding the sample. (CAUTION: Be careful in handling
the cooling mixture and cooling block; wear gloves and goggles. Mixtures
such as dry ice and acetone can produce severe frost bite.) (CAUTION:
Be careful in inserting the cooling block into the tester cup to prevent
damage to the cup.)
7.7.3 Introduce the sample as in 7.6.4. Allow the temperature to
rise under ambient conditions or increase the temperature of the cup by
rotating the heater controller clockwise slowly until the specification
temperature adjusted for barometric pressure is reached. Determine
whether the sample flashes as in 7.6.5 and 7.6.6.
7.7.4 Turn off the test and pilot flames. Clean up the apparatus.
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1020 / 5
7.8 Ambient to 110° C (230* F)
7.8.1 Preliminary or trial test: Follow steps 7.6.2 to 7.6.5
omitting the barometric reading and using an estimated finite flash
point instead of a specification flash point temperature.
7.8.2 After 1 min has elapsed, observe the temperature, apply the
test flame by slowly and uniformly opening the slide fully and closing
completely over a period of 2-1/2 sec. Watch for a flash. (NOTE: The
sample is considered to have flashed only if a comparatively large blue
flame appears and propagates itself over the surface of the liquid.
Occasionally, particularly near the actual flash point temperature,
application of the test flame may give rise to a halo; this should be
ignored.)
7.8.3 Finite flash point: If a flash is observed, proceed as
below.
7.8.3.1 Using a temperature of 5° C (9° F) lower than the
temperature observed in 7.8.2, repeat 7.8.1 and 7.8.2. (CAUTION:
Be careful in inserting the cooling block into the tester cup to
prevent damage to the cup.) If a flash is still observed, repeat
at 5° C (9° F) lower intervals until no flash is observed. (NOTE:
Never make a repeat test on the same sample. Always take a fresh
portion for each test.)
7.8.3.2 Repeat 7.8.1 and 7.8.2 with a new sample, stabilizing
the test cup temperature at the temperature at which no flash
occurred previously. Observe whether a flash occurs at this
temperature. If no flash occurs, increase the temperature at
0.5* C (1° F) intervals by making small incremental adjustment to the
temperature controller and allowing 1-min intervals between
each increment and the flash point test. Record the temperature at
which the flash actually occurs. Record the barometric pressure.
Turn off pilot and test flames and clean up tester.
7.8.4 Finite flash point: If no flash point is observed in 7.8.2,
proceed as follows.
7.8.4.1 Using a test temperature of 5° C (9° F) higher than
the temperature observed in 7.8.2, repeat steps 7.8.1 and 7.8.2.
(NOTE: Never make a repeat test on the same sample. Always take a
fresh portion for each test.) If no flash is observed, repeat at
5° C (9° F) higher intervals until a flash is observed.
7.8.4.2 Repeat step 7.8.3.2 with a new sample.
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6 / CHARACTERISTICS - Ignitability
7.9 0° C (32° F) to ambient temperature
7.9.1 Preliminary or trial test: Cool the sample to 3° to 5° C
(5* to 10* F) below the expected flash point.
7.9.2 Cool the tester to approximately the temperature of the
sample by inserting the cooling block filled with a cooling medium into
the sample well.
7.9.3 Insert the sample as in 7.6.4. Set the 1-min timing device.
After 1 min, apply the test flame by slowly and uniformly opening the
side fully and closing completely over a period of approximately
2-1/2 sec. Observe for a flash. Record the temperature.
7.9.4 Finite flash point: If a flash is observed, proceed as
follows.
7.9.4.1 Cool a new sample and the sample cup to 5" C (9° F)
below the previous temperature (7.9.3). After 1 min, check for a
flash as in 7.9.3. If the sample flashes, repeat test at 5° C
(9* F) lower intervals until no flash is observed.
7.9.4.2 Repeat with a new sample, cooling both sample and
tester to the temperature at which the sample did not flash. After
1 min, observe whether a flash occurs at this temperature. If not,
increase the temperature at 0.5° C (1° F) intervals by making small
incremental adjustments to the temperature controller, allowing
1 min between each increment and the test for the flash point.
Record the temperature at which the flash actually occurs. Record
the barometric pressure.
7.9.5 Finite flash point: If no flash point is observed proceed
as follows.
7.9.5.1 Using a test temperature of 5° C (9° F) higher than
the temperature observed in 7.9.3, repeat step 7.9.3. (CAUTION:
Be careful in inserting the cooling block into the tester cup to
prevent damage to the cup.) If no flash is observed, repeat at
5* C (9° F) higher intervals until flash is observed.
7.9.5.2 Using a new sample, repeat 7.9.4.2 until a flash
occurs. Record the temperature at which the flash occurs and the
barometric pressure.
7.10 Cleanup of apparatus and preparation for next test
7.10.1 To prepare for the next test, unlock the lid assembly of
the tester and raise to the hinge stop. Soak up liquid samples with an
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1020 / 7
absorbent paper tissue and wipe dry. Clean the underside of the lid and
filling orifice. A pipe cleaner may be of assistance in cleaning the
orifice.
7.10.2 If the sample is a viscous liquid or contains dispersed
solids, after soaking up most of the sample add a small amount of a
suitable solvent for the sample to the cup and then soak up the solvent
and wipe clean the interior surfaces of the cup with an absorbent tissue
paper. (NOTE: If necessary to remove residual high boiling solvent
residues, moisten tissue with acetone and wipe clean.) (NOTE: If any
further cleaning is necessary, remove the lid and shutter assembly.
Disconnect the silicone rubber hose and slide the lid assembly to the
right to remove. If warm, handle carefully.)
7.10.3 After the cup has been cleaned, its temperature may be
rapidly increased to some stand-by value by turning the temperature
control dial to an appropriate point. (NOTE: It is convenient to hold
the test cup at some stand-by temperature (depending on planned usage)
to conserve time in bringing the cup within the test temperature range.
The cup temperature may be quickly lowered by inserting the aluminum
cooling block filled with an apprcpriate cooling mixture into the cup.)
7.10.4 The syringe is easily cleaned by filling it several times
with acetone or any compatible solvent, discharging the solvent each
time, and allowing the syringe to air dry with the plunger removed.
Replace the plunger, and pump several times to replace any solvent vapor
with air.
7.11 Correction for barometric pressure
7.11.1 When the barometric pressure differs from 760 mm Hg
(101.3 kPa), calculate the flash point temperature by means of the
following equations:
Calculated flash point = C + 0.03 (760 - P)
= F + 0.06 (760 - P)
where:
C, F = observed flash point (°C or °F)
P = barometric pressure (mm Hg).
7.11.2 Likewise determine the corrected specification flash point by
the following equation:
C = S - 0.03 (760 - P)
F = S - 0.06 (760 - P)
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• 8 / CHARACTERISTICS - Ignitabi1ity; Corrosivity
where:
C, F = flash point to be observed to obtain the specification flash
point at standard pressure (S)
S = specification flash point.
7.12 Report
7.12.1 When using the flash/no flash method, report whether the
sample flashed at the required flash point and that the flash/no flash
method was used.
7.12.2 If an actual flash point was determined, report the average
of duplicate runs to nearest 0.5" C (1* F) provided the difference
between the two values does not exceed 1" C (2* F).
8.0 Quality Control
8.1 All quality control data should be available for review.
8.2 Duplicates and standard reference materials should be routinely
analyzed.
8.3 The flash point of the p-xylene reference standard must be determined
in duplicate at least once per sample batch. The average of the two analyses
should be 27' + 0.8* C (81° + 1.5° F).
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2.1.2 Corrosivity
Introduction
The corrosivity characteristic, as defined in 40 CFR 261.22, is designed
to identify wastes which might pose a hazard to human health or the environment
due to their ability to:
1. Mobilize toxic metals if discharged into a landfill environment,
2. Corrode handling, storage, transportation, and management equipment,
or
3. Destroy human or animal tissue in the event of inadvertent contact.
In order to identify such potentially hazardous materials, EPA has
selected two properties upon which to base the definition of a corrosive
waste. These properties are pH and corrosivity toward Type SAE 1020 steel.
The following sections present the regulatory background and the
regulation pertaining to the definition of corrosivity. The procedures for
measuring pH of aqueous wastes are detailed in Methods 9040 and 9041.
Method 1110 describes how to determine whether a waste is corrosive to
steel.
Regulatory Definition
The following material has been taken nearly verbatim from the RCRA
regulations.
1. A solid waste exhibits the characteristic of corrosivity if a
representative sample of the waste has either of the following
properties:
a. It is aqueous and has a pH less than or equal to 2 or greater
than or equal to 12.5, as determined by a pH meter using either
the test method specified in this manual (Method 9040) (also
described in "Methods for Analysis of Water and Wastes"
EPA 600/4-79-020, March 1979), or an equivalent test method
approved by the Administrator under the procedures set forth in
§§260.20 and 260.21.
b. It is a liquid and corrodes steel (SAE 1020) at a rate greater
than 6.35 mm (0.250 inch) per year at a test temperature of
55* C (130° F) as determined by the test method specified in
NACE (National Association of Corrosion Engineers) Standard
TM-01-69 as standardized in this manual (Method 1110) or an
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2 / CHARACTERISTICS - Corrosivity
equivalent test method approved by the Administrator under the
procedures set forth in §§260.20 and 260.21.
2. A solid waste that exhibits the characteristic of corrosivity, but
is not listed as a hazardous waste in Subpart D, has the EPA Hazardous
Waste Number of D002.
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METHOD 1110
CORROSIVITY TOWARD STEEL
1.0 Introduction
1.1 Method 11101 is used to measure the corrqsivity toward steel of
both aqueous and nonaqueous liquid wastes.
2.0 Summary of Method
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 corrosivity of the waste.
3.0 Interferences
3.1 In laboratory tests, such as this one, corrosion of duplicate
coupons is usually reproducible to within i 10%. However, large differences
in corrosion rates may occasionally occur under conditions where the metal
surfaces become passivated. Therefore, at least duplicate determinations of
corrosion rate should be made.
4.0 Apparatus and Materials
4.1 A versatile and convenient apparatus should be used, consisting of
a kettle or flask of suitable size (usually 500 to 5000 milliliters),
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 test is shown in Figure 1.'
4.2 The supporting device and container should not be affected by or
cause contamination of the waste under test.
4.3 The method of supporting the coupons will vary with the apparatus
used for conducting the test but 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, fluorocarbon or coated metal.
method is based on NACE Standard TM-01-69 (1972 Revision),
"Laboratory Corrosion Testing of Metals for the Process Industries," National
Association of Corrosion Engineers, 3400 West Loop South, Houston, TX
77027.
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mo / 2
H
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 is 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 * gas inlet, E * heating mantle, F = liquid
interface, G » opening in flask for additional apparatus that may be required, and H « reflux
condenser.
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1110 / 3
4.4 The shape and form of the coupon support should ensure free contact
with the waste.
4.5 A circular specimen of SAE 1020 steel of about 3.75 cm (1.5 inch)
diameter is a convenient shape for a coupon. With a thickness of approxi-
mately 0.32 cm (0.125 inch) and a 0.80-cm (0.4-in.) diameter hold 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 speci-
men is given by the following equation:
A = 3.14/2(D2-d2) + (t)(3.14)(D) + (t)(3.14)(d)
where t = thickness, D - diameter of the specimen, and d = diameter of the
mounting hole. If the hole is completely covered by the mounting support,
the last term (t)(3.14)(d) in the equation is omitted.
4.5.1 All coupons should be measured carefully to permit accurate
calculation of the exposed areas. An area calculation accurate to +_ 1%
is usually adequate.
4.5.2 More uniform results may be expected if a substantial layer
of metal is removed from the coupons prior to testing the corrosivity of
the waste. This can be accomplished either by chemical treatment
(pickling), electrolytic removal, or by grinding with a coarse abrasive.
At least 0.254 mm (0.0001 inch) or 2 to 3 mg/cm£ should be removed.
Final surface treatment should include finishing with #120 abrasive
paper or cloth. Final cleaning consists of scrubbing with bleachfree
scouring powder, followed by rinsing in distilled water, then acetone or
methanol, and finally air drying. After final cleaning, the coupon
should be stored in a desiccator until used.
4.5.3 The minimum ratio of volume of waste to area of the metal
coupon to be used in this test is 40 ml/cm2.
5.0 Reagents
5.1 Sodium hydroxide (20%).
5.2 Zinc dust.
5.3 Concentrated hydrochloric acid.
5.4 Stannous chloride.
5.5 Antimony chloride.
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1110 / 4
6.0 Sample Collection, Presentation, and Handling
6.1 All samples should be collected using a sampling plan that addresses
the considerations discussed in Section One of this manual.
7.0 Procedure
7.1 Assemble the test apparatus as described in Section 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.
7.4 Using the heating device bring the temperature of the waste to
55* C (130* F).
7.5 An accurate rate of corrosion is not required but only a
determination as to whether the rate of corrosion is less than or greater
than 6.35 mm per year. A 24-hour test period should be ample to determine
whether or not the rate of corrosion is greater than 6.35 mm per year.
7.6 In order to accurately determine 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 is the most popular of these methods. The others are used in
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 in 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
20% NaOH + 200 g/1 zinc dust
Soaking Time Temperature
5 min
Boiling
or
Cone. HC1 + 50 g/1 SnCl2 + 20 g/1 SbCl3 Until clean
Cold
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1110 / 5
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 is:
Solution 50 g/1 H2S04
Anode Carbon or lead
Cathode Steel coupon
Cathode current density 20 amp/cm2 (129 amp/in.2)
Inhibitor 2 cc organic inhibitor/liter
Temperature 74* C (165* F)
Exposure Period 3 minutes
NOTE: Precautions must be taken to ensure good electrical contact with
the coupon, to avoid contamination of the cleaning solution with easily
reducible metal ions, and to ensure that inhibitor decomposition has not
occurred. Instead of using a proprietary inhibitor, 0.5 g/1 or either
diorthotolyl thiourea or quinolin ethiodide can be used*
7.7 Whatever treatment is employed to clean the coupons, its effect in
removing sound metal should be determined 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
reweighed. 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 («py) - "'"'—Tti.^
where weight loss is in milligrams, area in square centimeters,
time in hours, and corrosion rate in 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.
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CHARACTERISTICS - Corrosivity; Reactivity
2.1.3 Reactivity
Introduction
The regulation in 40 CFR 261.23 defines reactive wastes to include
wastes which have any of the following properties: (1) readily undergo
violent chemical change; (2) react violently or form potentially explosive
mixtures with water; (3) generate toxic fumes when mixed with water or, in
the case of cyanide or sulfide-bearing wastes, when exposed to mild acidic
or basic conditions; (4) explode when subjected to a strong initiating force;
(5) explode at normal temperatures and pressures; or (6) fit within the
Department of Transportation's forbidden explosives, Class A explosives, or
Class B explosives classifications.
This definition is intended to identify wastes which, because of
their extreme instability and tendency to react violently or explode, pose
a problem at all stages of the waste management process. The definition is
to a large extent a paraphrase of the narrative definition employed by the
National Fire Protection Association. The Agency chose to rely on a
descriptive, prose definition of reactivity because the available tests
for measuring the variegated class of effects embraced by the reactivity
definition suffer from a number of deficiencies.
Regulatory Definition
Characteristic of Reactivity Regulation
A solid waste exhibits the characteristic of reactivity if a representa-
tive sample of the waste has any of the following properties:
1. It is normally unstable and readily undergoes violent change
without detonating.
2. It reacts violently with water.
3. It forms potentially explosive mixtures with water.
4. When mixed with water, it generates toxic gases, vapors or fumes
in a quantity sufficient to present a danger to human health or
the environment.
5. It is a cyanide- or sulfide-bearing waste which, when exposed to pH
conditions between 2 and 12.5, can generate toxic gases, vapors,
or fumes in a quantity sufficient to present a danger to human
health or the environment. (Methods 9010 and 9030 can be used to
detect the presence of cyanide and sulfide in wastes.)
6. It is capable of detonation or explosive reaction if it is
subjected to a strong initiating source or if heated under
confinement.
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2 / CHARACTERISTICS - Reactivity
7. It is readily capable of detonation or explosive decomposition or
reaction at standard temperature and pressure.
8. It is a forbidden explosive as defined in 49 CFR 173.51, or a
Class A explosive as defined in 49 CFR 173.53, or a Class B
explosive as defined in 49 CFR 173.88.
9. A solid waste that exhibits the characteristic of reactivity, but
is not listed as a hazardous waste in Subpart D, has the EPA
Hazardous Waste Number of D003.
Definition of Explosive Materials
For purposes of this regulation, a waste is a reactive waste by reason
of explosivity if it meets one or more of the following descriptions:
1. Is explosive and ignites spontaneously or undergoes marked
decomposition when subjected for 48 consecutive hours to a
temperature of 75° C (167° F).
2. Firecrackers, flash crackers, salutes, or similar commercial
devices which produce or are intended to produce an audible
effect, the explosive content of which exceeds 12 grains each in
weight; pest control bombs, the explosive content of which exceeds
18 grains each in weight; and any such devices, without respect to
explosive content, which on functioning are liable to project or
disperse metal, glass or brittle plastic fragments.
3. Fireworks that combine an explosive and a detonator or blasting
cap.
4. Fireworks containing an ammonium salt and a chlorate.
5. Fireworks containing yellow or white phosphorus.
6. Fireworks or firework compositions that ignite spontaneously or
undergo marked decomposition when subjected for 48 consecutive
hours to a temperature of 75° C (167° F).
7. Toy torpedoes, the maximum outside dimension of which exceeds
7/8 inch, or toy torpedoes containing a mixture of potassium
chlorate, black antimony and sulfur with an average weight of
explosive composition in each torpedo exceeding four grains.
8. Toy torpedoes containing a cap composed of a mixture of red
phosphorus and potassium chlorate exceeding an average of one-half
(0.5) grain per cap.
9. Fireworks containing copper sulfate and a chlorate.
-------
Regulatory Definition / 3
10. Explosives containing an ammonium salt and a chlorate.
11. Liquid nitroglycerin, diethylene glycol dinitrate or other liquid
explosives not authorized.
12. Explosives condemned by the Bureau of Explosives (except properly
packed samples for laboratory examinations).
13. Leaking or damaged packages of explosives.
14. Solid materials which can be caused to deflagrate by contact with
sparks or flame such as produced by safety fuse or an electric
squib, but cannot be detonated (see Note 1) by means of a No. 8
test blasting cap (see Note 2). Example: Black powder and low
explosives.
15. Solid materials which contain a liquid ingredient, and which, when
unconfined (see Note 3), can be detonated by means of a No. 8 test
blasting cap (see Note 2); or which can be exploded in at least
50 percent of the trials in the Bureau of Explosives' Impact
Apparatus (see Note 4) under a drop of 4 inches or more, but
cannot be exploded in more than 50 percent of the trials under a
drop of less than 4 inches. Example: High explosives, commercial
dynamite containing a liquid explosive ingredient.
16. Solid materials which contain no liquid ingredient and which can
be detonated, when unconfined (see Note 3), by means of No. 8 test
blasting cap (see Note 2); or which can be exploded in at least
50 percent of the trials in the Bureau of Explosives' Impact
Apparatus (see Note 4) under a drop of 4 inches or more, but
cannot be exploded in more than 50 percent of the trials under a
drop of less than 4 inches. Example: high explosives, commercial
dynamite containing no liquid explosive ingredient, trinitrotoluene,
amatol, tetryl, picric acid, ureanitrate, pentolite, commercial
boosters.
17. Solid materials which can be caused to detonate when unconfined
(see Note 3), by contact with sparks or flame such as produced by
safety fuse or an electric squib; or which can be exploded in the
Bureau of Explosives' Impact Apparatus (see Note 4), in more than
50 percent of the trials under a drop of less than 4 inches.
Example: initiating and priming explosives, lead azide, fulminate
of mercury, high explosives.
18. Liquids which may be detonated separately or when absorbed in
sterile absorbent cotton, by a No. 8 test blasting cap (see Note
2); but which cannot be exploded in the Bureau of Explosives'
Impact Apparatus (see Note 4), by a drop of less than 10 inches.
The liquid must not be significantly more volatile than nitro-
glycerine and must not freeze at temperatures above minus 10° F.
Example: high explosives, desensitized nitroglycerine.
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4 / CHARACTERISTICS - Reactivity
19. Liquids that can be exploded in the Bureau of Explosives' Impact
Apparatus (see Note 4) under a drop of less than 10 inches.
Example: nitroglycerine.
20. Blasting caps, these are small tubes, usually made of an alloy of
either copper or aluminum, or of molded plastic closed at one end
and loaded with a charge of initiating or priming explosives.
Blasting caps (see Note 5) which have been provided with a means
for firing by an electric current, and sealed, are known as
electric blasting caps.
21. Detonating primers which contain a detonator and an additional
charge of explosives, all assembled in a suitable envelope.
22. Detonating fuses, which are used in the military service to
detonate the high explosive bursting charges of projectiles,
mines, bombs, torpedoes, and grenades. In addition to a powerful
detonator, they may contain several ounces of a high explosive,
such as tetryl or dry nitrocellulose, all assembled in a heavy
steel envelope. They may also contain a small amount of radio-
active component. Those that will not cause functioning of other
fuses, explosives, or explosive devices in the same or adjacent
containers are classes as class C explosives and are not reactive
waste.
23. A shaped charge, consisting of a plastic, paper, or other suitable
container comprising a charge of not to exceed 8 ounces of a high
explosive containing no liquid explosive ingredient and with a
hollowed-out portion (cavity) lined with a rigid material.
24. Ammunition or explosive projectiles, either fixed, semi-fixed or
separate components which are made for use in cannon, mortar,
howitzer, recoil less rifle, rocket, or other launching device with
a caliber of 20 mm or larger.
25. Grenades. Grenades, hand or rifle, are small metal or other
containers designed to be thrown by hand or projected from a
rifle. They are filled with an explosive or a liquid, gas, or
solid material such as a tear gas or an incendiary or smoke
producing material and a bursting charge.
26. Explosive bombs. Explosive bombs are metal or other containers
filled with explosives. They are used in warfare and include
airplane bombs and depth bombs.
27. Explosive mines. Explosive mines are metal or composition
containers filled with a high explosive.
28. Explosive torpedoes. Explosive torpedoes, such as those used in
warfare, are metal devices containing a means of propulsion and a
quantity of high explosives.
-------
Regulatory Definition / 5
29. Rocket ammunition. Rocket ammunition (including guided missiles)
is ammunition designed for launching from a tube, launcher, rails,
trough, or other launching device, in which the propellant
material is a solid propellant explosive. It consists of an
igniter, rocket motor, and projectile (warhead) either fused or
unfused, containing high explosives or chemicals.
30. Chemical ammunition. Chemical ammunition used in warfare is all
kinds of explosive chemical projectiles, shells, bombs, grenades,
etc., loaded with tear, or other gas, smoke or incendiary agent,
also such miscellaneous apparatus as cloud-gas cylinders, smoke
generators, etc., that may be utilized to project chemicals.
31. Boosters, bursters, and supplementary charges. Boosters and
supplementary charges consist of a casing containing a high
explosive and are used to increase the intensity of explosion of
the detonator of a detonating fuse. Bursters consist of a casing
containing a high explosive and are used to rupture a projectile
or bomb to permit release of its contents.
32. Jet thrust units or other rocket motors containing a mixture of
chemicals capable of burning rapidly and producing considerable
pressure.
33. Propellant mixtures (i.e., any chemical mixtures which are
designed to function by rapid combustion with little or no smoke).
NOTE 1: The detonation test is performed by placing the sample in an open-end
fiber tube which is set on the end of a lead block approximately 1-1/2 in.
in diameter and 4 in. high which, in turn, is placed on a solid base. A
steel plate may be placed between the fiber tube and the lead block.
NOTE 2: A No. 8 test blasting cap is one containing two grams of a mixture
of 80% mercury fulminate and 20% potassium chlorate, or a cap of equivalent
strength.
NOTE 3: "Unconfined" as used in this section does not exclude the use of a
paper or soft fiber tube wrapping to facilitate tests.
NOTE 4: The Bureau of Explosives' Impact Apparatus is a testing device
designed so that a guided 8-1b weight may be dropped from predetermined
heights so as to impact specific quantities of liquid or solid materials
under fixed conditions. Detailed prints of the apparatus may be obtained
from the Bureau of Explosives, Association of American Railroads, Operations
and Maintenance Dept., Bureau of Explosives, American Railroad Building,
Washington, D.C. 20036; 202-293-4048. The procedures for operating this
apparatus are described in the following paragraphs.
Method for Testing Liquids. The anvil is inserted in the receptable in
the anvil housing. A new cup is dropped into the cup-positioning block.
One drop of the sample liquid (about 0.01 g) is dropped into the cup
-------
6 / CHARACTERISTICS - Reactivity; EP Toxicity
from a pipette and the cup is revolved until an even film forms on base.
The top striker and the main striker are inserted as far as possible
into the upper housing. The upper housing is then placed over the
cup-positioning block so that the end of the main striker goes into the
brass cup. When the upper housing is removed from the cup-positioning
block, the brass cup is picked up on the end of the main striker. When
the two housings are screwed together, the brass cup automatically rests
firmly on the anvil.
An 8-1b drop weight is dropped from predetermined heights until consistent
failure results using the new sample portion and cup each time. An
explosion is evidenced by flame or flame and noise, but in either event
the brass cup will be belled out or bulged.
After making the drop, the drop weight is raised, the test assembly
removed, and appropriate solvent is poured into the top end. The two
housings are then separated, the striker removed, and the brass cup
removed from the striker end.
All solvent is removed carefully and thoroughly before preparations are
started for next drop and the apparatus cooled and cleaned. The test is
then repeated in the same manner, but with a filter paper disc in the
base of the cup under the composition being tested.
Method for Testing Solids. The die is placed in the anvil assembly and
¥ small amount (about 0.01 g)l to make a thin film is placed into the
die assembly. The steel striker pellet (plug) is inserted carefully and
then the striker (plunger). The assembly is then placed in the apparatus
and the drop weight allowed to rest on the striker top to effect even
distribution of the explosive.
The 8-1b drop weight is then dropped on the striker from predetermined
heights until consistent failure results (i.e., explosion, etc.) using a
new sample portion each time.
The die assembly is removed carefully and the striker removed. A few
drops of appropriate solvent are poured into the die assembly before it
is disassembled.
All parts are cleaned and dried carefully before each test.
NOTE 5: Blasting caps, blasting caps with safety fuse, or electric blasting
caps in quantities of 1,000 or less are classified as class 0 explosives and
not subject to regulation as a reactive waste.
it is suggested that a tiny spoon be devised to measure the proper
amount of test sample, since this is much more convenient and safer than
other methods of measuring the sample.
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2.1.4 Extraction Procedure Toxicity
Introduction
The Extraction Procedure (EP) is designed to simulate the leaching a
waste will undergo if disposed of in a sanitary landfill. This test is
designed to simulate leaching that takes place in a sanitary landfill
only. It is a laboratory test in which a representative sample of a waste is
extracted with distilled water maintained at a pH of 5 using acetic acid.
The extract obtained from the EP (the "EP Extract") is then analyzed to
determine if any of the thresholds established for the eight elements
(arsenic, barium, cadmium, chromium, lead, mercury, selenium, silver), four
pesticides (Endrin, Lindane, Methoxychlor, Toxaphene), and two herbicides
(2,4,5-trichlorophenoxypropionic acid, 2,4-dichlorophenoxyacetic acid) have
been exceeded. If the EP Extract contains any one of the above substances in
an amount equal to or exceeding the levels specified in 40 CFR 261.24, the
waste possesses the characteristic of Extraction Procedure Toxicity and is a
hazardous waste.
Summary of Procedure
The Extraction Procedure consists of five steps (refer to Figure 1):
1. Separation Procedure
A waste containing unbound liquid is filtered and if the solid
phase is less than 0.5% of the waste, the solid phase is discarded and
the filtrate analyzed for trace elements, pesticides, and herbicides
(step 5). If the waste contains more than 0.5% solids, the solid phase
is extracted and the liquid phase stored for later use.
2. Structural Integrity Procedure/Particle Size Reduction
Prior to extraction, the solid material must pass through a 9.5-mm
(0.375-in.) standard sieve, have a surface area per gram of waste
of 3.1 cm2, or, if it consists of a single piece, be subjected to the
Structural Integrity Procedure. The Structural Integrity Procedure is
used to demonstrate the ability of the waste to remain intact after
disposal. If the waste does not meet one of these conditions it must be
ground to pass the 9.5-mm sieve.
3. Extraction of Solid Material
The solid material from step 2 is extracted for 24 hr in an
aqueous medium whose pH is maintained at or below 5 using 0.5 N acetic
acid. The pH is maintained either automatically or manually. (In
acidifying to pH 5, no more than 4.0 g of acid solution per g of material
being extracted may be used.)
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2 / CHARACTERISTICS - EP Toxicity
Wet Waste Sample Representative Wet Wast
Contains < 0.5% ^ Waste Sample ^ ^^^
Nonfilte
Solids
^
rable ^ ^luubrams r Nonfj|ter
— ^SnliHc
1 4-
^. Dry Waste Sample ^
Liquid Solid w 0
Separation ^bolld
Lie
Discard
•^
uid Partic
> 9.5mm 0.5%
able
L
4 o (jd Liquid Solid
Separation
r
e Size Lie
>mm Monolithic
i
Structural
Integrity
Procedure
T *
^ A Store
•^
r
Solid ^— Liquid Solid Separation
I
+ \
Discard
Liq
J
EPE
J
. ..._..k A 1 -
Ir
uid
,
I'
Ktract
I
Methods
uid
r
at4°C
= 2
Figure 1. Extraction Procedure Flowchart.
-------
Introduction; Regulatory Definition / 3
4. Final Separation of the Extraction from the Remaining Solid
After extraction, the liquid:solid ratio is adjusted to 20:1 and
the mixed solid and extraction liquid are separated by filtration.
the solid is discarded and the liquid combined with any filtrate obtained
in step 1. This is the EP Extract that is analyzed and compared to the
threshold listed in Table 1 of 40 CFR 261.24.
5. Testing (Analysis) of EP Extract
Inorganic and organic species are identified and quantified using
the appropriate methods in the 7000 and 8000 series of methods in this
manual.
Regulatory Definition
A solid waste exhibits the characteristic of EP toxicity if, using the
appropriate test methods described in this manual or equivalent methods
approved by the Administrator under the procedures set forth in 40 CFR 260.20
and 260.21, the extract from a representative sample of the waste contains
any of the contaminants listed in Table 1 at a concentration equal to or
greater than the respective value given in that Table. If a waste contains
less than 0.5% filterable solids, the waste itself, after filtering, is
considered to be the extract for the purposes of analysis.
A solid waste that exhibits the characteristic of EP toxicity, but is
not listed as a hazardous waste in Subpart D, is assigned EPA Hazardous
Waste Numbers that correspond to the toxic contaminants causing it to be
hazardous. These numbers are specified in Table 1.
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4 / CHARACTERISTICS - EP Toxicity
TABLE 1. MAXIMUM CONCENTRATION OF CONTAMINANTS
FOR CHARACTERISTIC OF EP TOXICITY
EPA Maximum
Hazardous Waste concentration
Number Contaminant (mg/1 )
D004
D005
D006
D007
D008
D009
D010
D011
D012
D013
D014
D015
D016
D017
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin (1,2,3,4,10,10-Hexachloro-l
7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l
4-endo, endo-5,8-dimethanonaph-
thalerte)
Lindane (1,2,3,4,5,6-
Hexachlorocyclohexane, gamma isomer
Methoxychlor (l,l,l-Trichloro-2,2-bis
(p-methoxypheriyl )ethane)
Toxaphene (CiQHiods* Technical
chlorinated camphene, 67-69%
chlorine)
2,4-D (2,4-Dichlorophenoxyacetic acid)
2,4,5-TP (Silvex) (2,4,5-
5.0
100.0
1.0
5.0
5.0
0.2
1.0
b.O
0.02
0.4
10.0
0.5
10.0
1.0
Trichlorophenoxypropionic acid)
-------
METHOD 1310
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST
1.0 Scope and Application
1.1 The extraction procedure (EP) described in this method is designed
to simulate the leaching a waste will undergo if disposed of in an improperly
designed sanitary landfill. Method 1310 is applicable to liquid, solid, and
multiphasic samples.
2.0 Summary of Method
2.1 If a representative sample of the waste contains more than 0.5%
solids, the solid phase of the sample is extracted with deionized water which
is maintained at a pH of 5 _+ 0.2 using acetic acid. The extract is analyzed
to determine if any of the threshold limits listed in Table 1 are exceeded.
Table 1 also specifies the approved method of analysis. Wastes that contain
less than 0.5* solids are not subjected to extraction, but are directly
analyzed and evaluated in a manner identical to that of extracts.
3-0 Interferences
3.1 Potential interferences that may be encountered during analysis are
discussed in the individual analytical methods referenced in Table 1.
4.0 Apparatus and Materials
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 extrac-
tion fluid. Examples of suitable extractors are shown in Figures 1-3 of this
method and Section 2.2 (Mobility) of this manual and are available from
Associated Designs & Manufacturing Co., Alexandria, Virginia; Glas-Col
Apparatus Co., Terre Haute, Indiana; Mi Hi pore, Bedford, Massachusetts; and
Rexnard, Milwaukee, Wisconsin.
4.2 pH Meter or pH Controller (Chemtrix, Inc., Hillsboro, Oregon
is a possible source of a pH controller).
4.3 Filter holder: A filter holder capable of supporting a 0.45-n
filter membrane and able to withstand 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/cm^ (75 psi) of
pressure. The type of filter holder used depends upon the properties of the
mixture to be filtered. Filter holders known to EPA and deemed suitable for
use are listed in Table 2.
Revised 4/84
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1310 / 2
TABLE 1. MAXIMUM CONCENTRATION OF CONTAMINANTS
FOR CHARACTERISTIC OF EP TOXICITY
Maximum
concentration
Contaminant (mg/1 )
Arsenic
Barium
Cadmium
Total Chromium
Hexavalent Chromium
Lead
Mercury
Selenium
Silver
Endrin (1,2,3,4,10,10-Hexachloro-l
7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l
4-endo, endo-5,8-dimethanonaph-
thalene)
Lindane (1,2,3,4,5,6-
Hexachlorocyclohexane, gamma isomer)
Methoxychlor (l,l,l-Trichloro-2,2-bis
(p-methoxyphenyl )ethane)
Toxaphene (C1QHiocl8» Tecnnica1
chlorinated camphene, 67-69%
chlorine)
2,4-D (2,4-Dichlorophenoxyacetic acid)
2,4,5-TP (Silvex) (2,4,5-
Trichlorophenoxypropionic acid)
5.0
100.0
1.0
5.0
5.0
5.0
0.2
1.0
5.0
0.02
0.4
10.0
0.5
10.0
1.0
Analytical
method
7060, 7061
7080, 7081
7130, 7131
7190, 7191
7195, 7196,
7197
7420, 7421
7470
7740, 7741
7760, 7761
8080
8080
8080
8080
8150
8150
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1310 / 3
5.0
.25
4.0
I
Non-Clogging Support Bushing
1 Inch Blade at 30° to Horizontal
9.0
Figure 1. Extractor.
-------
1310 / 4
a
a
2
5
5
3
I
X
LU
X
?5
•«
o
-------
1310 / 5
1
X
93
E
c.
LL.
n
a;
-------
1310 / 6
4.4 Filter membrane: Filter membrane suitable for conducting the
required filtration shall be fabricated from a material which: (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 3 lists filter media known to the agency and generally
found to be suitable for solid waste testing.
4.4.1 In cases of doubt, contact the filter manufacturer to
determine if the membrane or the prefilter are adversely affected
by the particular waste. If no information is available, submerge the
filter in the waste's liquid phase. After 48 hr, a filter that
undergoes visible physical change (i.e., curls, dissolves, shrinks, or
swells) is unsuitable for use.
TABLE 2. ERA-APPROVED FILTER HOLDERS
Manufacturer Size Model No. Comments
Vacuum Filters
Nalgene 500 ml 44-0045 Disposable plastic unit,
includes prefilter and
filter pads, and reservoir;
should be used when
solution is to be analyzed
for inorganic constituents
Nuclepore 47 mm 410400
Millipore 47 mm XX10 047 00
Pressure Filters
Nuclepore 142 mm 425900
Micro Filtration 142 mm 302300
Systems
Mi Hi pore 142 mm YT30 142 HW
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1310 / 7
TABLE 3. EPA-APPROVED FILTRATION MEDIA
Supplier
Filter to be used
for aqueous systems
Filter to be used
for organic systems
Coarse Prefilter
Gel man
Nuclepore
Millipore
Medium prefilters
Nuclepore
Millipore
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
210905, 211705
AP20 035 00,
AP20 124 50
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
210905, 211705
AP20 035 00,
AP20 124 50
Fine prefilters
Gel man
Nuclepore
Millipore
64798, 64803
210903, 211703
API5 035 00,
APIS 124 50
64798, 64803
210903, 211703
AP15 035 00,
AP15 124 50
Fine filters (0.45 urn)
Gel man
Pall
Nuclepore
Millipore
Selas
60173, 60177
NX04750, NX14225
142218
HAWP 047 00,
HAWP 142 50
83485-02,
83486-02
60540 or 66149,
60544 or 66151
1422183
FHUP 047 00,
FHLP 142 50
83485-02,
83486-02
aSusceptible to decomposition by certain polar organic solvents.
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1310 / 8
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 re-analyze. If the concen-
tration of the filtrate differs from the original standard, the
filter membrane leaches or absorbs one or more of th.e chemical
species.
4.5 Structural integrity tester: Having a 3.18-cm (1.25-in.) diameter
hammer weighing 0.33 kg (0.73 Ib) and having a free fall of 15.24 cm (6 in.)
shall be used. This device is available from Associated Design and Manufac-
turing Company, Alexandria, VA 22314, as Part No. 125, or it may be fabri-
cated to meet the specifications shown in Figure 4.
5.0 Reagents
5.1 Deionized water: Water should be monitored for impurities.
5.2 0.5 N acetic acid: This can be made by diluting concentrated
glacial acetic acid (17.5 N). The glacial acetic acid should be of high
purity and monitored for impurities.
5.3 Analytical standards should be prepared according to the analytical
methods referenced in Table 1.
6.0 Sample Collection, Preservation and Handling
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Section One 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 Section 7.9.
If the sample is liquid or multiphase, continue as follows. Weigh filter
membrane and prefliter to ±0.01 g. Handle membrane and prefilters with
blunt curved-tip forceps or vacuum tweezers, or by applying suction with a
pipette.
-------
1310 / 9
m: j*> 3 $
*rr.^ /*•" *j v**^
X P-' ^ '^
1\, ifT- '^ Iff-Njv
•a
O
^ TTi'd
a-
15.25 cm f]
(6")
Combined
f» Weignt
.33kg (.73 ib)
(3.15cm)
(1.25")
Sample
Eiastomenc
r»
'
Samni*
/ /s
fcL:.;^
7.1 cm
(2.8")
3.3 cm
(1.3")
U-
Elastomeric sample holaer fabricated of mater.al firm enough to sopoon the sample.
Figure 4. Compaction terrer.
-------
1310 / 10
7.2 Assemble filter holder, membranes, and prefilters following the
manufacturer's instructions. Place the 0.45-ujn membrane on the support
screen and add prefilters in ascending order of pore size. Do not prewet
filter membrane.
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 waste's or extraction
mixture's liquid phase. 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. This liquid will constitute part or all
of the extract (refer to Section 7.16). The liquid should be refrigerated
until time of analysis.
NOTE: Oil samples or samples which contain 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 extract. If the liquid portion of
the sample will not filter (this is usually the case with heavy oils or
greases) it is carried through the EP extraction as a solid.
7.6 Remove the solid phase and filter media and, while not allowing it
to dry, weight to +0.01 g. The wet weight of the residue is determined by
calculating the weTght difference between the weight of the filters (Section
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 of less than 0.5% solids. If the sample appears
to have less than 0.5% solids, the percent solids will be determined by the
following procedure.
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 filtered tared we-ight
solid and filters "_ of filters x 1QO = % solids
initial weight of waste material
NOTE: This procedure is only used to determine whether the solid
must be extracted or whether it can be discarded unextracted. It
Revised 4/84
-------
1310 / 11
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 comprises less than 0.5% of the waste, discard the
solid and proceed immediately to Section 7.17, treating the liquid phase as
the extract.
7.9 The solid material obtained from Section 7.5 and all materials that
do not contain free liquids should be evaluated for particle size. If the
solid material has a surface area per gram of material equal to or greater
than 3.1 cnr or passes through a 9.5-mm (0.375-in.) standard sieve, the
operator should proceed to Section 7.11. If the surface area is smaller or
the particle size larger than specified above, the solid material would 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 Section 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. For wastes that have 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 more than 0.5% solids, use the wet weight
of the solid phase obtained in Section 7.6 for purposes of calculating the
amount of liquid and acid to employ for extraction by using the following
equation:
W = Wf - Wt
where:
W = wet weight in grams of solid to be charged to extractor
Wf = wet weight in grams of filtered solids and filter media
W^. = weight in grams of tared filters.
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1310 / 12
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 Section 7.11)
into the extractor and add 16 times its weight of deionized water.
7.13 After the solid material and deionized water are placed in the
extractor, the operator should begin agitation and measure the pH of the
solution in the extractor. If the pH is greater than 5.0, the pH of the
solution should be decreased to 5.0 ± 0.2 by adding 0.5 N acetic acid. If
the pH is equal to or less than 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, 0.5 N 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 gram
of solid. The mixture should be agitated for 24 hr and maintained at
20*-40* C (68*-104* F) during this time. It is 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 Chemtrix, Inc., Hills-
boro, Oregon 97123 or its equivalent, in conjunction with a metering pump
and reservoir of 0.5 N acetic acid. If such a system is not available, the
following manual procedure shall be employed.
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 necessary,
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-min intervals, moving to the next longer interval if the pH
does not have to be adjusted more than 0.5 pH units.
7.13.3 The adjustment procedure should be continued for at least 6 hr.
7.13.4 If, at the end of the 24-hr extraction period, the pH of the
solution is not below 5.2 and the maximum amount of acid (4 ml per gram
of solids) has not been added, the pH should be adjusted to 5.0 + 0.2
and the extraction continued for an additional 4 hr, during whicF the
pH should be adjusted at 1-hr intervals.
7.14 At the end of the extraction period, deionized water should
be added to the extractor in an amount determined by the following equation:
V = (20)(W) - 16(W) - A
where:
V = ml deionized water to be added
W = weight in g of solid charged to extractor
A = ml of 0.5 N acetic acid added during extraction
-------
1310 / 13
7.15 The material in the extractor should be separated into its compo-
nent 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 Section 4.3 and 4.4).
7.15.2 Wet the filter with a small portion of the waste's or
extraction mixture's liquid phase. 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 Sections 7.5 and 7.15 should be combined.
This combined liquid (or the waste itself if it has less than 0.5% solids, as
noted in Section 7.8) is the extract and should be analyzed for the presence
of any of the contaminants specified in Table 1 using the Analytical Proce-
dures designated in Section 7.17.
7.17 The extract will be prepared and analyzed according to the analyt-
ical methods specified in Table 1. All of these analytical methods are
included in this manual. The method of standard addition will be employed
for all metal analyses.
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)(contaminant cone, in oil) + (1,000)(contaminant cone, of aqueous phase)
1,050 1,050
7.18 The extract concentrations are compared to the maximum contamina-
tion limits listed in Table 1. If the extract concentrations are equal to or
greater than the respective values, then the waste is considered to be EP
toxic.*
•^Chromium concentrations have to be interpreted differently. A waste
containing chromium will be determined to be EP toxic if (1) the waste extract
has an initial pH of less than 7 and contains more than 5 mg/1 of hexavalent
chromium in the resulting extract, or (2) the waste extract has an initial
pH greater than 7 and a final pH greater than 7 and contains more than 5 mg/1
of hexavalent chromium in the extract, or (3) the waste extract has an
initial pH greater than 7 and a final pH less than 7 and contains more than
5 mg/1 of total chromium, unless the chromium is trivalent. To determine
whether the chromium is trivalent, the sample must be processed according to
an alkaline digestion method (Method 3060) and analyzed for hexavalent
chromium (Methods 7195, 7196, or 7197).
-------
1310 / 14
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 suggested in the referenced analytical
methods should be followed.
-------
2.2 Mobility Procedures
Mobility procedures are used to determine the mobility of various
components in a waste. Although these procedures are used to evaluate a
waste, they are not to be confused with a hazardous characteristic as defined
by the RCRA Regulations, Part 261.
-------
METHOD 1410
MULTIPLE EXTRACTION PROCEDURE
This method is presently under development.
-------
SECTION FOUR
SAMPLE NORKUP TECHNIQUES
4.1 Inorganic Techniques (beginning of 3000 series)
Methods appropriate for sample workup prior to analysis by inorganic
techniques (6000 and 7000 series) are included on the following pages.
-------
METHOD 3010
ACID DIGESTION PROCEDURE FOR FLAME ATOMIC ABSORPTION SPECTROSCOPY
1.0 Scope and Application
1.1. This digestion procedure is approved for the preparation of
aqueous samples, EP and mobility procedure extracts, and wastes that contain
suspended solids for analysis, by flame atomic absorption spectroscopy (AAS),
for the metals listed below. The procedure is to be used when one is to
determine the total amount of the metal in the sample.
1.2 Metals for which Method 3010 is the approved flame AAS procedure
are:
Aluminum Lead
Antimony Magnesium
Barium Manganese
Beryllium Molybdenum
Cadmium Nickel
Calcium Potassium
Chromium Sodium
Cobalt Tin
Copper Vanadium
Iron Zinc
1.3 If a nonaqueous sample is not completely digested by this method
and determination as to the total concentration of a metal in the entire
sample is required, then the digestion methods described in Method 3030,
3040, or 3050 should be tried. Some wastes will require fusion techniques to
completely release metals from inorganic matrices. The appropriate fusion
method should be chosen from the literature and its applicability to the
sample of interest proven by analyzing spiked samples and relevant standard
reference materials.
1.4 This digestion procedure is not suitable for samples which will be
analyzed by graphite furnace atomic absorption spectroscopy, since hydro-
chloric acid can cause interferences during atomization.
2.0 Summary of Method
2.1 A mixture of nitric acid and the material to be analyzed is
heated to near dryness in a 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
near dryness, it is cooled and brought up in dilute hydrochloric acid.
Revised 4/84
-------
3010 / 2
3.0 Interferences
3.1 Interferences are discussed in the referring analytical method.
4.0 Apparatus and Materials
4.1 Griffin beakers of assorted sizes.
4.2 Qualitative filter paper or centrifugation equipment.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Hydrochloric acid (1:1): Prepared from deionized distilled water
(or equivalent) and hydrochloric acid. Hydrochloric acid should be analyzed
to determine level of impurities. If impurities are detected, all analyses
should be blank-corrected.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
distilled deionized water. Plastic and glass containers are both suitable.
6.3 Aqueous wastewaters must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Transfer a representative aliquot of the well-mixed sample to a
Griffin beaker and add 3 ml of cone. HN03. Cover the beaker with a 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 cone. HN03. Re-cover the
beaker with a watch glass and return to the hot plate. Increase the
-------
3010 / 3
temperature of the hot plate so that a gentle reflux action occurs. It
should be noted that if a sample is allowed to go to dryness, low recoveries
may result for tin and antimony.
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,
evaporate to near dryness and cool the beaker. Add a small quantity of
1:1 HC1 (5 ml/100 ml of final solution) and warm the beaker to dissolve any
precipitate or residue resulting from evaporation.
7.3 Wash down the beaker walls and watch glass with distilled 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 nitric acid. Adjust the volume to some predetermined value based on
the expected metal concentrations. The sample is now ready for analysis.
8.0 Quality Control
8.1 For each group of samples processed, procedural blanks (Type II
water and reagents) should be carried throughout the entire sample-preparation
and analytical process. These blanks Will be useful in determining if
samples are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate
the frequency, but 10% is recommended.
8.3 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.
8.4 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
8.5 The method of standard addition shall be used for the analysis
of all EP extracts and whenever a new sample matrix is being analyzed.
-------
METHOD 3020
ACID DIGESTION PROCEDURE FOR FURNACE ATOMIC ABSORPTION SPECTROSCOPY
1.0 Scope and Application
1.1 This digestion procedure is approved for the preparation of
aqueous samples, mobility procedure extracts, and certain nonaqueous
wastes for analysis, by furnace atomic absorption spectroscopy (AAS),
for the metals listed below. The procedure is to be used when one is to
determine the total amount of the metal in the sample.
1.2 Metals for which Method 3020 is the approved furnace AAS procedure
are:
Aluminum
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Manganese
Molybdenum
Nickel
Silver
Thallium
Vanadium
Zinc
1.3 If a nonaqueous sample is not completely digested by this method
and determination as to the total concentration of a metal in the entire
sample is required, then the digestion methods described in Method 3030,
3040, or 3050 should be tried. Some wastes will require fusion techniques to
completely release metals from inorganic matrices. The appropriate fusion
method should be chosen from the literature and its applicability to the
sample of interest proven by analyzing spiked samples and relevant standard
reference materials.
2.0 Summary of Method
2.1 A mixture of nitric acid and the material to be analyzed is
heated to near dryness in a 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
near dryness, it is cooled and brought up in dilute nitric acid such that the
final dilution contains 0.5% (v/v) HN03.
3.0 Interferences
3.1 Interferences are discussed in the referring analytical method.
-------
2 / WORKUP TECHNIQUES - Inorganic
4.0 Apparatus and Materials
4.1 Griffin beakers of assorted sizes.
4.2 Qualitative filter paper or centrifugation equipment.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
distilled deionized water. Plastic and glass containers are both suitable.
6.3 Aqueous wastewaters must be acidified to a pH of
less than 2 with nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Transfer a representative aliquot of the well-mixed sample to a
Griffin beaker and add 3 ml of cone. HN03. Cover the beaker with a
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 cone. HN03. Re-cover the
beaker with a watch glass and return to the hot plate. Increase the temper-
ature of the hot plate so that a gentle reflux action occurs. It should be
noted that if a sample is allowed to go to dryness, low recoveries may result
for tin and antimony.
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,
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.
-------
3020 / 3
7.3 Wash down the beaker walls and watch glass with distilled 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 nitric acid. Adjust the volume to some predetermined value based on
the expected metal concentrations. The sample is now ready for analysis.
8.0 Quality Control
8.1 For each group of samples processed, procedural blanks (Type II
water and reagents) should be carried throughout the entire sample-preparation
and analytical process. These blanks will be useful in determining if
samples are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate
the frequency, but 10% is recommended.
8.3 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.
8.4 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
8.5 The method of standard addition shall be used for the analysis
of all EP extracts and whenever a new sample matrix is being analyzed.
-------
METHOD 3030
ACID DIGESTION OF OILS. GREASES. OR WAXES
1.0 Scope and Application
1.1 This digestion procedure is approved for the preparation of samples
that contain substantial amounts of oils, greases, or waxes and that will be
analyzed for the total concentration of the following metals: arsenic,
cadmium, chromium, mercury, selenium, and silver. Since certain matrices
may result in poor recovery, the method of standard addition shall be used.
2.0 Summary of Method
2.1 A representative sample is placed in a Kjeldahl or similar flask
and is subjected to digestion by sulfuric acid, nitric acid, and hydrogen
peroxide. The digestate is diluted to volume and is ready for analysis.
3.0 Interferences
3.1 Interferences are discussed in the referring analytical method.
4.0 Apparatus and Materials
4.1 Ground-glass-stoppered 300-ml Kjeldahl flask (acid precleaned).
4.2 300-mm Allihin condenser filled to 50 mm with rashing rings or
glass beads (acid precleaned).
4.3 6-mm glass bead (acid precleaned).
4.4 Heating mantle.
5.0 Reagents
5.1 Concentrated nitric acid.
5.2 Concentrated sulfuric acid.
5.3 Concentrated hydrochloric acid.
5.4 30% hydrogen peroxide.
Revised 4/84
-------
3030 / 2
NOTE: The above reagents should be analyzed to determine the level of
impurities. If impurities are detected, all analyses should be blank-
corrected.
6.0 Sample Collection, Preservation, and Handling
6.1 Samples shall be stored in an undiluted state at room temperature.
6.2 Samples should be processed and analyzed as soon as possible.
7.0 Procedure
7.1 Weigh out a 100-g representative sample of the waste or extract.
Separate the phases if more than one is present, and weigh each phase. Weigh
2.0 g of the organic phase into the digestion or Kjeldahl flask. Add 10 ml
and a 6-mm glass bead. Swirl flask to mix the contents.
7.2 Approximately three-fourths of the neck of the Kjeldahl flask
should be cooled by directing an air stream against the neck of the flask.
If an Allihin condenser is employed, water will be used to cause ref luxation
and the air stream is not required.
7.3 Heat the flask gently and continue heating until dense white
fumes appear and the solution boils. Cautiously add 1 ml HN03 dropwise to
oxidize the organic material. This may be done through the condenser. When
the HN03 has boiled off and dense white fumes reappear, repeat the treat-
ment with an additional 1 ml of HN03- Continue the addition of HN03 in
1-ml increments until the digestion mixture is no darker than a straw color,
indicating that most of the organic matter has been oxidized.
7.4 Cool the flask slightly and add 0.5 ml (dropwise) of H202« Heat
until dense white fumes appear, and while boiling, cautiously add 1 ml of
HN03 dropwise. When the HNOo has boiled off and dense white fumes reappear,
repeat the treatment with H2®2 and HN(^3 unti^ tne digestion mixture is
colorless, at which time the organic material will be completely oxidized.
Four treatments will usually suffice.
7.5 When oxidation is complete, allow the flask to cool, wash down the
condenser with a small volume of distilled water (5 ml) and mix the contents.
Continue heating until dense white fumes appear.
7.6 Cool. If a precipitate forms, add 2 ml of cone. HC1 before
diluting to remove the precipitate. If the precipitate persists, filter or
centrifuge-the solution to remove the precipitate, and proceed to determine
As, Ba, Cd, Cr, Hg, Pb, and Se concentrations. Dilute to a total volume of
25 ml. HC1 should not be added if Ag concentrations are to be determined.
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3030 / 3
7.7 The digestate as well as any aqueous phases that may have been
present are analyzed for metal content by the appropriate method specified in
this manual. Metal concentrations should be reported as the weighted average
for both phases.
8.0 Quality Control
8.1 For each group of samples processed, procedural blanks (Type II
water and reagents) should be carried throughout the entire sample-preparation
and analytical process. These blanks will be useful in determining if
samples are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate
the frequency, but 10% is recommended.
8.3 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.
8.4 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
8.5 The method of standard addition shall be used for the analysis
of all EP extracts and whenever a new sample matrix is being analyzed.
-------
METHOD 3040
DISSOLUTION PROCEDURE FOR OILS, GREASES. OR WAXES
1.0 Scope and Application
1.1 Method 3040 is approved for the preparation of samples containing
oils, greases, or waxes which will be analyzed for barium, cadmium, chromium,
lead, and silver. While this method may also be applicable to the analysis
of other metals in these matrices, further work is necessary to validate the
method for other metals.
2.0 Summary of Method
2.1 A representative sample is dissolved in an appropriate solvent
(e.g., xylene or methyl isobutyl ketone). Organometallic standards are
prepared using the same solvent, and the samples and standards are analyzed
by atomic absorption spectroscopy (AAS) or inductively coupled argon plasma
emission spectroscopy (ICP).
3.0 Interferences
3.1 Diluted samples and diluted organometallic standards are often
unstable. Once standards and samples are diluted they should be analyzed as
soon as possible.
3.2 Solvent blanks should be used to thoroughly rinse nebulizers
following aspiration of high concentration standards or samples.
3.3 Viscosity differences can result in different rates of sample
introduction, so all analyses shall be performed by the method of standard
addition. Peristaltic pumps often prove useful when analysis is performed by
ICP.
4.0 Apparatus
4.1 Volumetric glassware.
4.2 Balance.
4.3 Atomic Absorption Spectrometer having an auxiliary oxidant
control and a mechanism for background correction.
4.4 Inductively Coupled Argon Plasma Emission Spectrometer system
having a mechanism for background correction and interelement interference
correction. A peristaltic pump is optional.
-------
2 / WORKUP TECHNIQUES - Inorganic
5.0 Reagents
5.1 Methyl isobutyl ketone (MIBK).
5.2 Xylene.
5.3 Organometallic standards (two possible sources are Continental Oil
Company, Ponca City, Oklahoma, and the U.S. Department of Commerce, National
Bureau of Standards, Washington, D.C. 20234).
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 Samples should be stored in an undiluted state at room temperature.
6.3 Solvent dissolution of samples should be performed as closely as
possible to the time of analysis.
7.0 Procedure
7.1 Weigh out a 100-g representative sample of the waste or extract.
Separate and weigh the phases if more than one phase is present.
7.2 Weigh an aliquot of the organic phase and dilute the aliquot in
the appropriate solvent. Warming facilitates the subsampling of crude-type
oils and greases and wax-type wastes. Xylene is usually the preferred
solvent for longer-chain hydrocarbons and for most analyses performed by
ICP. The longer-chain hydrocarbons usually require a minimum of a 1:10 dilu-
tion, while lighter oils may require only a 1:5 dilution if low detection
limits are required.
7.3 When analyzing samples for alkali and alkaline earth metals,
organometallic ionization suppressants (e.g., potassium cyclohexane butyrate)
are suggested as a means of improving detection limits.1 If ionization
suppressants are employed, they must be added to both samples and standards.
7.4 All metals must be analyzed by the method of standard additions.
Since the method of standard additions can account only for multiplicative
interferences (matrix or physical interferences), the analytical program must
account for additive interference (nonspecific adsorption and scattering in
^•The literature disagrees about the advantages of employing ionization
suppressants; the analyst should use his/her own judgment whether to use
these matrix modifiers.
-------
3040 / 3
AAS and nonspecific emission and interelement interference in ICP) by employ-
ing background correction.
7.5 Sample preparation for the method of standard additions can be
performed on a weight or volume basis. Sample aliquots of viscous wastes
should be weighed. Weigh identical amounts of the sample into three wide-
mouth vials. Dilute the first vial such that the final concentration falls
on the lower end of the linear portion of the calibration curve and signifi-
cantly above the detection limit. Add sufficient standard to the second
aliquot to increase the sample concentration by approximately 50%. Adjust
the third sample concentration so that it is approximately twice that of the
first. The second and third aliquots are then diluted to the same final
volume as the first aliquot.
7.6 Set up and calibrate the analytical instrumentation according to
the manufacturer's directions for nonaqueous samples.
7.7 Report data as the weighted average for all sample phases.
8.0 Quality Control
8.1 Procedural blanks (e.g., Conostan base oil or mineral oil plus
reagents) should be carried through the complete sample preparation and
analytical process on a routine basis. These blanks will be useful in
detecting and determining the magnitude of any sample contamination.
8.2 Duplicate samples should be processed on a routine basis. These
samples will be used to determine the precision of the method.
8.3 Samples and standards should be diluted as closely as possible to
the time of analysis.
8.4 All analyses must be performed by the method of standard additions.
8.5 Data must be corrected for background absorption and emission and
interelement interferences.
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METHOD 3050
ACID DIGESTION OF SLUDGES
1.0 Scope and Application
1.1 Method 3050 is an acid digestion procedure used to prepare sludge-
type and soil samples for analysis by flame or furnace atomic absorption
spectroscopy (AAS) or by inductively coupled argon plasma spectroscopy (ICP).
Samples prepared by Method 3050 may be analyzed by AAS or ICP for the
following metals:
Antimony Lead
Arsenic Nickel
Barium Selenium
Beryllium Silver
Cadmium Thallium
Chromium Zinc
Copper
1.2 Method 3050 may also be applicable to the analysis of other metals
in sludge-type samples. However, prior to using this method for other
metals, it must be evaluated using the specific metal and matrix.
2.0 Summary of Method
2.1 A dried and pulverized 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 as the final reflux
acid for the furnace analysis of Sb or the flame analysis of Sb, Ba, Be, Cd,
Cr, Cu, Pb, Ni, and Zn. Nitric acid is employed as the final reflux acid for
the furnace analysis of As, Ba, Be, Cd, Cr, Cu, Pb, Ni, Se, Ag, Tl, and Zn or
the flame analysis of Ag and Tl.
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. Nondestructive techniques such as
neutron activation analysis may also be helpful in evaluating the applicabil-
ity of this digestion method.
4.0 Apparatus and Materials
4.1 125-ml conical Phillips' beakers.
4.2 Watch glasses.
Revised 4/84
-------
3050 / 2
4.3 Drying ovens that can be maintained at 30* C.
4.4 Thermometer that covers range of 0* to 200* C.
4.5 Whatman No. 42 filter paper or equivalent.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank corrected.
5.3 Concentrated hydrochloric acid: Acid should be analyzed to deter-
mine level of impurities. If impurities are detected, all analyses should be
blank corrected.
5.4 Hydrogen peroxide (30%): Oxidant should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank corrected. ,
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and distilled deionized water. Plastic and glass containers are both
suitable.
6.3 Nonaqueous samples shall be refrigerated when possible, and
analyzed as soon as possible.
7.0 Procedure
7.1 Weigh and transfer to a 125-ml conical Phillips' beaker a 1.0-g
portion of sample which has been dried at 60" C, pulverized, and thoroughly
mixed.
7.2 Add 10 ml of 1:1 nitric acid (HNOs), mix the slurry, and cover
with a watch glass. Heat the sample at 95* C and reflux for 10 min. Allow
the sample to cool, add 5 ml of cone. HN03, replace the watch glass, and
reflux for 30 min. Do not allow the volume to be reduced to less than 5 ml
while maintaining a covering of solution over the bottom of the beaker.
Revised 4/84
-------
3050 / 3
7.3 After the second reflux step has been completed and the sample
has cooled, add 2 ml of Type II water and 3 ml of 30% hydrogen peroxide
Return the beaker to the hot plate for warming 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% ^Og 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 the furnace analysis of Ag and
Sb or direct aspiration analysis of Ag, Sb, Ba, Be, Cd, Cr, Cu, Pb, Ni, Tl, and
Zn, add 5 ml of 1:1 HC1 and 10 ml of Type II water, return the covered beaker
to the hot plate, and heat for an additional 10 min. After cooling, filter
through Whatman No. 42 filter paper (or equivalent) and dilute to 100 ml with
Type II water (or centrifuge the sample). The diluted sample has an approximate
acid concentration of 2.5% (v/v) HC1 and 0.5% (v/v) HN03 and is now ready for
analysis.
7.6 If the sample is being prepared for the furnace analysis of As, Ba,
Be, Cd, Cr, Cu, Pb, Ni, Se, Tl, and Zn, continue heating the acid-peroxide
digestate until the volume has been reduced to approximately 2 ml, add 10 ml
of Type II water, and warm the mixture. After cooling, filter through
Whatman No. 42 filter paper (or equivalent) and dilute to 100 ml with Type II
water (or centrifuge the sample). The diluted digestate solution contains
approximately 2% (v/v) HN03- For analysis, withdraw aliquots of appropriate
volume, add any required reagent or matrix modifier, and analyze by method of
standard additions.
8.0 Quality Control
8.1 For each group of samples processed, procedural blanks (Type II
water and reagents) should be carried throughout the entire sample-preparation
and analytical process. These blanks will be useful in determining if
samples are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate
the frequency, but 10% is recommended.
8.3 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.
8.4 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
8.5 The method of standard addition shall be used for the analysis
of all EP extracts and whenever a new sample matrix is being analyzed.
Revised 4/84
-------
METHOD 3060
ALKALINE DIGESTION
1.0 Scope and Application
1.1 Method 3060 is used to determine the total concentration of hexavalent
chromium in solid wastes.
2.0 Summary of Method
2.1 This method uses a basic digestion of the waste sample to solubilize
both water-insoluble and water-soluble hexavalent chromium compounds.
2.2 The sample is extracted with hot, 3% sodium carbonate-2% sodium
hydroxide solution to dissolve all Cr(VI) and to protect it from reduction to
trivalent chromium.
3.0 Interferences
3.1 Wastes containing high amounts of buffering capability may require
additional digestion solution (see section 5.5) to properly digest the sample.
4.0 Apparatus
4.1 Beakers: borosilicate, 600-ml, with watch glass covers.
4.2 Filtration apparatus: pressure 75 psi, with 0.45-n filter.
4.3 Volumetric flasks: 1-liter.
4.4 Hot Plate: 120-140° C.
4.5 Pipettes: assorted sizes, as necessary.
5.0 Reagents
5.1 Nitric acid: HNOs, concentrated, analytical reagent grade or
spectrograde quality.
5.2 Sodium carbonate: Na2C03, anhydrous, analytical reagent grade.
5.3 Sodium hydroxide: NaOH, analytical reagent grade.
5.4 Potassium dichromate: I^C^Oy, analytical reagent grade.
-------
2 / WORKUP TECHNIQUES - Inorganic
5.5 Digestion solution: Dissolve 20.0 g sodium hydroxide and 30.0 g
sodium carbonate in deionized distilled water in a 1-liter volu-
metric flask and dilute to the mark. Store the solution in a
tightly capped polyethylene bottle and prepare fresh monthly.
5.6 Potassium dichromate spiking solution (1 ml =1 mg Cr): Dissolve
28.29 g of dried potassium dichromate in deionized distilled water
in a 1-liter volumetric flask and dilute to the mark.
6.0 Sample Handling and Preservation
6.1 To retard the chemical activity of hexavalent chromium, the sample
and digestate should be stored at 4" C until analyzed.
6.2 Since the chemistry of hexavalent chromium is not fully understood,
all samples should be analyzed as soon as possible.
7.0 Procedure
7.1 Place 100 g of the waste into a 600-ml beaker.
7.2 Add 400 ml of digestion solution (see section 5.5). Cover the
beaker with the watch glass and heat it to near boiling on a hot plate with
constant mixing for 30 to 45 min. Do not allow to go to dryness, as hexa-
valent chromium may be lost due to side reactions in the waste.
7.3 Cool the solution and transfer it quantitatively to the filtration
apparatus with deionized distilled water rinses and filter. Rinse the inside
of the filter flask and filter pad with deionized distilled water and transfer
the filtrate and the rinses to a 1-liter volumetric flask.
7.4 If the sample will not be immediately analyzed, it should be stored
at a high pH. Just prior to analysis, place a magnetic stirring bar into the
flask, place the flask on a stirrer and, with constant stirring, slowly add
concentrated nitric acid to the flask in small aliquots. Bring the pH of the
solution to between 7 and 8. Caution: carbon dioxide will be evolved.
7.5 Remove the stirring bar and rinse the bar into the flask. Dilute
the contents of the flask to the mark with deionized distilled water.
7.6 Select one of the methods given for determining the concentration
of hexavalent chromium (7195, 7196, or 7197) and determine the amount of
hexavalent chromium in the digestate immediately.
7.7 Calculate the amount of hexavalent chromium in the sample in
mg/kg. A sample calculation could be as follows:
-------
3060 / 3
A digested 100-g waste sample was found to contain 12.0 nig/1 in the
final digestate, or 12.0 mg/100 g of hexavalent chromium in the waste.
This material would be considered hazardous since it could result in
the release of more than 5 mg/1 of hexavalent chromium in an EP leachate
(i.e., 12 mg hexavalent chromium in the final EP leachate volume of
2 liters would equal 6 mg/1).
8.0 Quality Control
8.1 For every sample matrix analyzed, verification is required to
determine that neither a reducing condition nor chemical interference affect-
ing the digestion is present. This must be accomplished by analyzing a
second 100-g aliquot of the waste that has been spiked with Cr(VI) (see
section 5.6). The amount of spike added should double the concentration
found in the original aliquot. Under no circumstance should the increase
be less than 0.10 mg/g. To verify the absence of an interference, the spike
recovery should be between 85% and 115%. If the result of verification
indicates a suppressive interference, the analysis will not be considered to
be valid, and further guidance should be obtained prior to basing any deci-
sions on the data obtained.
-------
4.2 Organic Techniques (end of 3000 series)
Methods appropriate for sample workup prior to analysis by organic
techniques (8000 series) are included on the following pages.
-------
METHOD 3510
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0 Scope and Application
1.1 Method 3510 is designed to quantitatively extract nonvolatile and
semivolatile organic compounds from liquid samples using standard separatory
funnel techniques. The sample and extracting solvent must be immiscible to
yield recovery of target compounds. Subsequent cleanup and detection methods
are described in the organic analytical method that will be used to analyze
the extract.
2.0 Summary of Method
2.1 Samples are adjusted to a specified extraction pH and extracted
with the appropriate solvent. Methylene chloride should be employed when a
solvent is not specified. The extraction pH and solvent to be used are
listed in each referring analytical method. Samples are extracted three
times, and the combined extracts are dried with anhydrous sodium sulfate and
concentrated in a Kuderna-Danish apparatus.
3.0 Interferences
3.1 A procedural 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 Procedures for the removal of interfering compounds coextracted
with target compounds are described in the referring analytical methods.
4.0 Apparatus
4.1 Separatory funnel: 2-liter, with Teflon stopcock.
4.2 Drying column: 20-mm I.D. Pyrex chromatographic column with coarse
frit.
4.3 Kuderna-Danish (K-D) apparatus.
4.4 Boiling chips: Solvent extracted, approximately 10/40 mesh.
4.5 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+2° C). The bath should be used in a hood.
-------
2 / WORKUP TECHNIQUES - Organic
4.6 pH indicator paper with a pH range including the desired extrac-
tion pH.
5..0 Reagents
5.1 The specific reagents to be employed in this method may be listed
under the organic analytical method that will be used to analyze the extract.
Check analytical method for specific extraction reagent. If a specific
extracting reagent is not listed for the compound(s) of interest, methylene
chloride shall be used.
5.2 The solvent of choice should be appropriate for the method of
measurement to be used, and it should give an analyte-to-solvent partition
coefficient of at least 1 to 1000.
5.3 Sodium sulfate: (ACS) Granular anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Sodium hydroxide: (ACS) 10 N in distilled water.
5.5 Sulfuric acid: (1:1) Mix equal volumes of concentrated H2S04 (ACS)
with distil led water.
5.6 Distilled water.
5.7 Methylene chloride: Pesticide quality or equivalent.
6.0 Sample Collection, Preservation, and Handling
6.1 Adhere to those procedures specified in the referring analytical
methods for collection, preservation, and handling.
7.0 Procedure
7.1 Transfer 1 liter of sample to the separatory funnel. If less than
1 liter of sample is available or if high concentrations are anticipated, use
a smaller volume of sample and, if necessary, add laboratory distilled water
until sample volume is suitable for extraction.
7.2 Adjust the pH of the sample to that indicated in the referring
method.
7.3 Add 60 ml of the appropriate extraction solvent, as indicated in
the referring method.
7.4 Seal and shake the separatory funnel for 60 sec with periodic
venting to release vapor pressure.
-------
3510 / 3
7.5 Allow the phases to separate for a minimum of 10 min. 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, but may
include stirring, filtration of the emulsion through glass wool, or centri-
fugation.
7.6 Collect the extract and then repeat the extraction two more times
using fresh portions of solvent.
7.7 Combine the three extracts and appropriately discard the now
extracted waste, if no further extractions are to be performed.
7.8 Dry the extract by passing it through a column of anhydrous sodium
sulfate. Collect the dried extract in a Kuderna-Danish evaporative concen-
trator equipped with a 10-ml collection ampule.
7.9 Add 1 or 2 clean boiling chips to the flask and attach a three-ball
Snyder column. Prewet the Snyder column by adding about 1 ml solvent to the
top. Place the K-D apparatus on a steam or hot water bath so that the
concentrator tube and the entire lower rounded surface of the flask are bathed
in hot water or vapor. Adjust the vertical position of the apparatus and the
water temperature as required to complete the concentration in 15-20 min. At
the proper rate of distillation, the balls of the column will actively chatter
but the chambers will not flood. When the apparent volume of liquid reaches
1 ml, remove the K-D apparatus and allow it to drain for at least 10 min
while cooling.
7.10 Rinse the K-D apparatus with a small volume of solvent. Adjust
the sample volume to 10.0 ml with the solvent to be used in instrumental
analysis. Proceed with analysis and cleanup if necessary.
8.0 Quality Control
8.1 Comprehensive quality control procedures are specified for each
target compound in the referring analytical method.
8.2 By fortifying distilled water or another liquid similar to the
sample matrix, the analyst should demonstrate that the compound(s) of interest
are being quantitatively recovered before applying this method to actual
samples.
-------
METHOD 3520
CONTINUOUS LIQUID-LIQUID EXTRACTION
1.0 Scope and Application
1.1 Method 3520 is designed to quantitatively extract nonpurgeable
organic compounds from liquid samples using a continuous extraction apparatus.
This method is available as an alternative to Method 3510, which is a sepa-
ratory funnel extraction procedure. Method 3520 is advantageous compared to
standard separatory funnel techniques because it minimizes emulsion formation.
The sample and extracting solvent must be immiscible to yield recovery of
target compounds. Subsequent cleanup and detection are described in referring
analytical methods.
1.2 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 The sample is placed into the continuous extraction apparatus,
adjusted to the proper extraction pH and extracted with the appropriate
solvent. Methylene chloride should be employed when a solvent is not specified.
The extraction pH and solvent to be used are listed in the quantification
method. Samples are extracted for 16 hr; the extract is collected, dried
with anhydrous sodium sulfate, and concentrated with a Kuderna-Danish apparatus.
In some cases, the sample pH is adjusted after the first extraction, and
continuous extraction is carried out for 16 hr to recover an additional class
of compound.
3.0 Interferences
3.1 A procedural 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 Procedures for the removal of interfering compounds coextracted
with target compounds are described in the organical analytical method
that will be used to analyze the sample.
-------
2 / WORKUP TECHNIQUES - Organic
4.0 Apparatus and Materials
4.1 Continuous liquid-liquid extractor (Hershberg-Wolfe type, Lab Glass
#LG-6915; or equivalent).
4.2 Drying column: 20-rnm I.D. Pyrex chromatographic column with coarse
frit.
4.3 Kuderna-Danish (K-D) apparatus.
4.4 Boiling chips: Solvent extracted, approximately 10/40 mesh.
4.5 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+_2° C). The bath should be used in a hood.
4.6 pH indicator paper with a pH range that includes the desired
extraction pH.
4.7 Rheostat controlled heating mantle.
5.0 Reagents
5.1 The specific reagents to be employed in this method may be listed
under the organic analytical method that will be used to analyze the extract.
Check analytical method for specific extraction reagent. If a specific
extracting reagent is not listed for the compound(s) of interest, methylene
chloride shall be used.
5.2 The solvent of choice should be appropriate for the method of
measurement to be used and should give an analyte-to-solvent partition
coefficient of at least 1 to 1000.
5.3 Sodium sulfate: (ACS) Granular anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Sodium hydroxide: (ACS) 10 N in distilled water.
5.5 Sulfuric acid: (1:1) Mix equal volumes of concentrated H2S04
(ACS) with distilled water.
5.6 Distilled water.
5.7 Methylene chloride: Pesticide quality or equivalent.
6.0 Sample Collection, Preservation, and Handling
6.1 Adhere to those procedures specified in the referring analytical
methods for collection, preservation, and handling.
-------
3520 / 3
7.0 Procedure
7.1 Refer to Figure 1 to aid in understanding the procedures described
in Sections 7.2-7.6 for setting up the continuous extractor. The analyst is
reminded that the following steps apply to sample/solvent systems where the
solvent is more dense than the sample.
7.2 Place 150 ml of extracting solvent in the extractor and 350 ml of
extracting solvent in the 500-ml distilling flask. Add several boiling chips
to the distilling flask.
7.3 Measure out 1 liter of sample to be extracted. If less than
1 liter of sample is available or if high concentrations are anticipated, use
a smaller volume of sample and, if necessary, add laboratory distilled water
to bring the sample volume to 1 liter. Adjust the sample to the proper
extraction pH, add surrogate standards, and add the sample to the extraction
apparatus.
7.4 Add enough solvent to the extraction device to bring the sample
level above the U-tube connector. Using the controlling rod, balance the
distilling rate from the 500-ml distilling flask with the return flow
through the U-tube connector.
7.5 Turn on the cooling water and the heating mantle and extract the
sample for 16 hr.
7.6 Let the system cool and remove the extract contained in the 500-ml
distilling flask.
7.7 If an additional extraction is to be performed, adjust the sample
pH accordingly. Attach a 500-ml distilling flask containing 350 ml of
extracting solvent, add several boiling chips, and proceed from step 7.4.
7.8 Dry the extract by passing it through a column of anhydrous sodium
sulfate. Collect the dried extract in a Kuderna-Danish evaporative concen-
trator equipped with a 10-ml collection ampule.
7.9 Add 1 or 2 clean boiling chips to the flask and attach a three-ball
Snyder column. Prewet the Snyder column by adding about 1 ml solvent to the
top. Place the K-D apparatus on a steam or hot water bath so that the
concentrator tube and the entire lower rounded surface of the flask are
bathed in hot water or vapor. Adjust the vertical position of the apparatus
and the water temperature as required to complete the concentration in
15-20 min. At the proper rate of distillation, the balls of the column will
actively chatter but the chambers will not flood. When the apparent volume
of liquid reaches 1 ml, remove the K-D apparatus and allow it to drain for at
least 10 minutes while cooling.
7.10 Rinse the K-D apparatus with a small volume of solvent. Adjust
sample volume to 10.0 ml with the solvent to be used in instrumental analysis.
Proceed with analysis and cleanup if necessary.
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4 / WORKUP TECHNIQUES - Organic
Heating Mantle
Figure 1. Continuous liquid-liquid extractor.
-------
3520 / 5
8.0 Quality Control
8.1 Comprehensive quality control procedures are specified for each
target compound in the referring analytical method.
8.2 By fortifying distilled water or another liquid similar to the
sample matrix, the analyst should demonstrate that the compounds of interest
are being quantitatively recovered before applying this method to actual
samples.
-------
METHOD 3530
ACID-BASE CLEANUP EXTRACTION
1.0 Scope and Applications
1.1 Method 3530 is a sample cleanup procedure to be used when inter-
ferences prevent direct chromatographic measurement of the compound being
analyzed for. The method makes use of the differential solubility of the
compounds of interest and the interfering species.
2.0 Summary of Method
2.1 Interferences are removed by a series of liquid-liquid extractions
using a specified pH/solvent system.
3.0 Interferences
3.1 A procedural 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 for this method may
be necessary for reagent purification.
4.0 Apparatus and Materials
4.1 125-ml separatory funnel with Teflon stopcock.
4.2 Kuderna-Danish (K-D) apparatus equipped with a three-ball Snyder
column.
4.3 Boiling chips: Solvent extracted, approximately 10/40 mesh.
4.4 Drying column: 20-mm I.D. Pyrex chromatographic column with coarse
frit.
4.5 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+2' C). The bath should be used in a hood.
4.6 pH indicator paper with a pH range including the desired sample
pH.
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2 / WORKUP TECHNIQUES - Organic
5.0 Reagents
5.1 The specific reagents to be employed in this method may be listed
under the organic analytical method that will be used to analyze the extract
following cleanup. Check analytical method for specific extraction reagent.
If a specific extracting reagent is not listed for the compound(s) of interest,
methylene chloride shall be used.
5.2 The solvent of choice should be appropriate for the method of
measurement to be used and should give an analyte-to-solvent partition
coefficient of at least 1 to 1000.
5.3 Sodium sulfate: (ACS) Granular anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Sodium hydroxide: (ACS) 10 N in distilled water.
5.5 Sulfuric acid: (1:1) Mix equal volumes of concentrated ^$04
(ACS) with distilled water.
5.6 Distilled water.
5.7 Methylene chloride: Pesticide quality or equivalent.
6.0 Sample Collection, Preservation and Handling
6.1 Adhere to those procedures specified in the referring analytical
methods for collection, preservation and handling.
7.0 Procedure^
7.1 Place 10 ml of the extract or organic liquid waste to be cleaned up
into the separatory funnel.
7.2 Add 20 ml of the solvent indicated in Table 1.
7.3 Add 20 ml of distilled water and adjust the pH to 12-13 with sodium
hydroxide. Partition the sample into the solvent and aqueous phases by
shaking the funnel for 1 min with periodic venting to release vapor
pressure. Allow the organic layer to separate from the water phase for a
minimum of 10 min. 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, but may include stirring, filtration of the emulsion through
glass wool, or centrifugation.
7.4 Separate the aqueous phase and transfer to a 125-ml Erlenmeyer
flask.
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3530 / 3
TABLE 1. APPROPRIATE CLEANUP SOLVENT AND
STEP 7.6 PHASE FOR INDIVIDUAL COMPOUNDS
Compound being analyzed for
Benzo(a)anthracene
Benzo(a)pyrene
Benzotrichloride
Benzyl chloride
Benzo(b)f1uoranthene
Chlordane
Chlorinated dibenzodioxins
2-Chlorophenol
Chrysene
Creosote9
Cresol(s)
Cresylic acid(s)
Dichlorobenzene(s)
Dichlorophenoxy-acetic acid
Dichloropropanol
2,4-Dimethylphenol
Di nitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrotoluene
Endrin
Heptachlor
Hexachlorobenzene
Hexachlorobutadi ene
Hexachloroethane
Hexachlorocyclopentadiene
Lindane
Maleic anhydride
Methomyl
Naphthalene
Naphthoquinone
Nitrobenzene
4-Nitrophenol
Pentachlorophenol
Phenol
Phorate
Phosphorodithioic acid esters
Phthalic anhydride
2-Picoline
Pyridine
Tetrachlorobenzene(s)
Tetrachlorophenol
Toluenediainine
Toxaphene
Trichlorophenol (s)
2,4,5-TP (Silvex)
Solvent
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Ethyl ether
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Dichloromethane
Ethyl ether
Step 7.6 phase
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Aqueous
Solvent
Solvent
Aqueous
Aqueous
Solvent
Aqueous
Solvent
Aqueous
Solvent
Aqueous
Solvent
Sol vent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Aqueous
Aqueous
Aqueous
Solvent
Solvent
Solvent
Solvent
Solvent
Solvent
Aqueous
Solvent
Solvent
Aqueous
Aqueous
aPhenolic compounds will partition into the aqueous phase while
polynuclear hydrocarbon components will partition into dichloromethane.
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4 / WORKUP TECHNIQUES - Organic
7.5 Reextract the solvent layer twice more with 20-ml portions of
distilled water at pH 12-13. Combine aqueous extract.
7.6 At this point the species being analyzed for will be in either the
organic or the aqueous phase (see Table 1). If the species is in the aqueous
phase, discard the organic phase and proceed to step 7.7. If the species is
in the organic phase, discard the aqueous phase and proceed to step 7.12.
7.7 Transfer the aqueous phase to a clean separatory funnel.
7.8 Adjust the aqueous layer to a pH of 1-2 with sulfuric acid.
7.9 Add 20 ml of solvent to the funnel and shake for 2 min. Allow
the solvent to separate from the aqueous phase and collect the solvent
in a 100-ml Erlenmeyer flask.
7.10 Add a second 20-ml volume of solvent to the separatory funnel and
reextract at pH 1-2 a second time, combining the extracts in the Erlenmeyer
flask.
7.11 Perform a third extraction in the same manner.
7.12 Pour the combined organic extracts through a drying column con-
taining 10 cm of anhydrous sodium sulfate, and collect it in a Kuderna-Danish
(K-D) flask equipped with a 10-ml concentrator tube. Rinse the Erlenmeyer
flask and column with 20 ml of solvent to complete the quantitative transfer.
7.13 Add 1 or 2 clean boiling chips to the flask and attach a three-ball
Snyder column. Prewet the Snyder column by adding about 1 ml of solvent to
the top. Place the K-D apparatus on a steam or hot water bath so that the
concentrator tube and the entire lower rounded surface of the flask is bathed
in hot water or vapor. Adjust the vertical position of the apparatus and the
water temperature as required to complete the concentration in 15-20 min.
At the proper rate of distillation, the balls of the column will actively
chatter but the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow it to drain for at least
10 min while cooling.
7.14 If the appropriate analytical solvent is the same as that used for
the above extraction, transfer the extract to a 10-ml volumetric flask
and adjust the volume to 10 ml. If a different solvent is to be used for
sample measurement, proceed as in step 7.15.
7.15 Increase the temperature of the hot water bath to 95-100° C.
Remove the Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1-2 ml of the extraction solvent. Note: A 5-ml
syringe is recommended for this operation. Attach a micro-Snyder column to
the concentrator tube and prewet the column by adding about 0.5 ml of the
solvent to the top. Place the micro K-D apparatus on the water bath so
that the concentrator tube is partially immersed in the hot water. Adjust
-------
3530 / 5
the vertical position of the apparatus and the water temperature as required
to complete concentration in 5-10 min. At the proper rate of distillation,
the balls of the column will actively chatter but the chambers will not
flood. When the apparent volume of the liquid reaches 2.5 ml, remove the K-D
apparatus and allow it to drain for at least 10 min while cooling. Add an
additional 2 ml of the extraction solvent through the top of the micro-Snyder
column and resume concentrating as before. When the apparent volume of
liquid reaches 0.5 ml, remove the K-D apparatus and allow it to drain for at
least 10 min while cooling. Remove the micro-Snyder column and rinse its
lower joint into the concentrator tube with a minimum amount of the extraction
solvent. Transfer to a 10-ml volumetric flask and adjust the extract volume
to 10 ml. Store in refrigerator, if further processing will not be performed
immediately. If the sample extract requires no further cleanup, proceed with
gas chromatographic analysis. If the sample requires further cleanup,
proceed as appropriate.
8.0 Quality Control
8.1 Comprehensive quality control procedures are specified for each
target compound in the referring analytical method.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
-------
METHOD 3540
SOXHLET EXTRACTION
1.0 Scope and Application
1.1 Method 3540 is a procedure for extracting nonvolatile and semivola-
tile organic compounds from solids such as soils and sludges. The Soxhlet
extraction process ensures intimate contact of the sample matrix with the
extraction solvent. Subsequent cleanup and detection are described in the
organic analytical method that will be used to analyze the extract.
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. Methylene chloride should be
employed when a solvent is not specified. The extract is then dried and
concentrated, and either cleaned up further or analyzed directly by the
appropriate measurement technique.
3.0 Interferences
3.1 A procedural 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 Procedures for the removal of interfering compounds coextracted
with target compounds are described in the organic analytical method that will
be used to analyze the extract.
4.0 Apparatus and Materials
4.1 Soxhlet extractor: 40-mm I.D., with 500-ml round-bottom flask.
4.2 Kuderna-Danish apparatus with three-ball Snyder column.
4.3 Chromatographic column: Pyrex, 20-mm I.D., approximately 400 mm
long, with coarse-fritted plate on bottom and an appropriate packing medium.
4.4 Glass or paper thimble or glass wool to retain sample in Soxhlet
extraction device. Should drain freely and may require purification before use.
4.5 Boiling chips: Approximately 10/40 mesh. Heat to 400° C for
30 min or Soxhlet extract with methylene chloride.
4.6 Rheostat controlled heating mantle.
-------
2 / WORKUP TECHNIQUES - Organic
5.0 Reagents
5.1 The specific reagents to be employed in this method may be listed
under the organic analytical methods that will be used to analyze the extract.
Check analytical method for specific extraction reagent. If a specific
extracting reagent is not listed for the compound(s) of interest, methylene
chloride shall be used.
5.2 The solvent of choice should be appropriate for the method of
measurement to be used and should give an analyte-to-solvent partition
coefficient of at least 1 to 1000.
5.3 Sodium sulfate: (ACS) Granular anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Soil samples: Soil samples shall be extracted using either of the
following solvent systems.
5.4.1 Toluene/Methanol, 10:1 v/v ACS reagent grade only.
5.4.2 Acetone/Hexane, 1:1 v/v ACS reagent grade only.
5.5 Methylene chloride: Pesticide quality or equivalent.
6.0 Sample Collection, Preservation, and Handling
6.1 Adhere to those procedures specified in the referring analytical
methods for collection, preservation, and handling.
7.0 Procedure
7.1 Blend 10 g of the solid sample with an equal weight of anhydrous
sodium sulfate and place in either a glass or paper extraction thimble. The
extraction thimble must drain freely for the duration of the extraction
period. The use of a glass wool plug above and below the sample is also
acceptable.
7.2 Place 300 ml of the extraction solvent into a 500-ml round-bottom
flask containing a boiling stone. Attach the flask to the extractor, and
extract the solids for 16 hr.
7.3 Allow the extract to cool after the extraction is complete. Rinse
the condenser with the extraction solvent and drain the Soxhlet apparatus
into the collecting round-bottom flask. Filter the extract and dry it by
passing it through a 4-in. column of sodium sulfate which has been washed
with the extracting solvent. Collect the dried extract in a 500-ml Kuderna-
Danish (K-D) flask fitted with a 10-ml graduated concentrator tube. Wash the
extractor flask and sodium sulfate column with 100-125 ml of the extracting
solvent.
-------
3540 / 3
7.4 Add 1 or 2 clean boiling chips to the flask and attach a three-ball
Snyder column. Prewet the Snyder column by adding about 1 ml solvent to the
top. Place the K-D apparatus on a steam or hot water bath so that the
concentrator tube and the entire lower rounded surface of the flask are
bathed in hot water or vapor. Adjust the vertical position of the apparatus
and the water temperature as required to complete the concentration in
15-20 min. At the proper rate of distillation, the balls of the column will
actively chatter but the chambers will not flood. When the apparent volume
of liquid reaches 1 ml, remove the K-D apparatus and allow it to drain for at
least 10 min while cooling.
7.5 Rinse the K-D apparatus with a small volume of solvent. Adjust the
sample volume to 10.0 ml with the solvent to be used in instrumental analysis.
Proceed with analysis and cleanup if necessary.
8•° Quality Control
8.1 Comprehensive quality control procedures are specified for each
target compound in the referring analytical method.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
-------
METHOD 3550
SONICATION EXTRACTION
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 and sludges. The
sonication process ensures intimate contact of the sample matrix with the
extraction solvent. Subsequent cleanup and detection are described in the
organic analytical method that will be used to analyze the extract.
2.0 Summary of Method
2.1 A weighed sample of the solid waste is ground, mixed with the
extraction medium, then dispersed into the solvent using sonication. The
extract is then dried with anhydrous sodium sulfate and concentrated with
Kuderna-Danish apparatus. The resulting solution may then be cleaned up
further or analyzed directly using the appropriate technique.
3.0 Interferences
3.1 A procedural 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 Procedures for the removal of interfering compounds coextracted
with target compounds are described in the organic analytical method that
will be used to analyze the extract.
4.0 Ap p a rat us a n d Ma t e r i a1s
4.1 Apparatus for grinding: If the sample will not pass through a 1-mm
standard sieve or cannot be extruded through a 1-mm opening, it should be
processed into a homogeneous sample that meets these requirements. Fisher
Mortar Model 155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or
an equivalent brand and model, is recommended for sample processing. This
grinder should handle most solid samples except gummy, fibrous, or oily
materials.
4.2 Sonication: A horn-type sonicator equipped with a titanium tip
should be used. The following sonicators, or an equivalent brand and model,
are recommended: Sonifer/cell disrupter, model W-350, Ultrasonics Inc., or
-------
2 / WORKUP TECHNIQUES - Organic
Sonic dismembrator, model 300, Fisher Scientific Co., Catalog Number 15-338-
40.
4.3 Kuderna-Danish apparatus with three-ball Snyder column.
4.4 Chromatographic column: Pyrex, 20-mm I.D., approximately 400-mm
long, with coarse-fritted plate on bottom.
4.5 Rheostat-controlled heating mantle.
5.0 Reagents
5.1 The specific reagents to be employed in this method may be listed
under the organic analytical method that will be used to analyze this extract.
Check analytical method for specific extraction reagent. If a specific
extracting reagent is not listed for the compound(s) of interest, methylene
chloride shall be used.
5.2 The solvent of choice should be appropriate for the method of
measurement to be used and should give an analyte-to-solvent partition
coefficient of at least 1 to 1000.
5.3 Sodium sulfate: (ACS) Granular anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Sodium hydroxide: (ACS) 10 N in distilled water.
6.0 Sample Collection, Preservation, and Handling
6.1 Adhere to those procedures specified in the referring analytical
methods for collection, preservation, and handling.
7.0 Procedure
7.1 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 Weigh 10.0 g of suitably dispersed material into a 75-ml glass
flask, and add 30 ml of an appropriate solvent. Sonicate with agitation for
approximately 15 min. Filter the resulting suspension. Reextract the solid
residue with an additional 30-ml portion of solvent. Repeat the extraction a
third time so as to sonicate for a total of 45 min.
7.3 After the extraction is complete, filter the extract and dry it by
passing it through a 4-in. column of sodium sulfate which,has been washed
-------
3550 / 3
with the extracting solvent. Collect the dried extract in a 500-ml Kuderna-
Danish (K-D) flash fitted with a 10-ml graduated concentrator tube and a
three-ball Snyder solumn. Wash the extractor flask and sodium sulfate column
with 100-125 ml of the extracting solvent.
7.4 Add 1 or 2 clean boiling chips to the flask and attach a three-ball
Snyder column. Prewet the Snyder column by adding about 1 ml solvent to the
top. Place the K-D apparatus on, a steam or hot water bath so that the
concentrator tube and the entire lower rounded surface of the flask are
bathed in hot water or vapor. Adjust the vertical position of the apparatus
and the water temperature as required to complete the concentration in
15-20 min. At the proper rate of distillation, the balls of the column will
actively chatter but the chambers will not flood. When the apparent volume
of liquid reaches 1 ml, remove the K-D apparatus and allow it to drain for at
least 10 min while cooling. Transfer to a 10-ml volumetric flask and adjust
the volume to 10 ml.
7.5 Rinse the K-D apparatus with a small volume of solvent. Adjust
the sample volume to 10.0 ml with the solvent to be used in instrumental
analysis. Proceed with analysis and cleanup if necessary.
8.0 Quality Control
8.1 Comprehensive quality control procedures are specified for each
target compound in the referring analytical method.
8.2 The analyst should demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
-------
SECTION FIVE
SAMPLE INTRODUCTION TECHNIQUES
The methods on the following pages (5000 series) are appropriate for
sample introduction into instrumentation specified by organic analytical
techniques (8000 series).
-------
METHOD 5020
HEADSPACE METHOD
1.0 Scope and Application
1.1 Method 5020 is a static headspace technique for extracting volatile
organic compounds in pastes, solids, and liquids. It is a simple method that
allows large numbers of samples to be analyzed in a relatively short period
of time. Because of the large variability and complicated matrices of waste
samples in the solid and paste forms, detection limits for this method may
vary widely among samples. The method works best for compounds with boiling
points of less than 125" C. The sensitivity of this method will depend on the
equilibria of the various compounds between the vapor and dissolved phases.
1.2 This method is recommended for use by, or under the supervision
of, analysts experienced in the operation of gas chromatographs and in the
interpretation of chromatograms.
2.0 Summary of Method
The sample is collected in sealed glass containers and allowed to
equilibrate at 90" C. A sample of the headspace gas is withdrawn with a
gas-tight syringe for analysis by the appropriate gas chromatographic method
(8010, 8015, 8020, or 8030).
3.0 Interferences
Refer to Methods 8010, 8015, 8020, or 8030.
4.0 Apparatus and Materials
4.1 Gas-tight syringe: 5-cc with chromatographic needles.
4.2 Headspace standard solutions: Prepare according to procedures
in 8010, 8015, 8020, or 8030 at 50 ng/ul and 250 ng/ul concentrations.
4.3 Vials: 125-ml Hypo-Vials (Pierce Chemical Co., #12995, or
equivalent).
4.4 Septa: Tuf-Bond (Pierce #12720, or equivalent).
4.5 Seals: Aluminum (Pierce #13214, or equivalent).
-------
2 / SAMPLE INTRODUCTION TECHNIQUES
4.6 Crimper: Hand (Pierce #13212, or equivalent).
5.0 Reagents
5.1 Refer to Methods 8010, 8015, 8020, or 8030.
6.0 Sample Collection, Preservation, and Handling
6.1 Refer to Methods 8010, 8015, 8020, or 8030.
7.0 Procedure
7.1 Place 10.0 g each of the well-mixed waste sample into three
separate 125-ml septum seal vials.
7.2 Dose one sample vial through the septum with 200 u,l of a 50-ng/u.l
methanolic standard of the compounds of interest. Label this "1-ppm spike."
7.3 Dose a separate (empty) 125-ml septum seal vial with 200 ul of the
50 ng/ul standard methanol solution. Label this "1-ppm standard."
7.4 Place the sample, 1-ppm-spike, and 1-ppm-standard vials into
a 90° C water bath for 1 hr. Store the remaining sample vial at 4.0° C for
possible future analysis.
7.5 While maintaining the vials at 90° C, withdraw 2 ml of the headspace
gas with a gas-tight syringe and analyze by injecting into a GC, operating
under the appropriate conditions for the GC measurement method being used
(8010, 8015, 8020, or 8030).
7.6 Analyze the 1-ppm standard and adjust instrument sensitivity to
give a minimum response of at least 2x the background. Record retention
times (RT) and peak areas of compounds of interest.
7.7 Analyze the 1-ppm spiked sample in the same manner. Record RT's
and peak areas.
7.8 Analyze the undosed sample as in Section 7.7.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
-------
5020 / 3
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed to
validate the sensitivity and accuracy of the analysis. If the fortified
samples do not indicate sufficient sensitivity to detect less than or equal
to 1 u.g/g of sample, then the sensitivity of the instrument should be
increased. Where doubt exists over the identification of a peak on the
chromatograph, confirmatory techniques such as mass spectroscopy should be
used.
9.0 References
1. Hachenberg, H. and Schmidt, A. 1979. Gas chromatographic headspace
analysis. Philadelphia: Hayden & Sons Inc.
2. Friant, S.L. and Suffet, I.H. 1979. Interactive effects of temper-
ature, salt concentration, and pH on headspace analysis for isolating
volatile trace organics in aqueous environmental samples. Anal. Chem.
51:2167-2172.
-------
METHOD 5030
PURGE-AND-TRAP METHOD
1.0 Scope and Application
1.1 Method 5030 is used to determine the concentration of volatile
organic compounds in a variety of liquid and solid waste matrices.
1.2 This method is applicable to nearly all types of samples, regardless
of water content, including aqueous sludges, caustic liquors, acid liquors,
waste solvents, oily wastes, groundwater, mousses, tars, fibrous wastes,
polymeric emulsions, filter cakes, spent carbons, spent catalysts, soils, and
sediments.
1.3 For highly volatile matrices, direct injection preceded by dilu-
tion should be used to prevent gross contamination of the instrumentation.
For pastes, dilution of the sample until it becomes free-flowing is used to
ensure adequate interfacial area. The success of this method also depends on
the level of interferences in the sample; results may vary due to the large
variability and complicated matrices of solid waste samples.
1.4 Method 5030 is based upon a purge-and-trap, gas chromatographic
procedure.
1.5 This method is recommended for use by, or under the supervision of,
analysts experienced in the use of purge-and-trap systems and gas chromato-
graphs and skilled in the interpretation of chromatograms.
2.0 Summary of Method
2.1 A portion of solid waste is dispersed in polyethylene glycol (PEG)
or distilled-in-glass methanol to dissolve the volatile organic constituents.
A portion of the PEG or methanol solution is combined with water in a specially
designed purging chamber. For liquid and some semiliquid samples, PEG or
methanolic extraction will not be necessary. An inert gas is then 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 trapped.
After purging is completed, the sorbent column is heated and backflushed with
inert gas to desorb the components onto a gas chromatographic column.
(SPECIAL NOTE: For Methods 8020 and 8030, drying of the trap for 4 min under
helium flow is required. See Figure 5 for configuration.) The gas chromato-
graphic column is heated to elute the components which are detected by the
appropriate detector (Methods 8010, 8020, 8030).
-------
5030 / 2
3.0 Interferences
3.1 Low molecular weight impurities in PEG can be volatilized during
the purging procedure. Thus, the PEG employed in this method must be purified
before use as described in Section 5.3.
3.2 Impurities in the purge gas and organic compounds out-gasing from
the plumbing ahead of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from contam-
ination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-TFE plastic tubing, non-TFE thread sealants, or flow
controllers with rubber components in the purging device should be avoided.
3.3 Samples can be contaminated by diffusion of volatile organics
(particularly fluorocarbons and methylene chloride) through the septum seal
into the sample during shipment and storage. A field reagent blank prepared
from reagent water and carried through the sampling and handling protocol can
serve as a check on such contamination.
3.4 Contamination by carryover can occur whenever high-level and low-
level samples are analyzed sequentially. Whenever an unusually concentrated
sample is encountered, it should be followed by an analysis of reagent water
(PEG or methanol solution) to check for cross contamination. After each use,
the purging chamber is cleaned as described in Section 7.12. The trap and
other parts of the system are also subject to contamination; therefore,
frequent additional bakeout and purging or the entire system may be required.
4.0 Apparatus and Materials
4.1 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: the purging chamber, trap, and the desorber.
Several complete devices are commercially available.
4.1.1 The purging chamber must be designed to accept 5-ml or
25-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 bubb-les wtth 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 purging chamber,
illustrated in Figure 1, meets these design criteria.
4.1.2 The sorbent trap consists of a 1/8-in. O.D. (0.105-in.
I.D.) x 25-cm-long stainless steel tube packed with the appropriate
absorbents as described in Table 1 (see Figures 2 and 3).
4.1.3 The desorber must be capable of rapidly heating the trap
to 180* C within 30 sec.
-------
5030 / 3
OPTIONAL
FOAM TRAP
Exit '/« Inch 0. D.
14 mm 0. 0.
Inlet V« Inch 0. D.
Inch 0. D. Exit
10 mm Glass Fnt
Medium Porosity
Sample Inlet
2-Way Syringe Valve
17 cm, 20 Gauge Syringe Needle
6 mm 0. D. Rubber Septum
— 10 mm 0. D.
Iniet
/• Inch 0. D.
II
1/16 Inch 0 D.
Stainless Steei
13x Moiecuiar
Sieve Purge
Gas Filter
Purge Gas
Flow Control
Figure 1. Purging chamber.
-------
5030 / 4
TABLE 1. PURGE-AND-TRAP PARAMETERS
Purge Gas
Purge Gas Flow
Rate (ml/mi'n)
Purge Time (min)
Purge Temperature
Desorb Temperature (*C)
Sorbents to be used
in packing tube
8010
Nitrogen or
Helium
40
11.0
Ambient
180*
A
Analysis
8015
Helium
40
12.0
Ambient
180*
B
method3
8020
Nitrogen or
Helium
40
12.0
Ambient
180'
B
8030
Helium
20 + 1
30.0
85' C
100*
B
Measurement method to be employed for identification and quanti-
fication.
KEY: A = Porous polymer packing, 60/80 mesh, chromatographic
grade Tenax GC (2,6-Diphenylene oxide).
Three percent OV-1 on Chromosorb-W 60/80 mesh (optional).
Silica gel, 35/60 mesh Davison grade-15 or equivalent.
Coconut charcoal, 6/10 mesh, Barnaby Chaney C.A. - 580-26
lot #M-2649 or equivalent.
Refer to Figure 2 for column packing.
B = Porous polymer packing, 60/80 mesh, chromatographic grade
Tenax GC (2,6-Diphenylene oxide).
Three percent OV-1 on Chromosorb-W 60/80 mesh (optional).
Refer to Figure 3 for column packing.
Revised 4/84
-------
5030 / 5
Packing Procedure
Construction
Glass Wool
Activated
Charcoal
Grade 15
Sihca Gei
3% OV-1
Glass Wool
7.7 cm
Tenax 7.7 cm
1 cm
5 mm
M
Resistance
Wire Wrapped
Solid
(Double Layer)
Resistance
W.re Wrapped
Scud
(Sing:e Layer)
8 cm
Compression
Fining Nut
and Ferrules
Thermocouple/
Controller
Sensor
Electronic
Temperature
Control and
Pyrometer
Tubing 25 cm
0.105 In. I.D.
0.125 In.O.D.
Stainless Steel
Trap Inlet
Figure 2. Trap packings and construction for Method 8010.
-------
5030 / 6
Packing Procedure
Construction
Glass Wool 5 mm
r>/s
Tenax 23 cm
3% 0V—1 1 cm
Glass Wool 5 mm
%
n
<•-
ft*
^
Compression Fining Nut
and Ferrules
14 Ft. 7ft/Foot Resistance
Wire Wrappefl Solid
Thermocouple/Controller Sensor
Electronic
Temperature
Control and
Pyrometer
Tubing 25 cm
0.105 In. I.D.
0.125 In. O.D.
Stainless Steei
Trap Inlet
Figure 3. Trap packing and construction for Methods 8020 and 8030.
-------
SECTION SIX
MULTIELEMENT INORGANIC ANALYTICAL METHODS
Methods appropriate for multielement inorganic analysis of samples
(6000 series) are included on the following pages.
-------
SECTION SEVEN
INORGANIC ANALYTICAL METHODS
Methods appropriate for inorganic analysis (7000 series) for specific
elements of interest are included on the following pages.
-------
5030 / 7
4.1.4 The purge-and-trap device may be assembled as a separate
unit or be coupled to a gas chromatograph as illustrated in
Figures 4 through 6.
4.2 Syringes: 5-ml and 25-ml glass hypodermic, equipped with 20-gauge
needle, at least 15 cm in length.
4.3 Micro syringes: 10 u.1, 25 u.1, 100 u.1, 250 ul, 500 u.1, and
1,000 u.1. These syringes should be equipped with 20-gauge needles
having a length sufficient to extend from the sample inlet to within
1 cm of the glass frit in the purging device (see Figure 1). The needle
length required will depend, upon the dimensions of the purging device
employed.
4.4 Centrifuge tubes: 50-ml round-bottom glass centrifuge tubes
with Teflon-lined screw caps. The tubes must be marked before use to
show an approximate 20-ml graduation (Kimble #45212 or equivalent).
4.5 Centrifuge: Capable of accommodating 50-ml glass tubes.
4.6 Syringe valve: 2-way, with Luer ends (2 each; Hamilton #86725
valve equipped with one Hamilton #35033 Luer fitting or equivalent).
4.7 Syringe: 5-ml, gas-tight with shutoff valve.
4.8 Bottle: 15-ml, screw-cap, Teflon cap liner.
4.9 Balance: Analytical, capable of accurately weighing 0.0001 g.
4.10 Rotary evaporator: Equipped with Teflon-coated seals (Buchi
Rotavapor R-110 or equivalent).
4.11 Vacuum pump: Mechanical, two-stage.
5.0 Reagents
5.1 Trap materials (see Table 1 and Figures 2 and 3 for configuration).
5.1.1 2,6-Diphenylene oxide polymer: 60/80 mesh Tenax,
chromatographic grade or equivalent.
5.1.2 Methyl silicone packing: 3% OV-1 on 60/80 mesh Chromo-
sorb-W or equivalent.
5.1.3 Silica gel, Davison Chemical (35/60 mesh), grade 15 or
equivalent.
-------
5030 / 8
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5030 / 11
5.2 Reagent water: Reagent water is defined as a water in which
an interferent is not observed at the method detection limit of the
compounds of interest.
5.2.1 Reagent water may be generated by passing tap water
through a carbon filter bed containing about 500 g of activated
carbon (Calgon Corp., Filtrasorb-300 or equivalent).
5.2.2 A water purification system (Millipore Super-Q or
equivalent) may be used to generate reagent water.
5.2.3 Reagent water may also be prepared by boiling water for
15 min. Subsequently, while maintaining the temperature at 90* C,
bubble a contaminant-free inert gas through the water for 1 hr.
While still hot, transfer the water to a narrow-mouth screw-cap
bottle and seal with a Teflon-lined septum and cap.
5.3 Reagent PEG (polyethylene glycol; for solid samples): Reagent PEG
is defined as PEG having a nominal average molecular weight of 400, and in
which interferents are not observed at the method detection limit for com-
pounds of interest. Methanol which has been distilled in glass can be used
as a substitute for PEG.
5.3.1 Reagent PEG is prepared by purification of commercial
PEG having a nominal average molecular weight of 400. The PEG 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 in a water bath at 90-100* C and vacuum is maintained at
less than 10 mm Hg for at least 1 hr 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.
5.3.2 In order to demonstrate that all interfering volatiles
have been removed from the PEG, a reagent water/PEG blank must be
analyzed.
6.0 Sample Collection, Preservation, and Handling
6.1 Refer to Method 8010, 8020, or 8030 for pertinent information.
7.0 Procedures
7.1 Assemble the purge-and-trap device (see Figures 4 through 6).
Purge parameters to be used depend on the compounds being analyzed for;
see Table 1. Pack the trap as shown in Figure 2 or 3 and condition
overnight at a nominal 180* C by backflushing with an inert gas flow of at
least 20 ml/min. Daily, prior to use, condition the trap for 10 min by
backflushing at 180* C.
-------
5030 / 12
7.2 Remove standards and samples from cold storage (approximately
an hour prior to an analysis) and bring to room temperature by placing in
a warm water bath at 20-25* C.
7.3 Adjust the purge gas (nitrogen or helium) flow rate according
to Table 1.
7.4 Operate the gas chromatograph using the conditions described in
the appropriate method, 8010, 8020, or 8030.
7.5 Attach the trap inlet to the purging device, and set the
device to the purge mode. Open the syringe valve located on the purging
device sample introduction needle.
7.6 Remove the plunger from a 5-ml syringe and attach a closed
syringe valve. Open the sample bottle (or standard) and carefully pour
the sample into the syringe barrel until it overflows. (NOTE: For pastes
it may be necessary to dilute the sample by adding a nonvolatile solvent to
the sample. In such cases diluting can be performed in the purging device.)
7.7 PEG extraction procedure for solids (methanol which has been
distilled in glass can be used as a substitute for PEG). Sample aliquots for
extraction should be transferred as quickly as possible to minimize loss of
volatiles from the sample.
7.7.1 To a 50-ml glass centrifuge tube with Teflon-lined cap,
add 40'ml of reagent PEG. Weigh the capped centrifuge tube and PEG
on an analytical balance.
7.7.2 Using an appropriate implement, transfer approximately
2 g of sample to the PEG in the centrifuge tube in such a fashion
that the sample is dissolved in or submerged in the PEG as quickly
as possible. Take care not to touch the sample-transfer implement
to the PEG. Recap the centrifuge tube immediately and weigh on
an analytical balance to determine an accurate sample weight.
7.7.3 Disperse the sample by vigorous agitation for 1 min.
The mixture may be agitated manually or with the aid of a vortex-mixer.
If the sample does not disperse during this process, sonify the mixture
in an ultrasonic bath for 30 min. Allow the mixture to stand until a
clear supernatant is obtained as the sample extract. Centrifuge if
necessary to facilitate phase separation.
7.7.4 The sample extract may be stored /or future analytical
needs. If this is desired, transfer the solution to a 10-ml screw
cap vial with Teflon cap liner. Store at -10 to -20* C, and protect
from light.
7.7.5 Add an aliquot of the sample extract to 5 ml reagent
water.
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5030 / 13
7.8 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. Since this process of taking an aliquot destroys the
validity of the liquid samples for future analysis, the analyst should
fill a second syringe at this time to protect against possible loss of
data.
7.9 Attach the syringe-valve assembly to the syringe valve on the
purging device. Open the syringe valve and inject the sample into the
purging chamber. Close both valves and purge the sample for the time
specified in Table 1. If Method 8020 will be used for analysis of
the sample, dry the trap by maintaining a flow rate of 40 ml/min dry
purge for 4 min.
7.10 Attach the trap to the chromatograph, and adjust the device
to the desorb mode. Introduce the trapped materials to the GC column
by rapidly heating the trap to the backflush temperature indicated in
Table 1, while backflushing the trap with an inert carrier gas at
20 to 60 ml/min for 4 min. If rapid heating cannot be achieved, the gas
chromatographic column must be used as a secondary trap by cooling it to
30* C (or subambient, if problems persist) instead of the initial program
temperature of 45* or 50* C.
7.11 Return the purge trap device to the purge mode. '
7.12 Allow the trap to cool for 8 min. Replace the purging chamber
with a clean purging chamber. The purging chamber is cleaned after each
use by sequential washing with acetone, methanol, detergent solution, and
distilled water and drying at 105* C.
7.13 Close the syringe valve on the purging chamber after 15 sec to
begin gas flow through the trap. Purge the trap at ambient temperature
for 4 min. Recondition the trap by heating it to 180* C. Do not allow
the trap temperature to exceed 180* C, since the sorption/desorption is
adversely affected by heating the trap to higher temperatures. After
heating the trap for approximately 7 min, turn off the trap heater. When
cool, the trap is ready for the next sample.
7.14 The analysis of blanks is most important in the purge-and-trap
technique since the purging device and the trap can become contaminated
by residues from very concentrated samples or by vapors in the labora-
tory. Prepare blanks by filling a sample bottle with organic-free water.
Blanks should be sealed, stored at 4* C, and analyzed with each group of
samples.
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5030 / 14
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed to
validate the sensitivity and accuracy of the analysis. If the fortified
samples do not indicate sufficient sensitivity to detect less than or equal
to 1 ug/g of sample, then the sensitivity of the instrument should be increased
or the extract subjected to additional cleanup. Where doubt exists over the
identification of a peak on the chromatograph, confirmatory techniques such
as mass spectroscopy should be used.
9.0 References
3.
4.
Bellar, T.A., and J.J. Lichtenberg.
Assoc. 66(12) :739-744.
1974. J. Amer. Water Works
Bellar, T.A., and J.J. Lichtenberg. 1979. 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.
Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 11 - Purgeables and
Category 12 - Acrolein, Acrylonitrile, and Dichlorodif luoromethane.
Report for EPA Contract 68-03-2635 (in preparation).
Ligon, W.V. and H. Grade. 1981. Poly(ethylene glycol ) as a diluent
for preparation of standards for volatile organics in water. Anal.
Chem. 53:920-921.
-------
METHOD 7040
ANTIMONY (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7040 is an atomic absorption procedure approved for deter-
mining the concentration of antimony in wastes, mobility procedure extracts,
soils, and groundwater. 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 7040, samples must be prepared for
direct aspiration. The method of sample preparation will vary according
to the sample matrix. Aqueous samples are subjected to an acid digestion
procedure (Method 3010). Sludge samples are prepared using the procedure
described in Method 3050. For samples containing oils, greases, or waxes,
the procedures described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a repre-
sentative aliquot is aspirated into an air/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the antimony
concentration. Background correction must be employed for all analyses.
2.3 Typical detection limits for this method are 0.2 mg/1; typical
sensitivities are 0.2 mg/1.
3.0 Interferences
3.1 Background correction is required since nonspecific absorption and
light scattering can be significant at the analytical wavelength.
3.2 Excess concentrations of copper and nickel (and possibly other
elements) as well as acids can interfere with antimony analyses. If the
sample contains these matrix types, either matrices of the standards should
be matched to those of the sample 0£ the sample should be analyzed using a
nitrous oxide/acetylene flame.
3.3 High lead concentrations may cause a measurable spectral inter-
ference on the 217.6-nm line. If this interference is expected, a secondary
wavelength should be employed.
3.4 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
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2 / INORGANIC ANALYTICAL METHODS
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, pho-
tomultiplier detector, adjustable slits, and provisions for background
correction.
4.2 Antimony hollow cathode lamp or electrodeless discharge lamp.
4.3 Strip chart recorder (optional).
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Antimony standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, £r_
dissolve 2.7426 g of antimony potassium tartrate (analytical reagent grade) in
distilled deionized water and dilute to 1 liter.
5.4 Antimony working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
5.5 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.6 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
the flame conditions by replacing the cylinder before the pressure has fallen
to 50 psig.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
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7040 / 3
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3010; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 217.6-nm line is suggested as the analytical wavelength of
choice. However, under the conditions discussed in Section 3.3, a less
sensitive secondary wavelength may be useful. Background correction should
be employed for all analyses.
7.3 Air/acetylene flames should be fuel lean.
7.4 Follow the manufacturer's operating instructions for all other
instrument parameters.
7.5 Either (1) run a series of antimony standards and construct a
calibration curve by plotting the concentrations of the standards against
the absorbances o£ (2) for the method of standard additions, plot added
concentration versus absorbance. For instruments that read directly in
concentration, set the curve corrector to read out the proper concentration.
7.6 Analyze, by the method of standard additions, all EP extracts, all
samples analyzed as part of a deli sting petition, and all samples that suffer
from matrix interferences.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 The final calculated concentration should take into account all
dilution and concentration factors.
8.0 quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
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4 / INORGANIC ANALYTICAL METHODS
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
ft
METHOD 7041
ANTIMONY (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 Scope and Application
1.1 Method 7041 is an atomic absorption procedure approved for
determining the concentration of antimony in wastes, mobility procedure
extracts, soils, and groundwater. 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 7041, samples must be prepared in order
to convert organic forms of antimony 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. For samples containing oils, greases, or waxes, the procedures
described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the antimony concen-
tration.
2.3 The typical detection limit for this method is 3 u.g/1.
3.0 Interferences
3.1 Temperature and times for the dry and char (ash) cycles must be
carefully selected since antimony is volatile in the presence of certain
chloride salts (e.g., ammonium chloride).
3.2 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result in severe
physical and chemical interferences. Furnace parameters must be optimized
to minimize these effects.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, antimony 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.
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2 / INORGANIC ANALYTICAL METHODS
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, the tube should be cleaned by operating the furnace at higher
atomization temperatures.
3.5 High lead concentrations may cause a measurable spectral inter-
ference on the 217.6-nm line. If this interference is expected, a secondary
wavelength should be employed.
4.0 Apparatus and Materials
4.1 Griffin beakers of assorted sizes.
4.2 Qualitative filter paper.
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
strip chart recorder.
4.4 Antimony hollow cathode lamp or electrodeless discharge lamp.
4.5 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.6 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any prob-
lems 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 1000 u.1 as required.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Hydrochloric acid (1:1): Prepared from Type II water and hydro-
chloric acid. Hydrochloric acid should be analyzed to determine level
of impurities. If impurities are detected, all analyses should be blank-
corrected.
-------
7041 / 3
5.4 Antimony standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or^
dissolve 2.7426 g of antimony potassium tartrate (analytical reagent grade)
in Type II water and dilute to 1 liter.
5.5 Antimony working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared in the
manner described in Sections 7.1.1-7.1.3. Sludge-type samples should be
prepared according to Method 3050, and samples containing oils, greases, or
waxes may be prepared according to Methods 3030 or 3040. 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 representative aliquot of the well-mixed sample
to a Griffin beaker and add 3 ml of cone. HN03. Cover the beaker with
a 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. Low recoveries for antimony may result if the sample is allowed
to go to dryness.) Cool the beaker and add another 3-ml portion of
cone. HN03. Re-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.
7.1.2 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 reflux-
ing). Again, evaporate to near dryness and cool the beaker. Add a
small quantity of redistilled 1:1 HC1 (5 ml/100 ml of final solution)
and warm the beaker to dissolve any precipitate or residue resulting
from evaporation.
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4 / INORGANIC ANALYTICAL METHODS
7.1.3 Wash down the beaker walls and watch glass with distilled
water and, when necessary, filter or centrifuge the sample to remove
silicates and other insoluble material that could clog the nebulizer.
(NOTE: Filtration should be done only if there is concern that insolu-
ble materials will clog the nebulizer since this additional step is
liable to cause sample contamination unless the filter and filtering
apparatus are thoroughly cleaned and prerinsed with dilute nitric acid.)
Adjust the volume to some predetermined value based on the expected
metal concentrations. The sample is now ready for analysis.
7.2 The 217.6-nm line is suggested as the analytical wavelength of
choice. However, under the condition discussed in Section 3.5, a secondary
wavelength may be useful.
7.3 Background correction shall be employed for all analyses.
7.4 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.5 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Since temperature-sensing mechanisms and temperature con-
trollers 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.
7.6 Inject a measured u.1 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.
7.7 Either (1) run a series of antimony 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 concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.8 Analyze, by the method of standard additions, all EP extracts and
all samples that suffer from matrix interferences.
7.9 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.10 Duplicates, spiked samples, and check standards should be routinely
analyzed.
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7041 / 5
7.11 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 or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole 'sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7060
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 Scope and Application
1.1 Method 7060 is an atomic absorption procedure approved for deter-
mining the concentration of arsenic in wastes, mobility procedure extracts,
soils, and groundwater. 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. For samples containing oils, greases, or waxes, the procedures
described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive 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 radiation
during atomization will be proportional to the arsenic concentration.
2.3 The typical detection limit for this method is 1 ug/1.
3.0 Interferences
3.1 Elemental arsenic and many of its compounds are volatile and
therefore samples may be subject to losses of arsenic during sample prepa-
ration. Spike samples and relevant standard reference materials should be
processed to determine if the chosen dissolution method is appropriate.
3.2 Likewise, caution must be employed during the selection of tem-
perature and times for the dry and char (ash) cycles. A nickel nitrate
solution must be added to all digestate prior to analysis to minimize vola-
tilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graph-
ite furnace analysis, arsenic analysis can suffer from severe nonspecific
absorption and light scattering caused by matrix components during atomiza-
tion. Arsenic analysis is particularly susceptible to these problems because
of its low analytical wavelength (193.7 nm). Simultaneous background correc-
tion must be employed to avoid erroneously high results.
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2 / INORGANIC ANALYTICAL METHODS
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
4.1 250-ml Griffin beaker.
4.2 10-ml volumetric flasks.
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 strip chart recorder.
4.4 Arsenic hollow cathode lamp or electrodeless discharge lamp.
4.5 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.6 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any prob-
lems 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 1000 u.1 as required.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Hydrogen peroxide (30%); Oxidant should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.4 Arsenic standard stock solution (1000 mg/1): Either procure a certified
aqueous standard from a supplier (Spex Industries, Alpha Products, or Fisher
Scientific) and verify by comparison with a second standard, or dissolve
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7060 / 3
1.320 g of arsenic trioxide (AsgOs, analytical reagent grade) or
equivalent in 100 ml of Type II water containing 4 g NaOH. Acidify the
solution with 20 ml cone. HN03 and dilute to 1 liter.
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent
grade Ni (N03)2*6H20 or equivalent in Type II water and dilute to 100 ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel
nitrate to 100 ml with Type II water.
5.7 Arsenic working standards: Prepare dilutions of the stock solution
to be used as calibration standards at the time of analysis. Withdraw
appropriate aliquots of the stock solution, add 1 ml of cone. HN03, 2 ml of
30% H202, and 2 ml of the 5% 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 in Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and distilled deionized 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 less than 2 with
nitric acid.
6.5 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared in the
manner described in Sections 7.1.1-7.1.3. Sludge-type samples should be pre-
pared according to Method 3050, and samples containing oils, greases, or
waxes may be prepared according to Methods 3030 or 3040. 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% ^2 and sufficient cone. HNOa to result
in an acid concentration of 1% (v/v). Heat for 1 hr at 95° C or until
the volume is slightly less than 50 ml.
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4 / INORGANIC ANALYTICAL METHODS
7.1.2 Cool and bring back to 50 ml with Type II 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 and dilute to 10 ml
with Type II water. The sample is now ready for injection
into the furnace.
7.2 The 193.7-nm wavelength line and a background correction system
must be employed. Follow the manufacturer's suggestions for all other
spectrophotometer parameters.
7.3 Furnace parameters suggested by the manufacturer should be em-
ployed 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.
7.4 Inject a measured u.1 aliquot of sample into the furnace and
atomize. If the concentration found is greater than the highest stand-
ard, the sample should be diluted in the same acid matrix and reanalyzed.
The use of multiple injections can improve accuracy and help detect furnace
pipetting errors.
7.5 Analyze, 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.
7.6 Run a check standard after approximately every 10 sample injec-
tions. Standards are run in part to monitor the life and performance of the
graphite tube. Lack of reproducibility or significant change in the signal
for the standard indicates that the tube should be replaced.
7.7 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 or wet
samples must be appropriately qualified (e.g., 5 u.g/g dry weight).
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
-------
7060 / 5
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7061
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
groundwater. Method 7061 is approved only for sample matrices that do not
contain high concentrations of chromium, copper, mercury, nickel, silver,
cobalt, and molybdenum. All samples must be subjected to an appropriate
solution 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. Next, the arsenic in the digestate is
reduced to the trivalent form using tin chloride. The trivalent arsenic is
then converted to a volatile hydride using hydrogen produced from a zinc/HCl
reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located in
the optical path of an atomic absorption spectrophotometer. The resulting
absorption of the hollow cathode radiation is proportional to the arsenic
concentration.
2.3 The typical detection limit for this method is 0.002 mg/1.
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 workup can result
in analytical interferences. Nitric acid must be distilled off by heating
the sample until fumes of $03 are observed.
3.3 Elemental arsenic and many of its compounds are volatile and
therefore certain samples may be subject to losses of arsenic during sample
preparation.
4.0 Apparatus and Materials
4.1 100-ml beaker.
4.2 Electric hot plate.
-------
7061 / 2
4.3 A commercially available zinc slurry/hydride generator or a generator
constructed from the following materials (see Figure 1).
4.3.1 Medicine dropper that can be fitted into a size "0" rubber
stopper and that is capable of delivering 1.5 ml.
4.3.2 50-ml pear-shaped reaction flask 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
joi nt.
4.3.4 Magnetic stirrer to homogenize the zinc slurry.
4.3.5 10-cm polyethylene drying tube filled with glass to prevent
particulate matter from entering the burner.
4.3.6 Flow meter capable of measuring 1 liter/minute.
4.4 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument having a grating monochromator, photo-
multiplier detector, adjustable slits, a wavelength range of 190 to 800 nm,
and provisions for interfacing with a strip chart recorder.
4.5 Burner recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Arsenic hollow cathode lamp or arsenic electrodeless discharge
lamp.
4.7 Strip chart recorder.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Concentrated sulfuric acid: Acid should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should
be blank-corrected.
5.4 Concentrated hydrochloric acid: Acid should be analyzed to deter-
mine levels of impurities. If impurities are detected, all analyses should
be blank-corrected.
-------
7061 / 3
Argon
Flow Meter
JM-3325
Meaicne
Droooer in
Size "0"
Rubber
Stooper
JM-5835
(Auxiliary Air)
Argon (Nebulizer Air)
Figure 1. Zinc slurry hydride generator apparatus set-up and AAS sample introduction system.
-------
7061 / 4
5.5 Diluent: Add 100 ml 18 N H2S04 and 400 ml concentrated HC1 to
400 ml Type II water and dilute to a final volume of 1 liter with Type II
water.
5.6 Potassium iodide solution: Dissolve 20 g KI in 100 ml Type II
water.
5.7 Stannous chloride solution: Dissolve 100 g SnCl2 in 100 ml cone.
HC1.
5.8 Arsenic solutions
5.8.1 Arsenic standard solution (1,000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha
Products or Fisher Scientific) and verify by comparison with a second
standard, 0£ dissolve 1.320 g of arsenic trioxide I\S2®3 (analytical
reagent grade) or equivalent in 100 ml of Type II water containing 4 g
NaOH. Acidify the solution with 20 ml cone. HN03 and dilute to 1 liter.
5.8.2 Intermediate arsenic solution: Pipet 1 ml stock arsenic
solution into a 100-ml volumetric flask and bring to volume with deionized
distilled water containing 1.5 ml concentrated HN03/liter (1 ml = 10 u,g As),
5.8.3 Standard arsenic solution: Pipet 10 ml intermediate arsenic
solution into a 100-ml volumetric flask and bring to volume with deionized
distilled water containing 1.5 ml concentrated HN03/liter (1 ml =1 u.g 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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
distilled deionized 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 less than 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 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 cone.
Revised 4/84
-------
7061 / 5
HN03 and 12 ml 18 N ^SO^. Evaporate the sample in the hood on an elec-
tric hot plate until white $03 fumes are observed (a volume of about
20 ml). Do not let the sample char. If charring occurs, immediately turn
off the heat, co9l, and add an additional 3 ml of HNOj. Continue to add
additional HN03 in order to maintain an excess (as evidenced by the forma-
tion 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 $03 fumes, the digestion is complete. Cool the sample, add
about 25 ml Type II water, and again evaporate until $03 fumes are produced
in orcfer 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 Type II 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 from each of these standards into separate 50-ml volumetric
flasks. Add 10 ml of the prepared sample to each flask. Bring to volume
with Type II water containing 1.5 ml HN03/liter.
7.4 Add 10 ml of prepared sample to a 50-ml volumetric flask. Bring to
volume with Type II water containing 1.5 ml HN03/1iter. This is the blank.
NOTE: The absorbance from the blank will be one-fifth that produced by
the prepared sample. The absorbance from the spiked standards will be
one-half that produced by the standards plus the contribution from
one-fifth of the prepared sample. Keeping these in mind, the correct
dilutions to produce optimum absorbance can be judged.
7.5 Transfer a 25-ml portion of the digested sample or standard to the
reaction vessel, and add 1 ml potassium iodide solution. 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 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.
7.6 Use the 193.7-nm wavelength and background correction for the
analysis of arsenic.
-------
7061 / 6
7.7 Follow the manufacturer's instructions for operating an argon
hydrogen flame. The argon-hydrogen flame is colorless, so 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-tenth 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 calibra-
tion curve.
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7080
BARIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7080 is an atomic absorption procedure approved for deter-
mining the concentration of barium in wastes, mobility procedure extracts,
soils, and groundwater. 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 7080, samples must be prepared for
direct aspiration. The method of sample preparation will vary according
to the sample matrix. Aqueous samples are subjected to an acid digestion
procedure (Method 3010). Sludge samples are prepared using the procedure
described in Method 3050. For samples containing oils, greases, or waxes,
the procedures described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, an ionization
suppressant is added and a representative aliquot is aspirated into a nitrous
oxide/acetylene flame. The resulting absorption of hollow cathode radiation
will be proportional to the barium concentration. When possible, background
correction should be employed.
2.3 The typical detection limit for this method is 0.1 mg/1; typical
sensitivity is 0.4 mg/1.
3.0 Interferences
3.1 High hollow cathode current settings and a narrow spectral band
pass must be used since both barium and calcium emit strongly at barium's
analytical wavelength.
3.2 Barium undergoes significant ionization in the nitrous oxide/
acetylene flame, resulting in a significant decrease in sensitivity.
Therefore an ionization suppressant must be added to both standards and
samples.
3.3 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
3.4 If an air/acetylene flame is used, then the presence of phosphate
silicon and aluminum will decrease the sensitivity. This problem can be
overcome by adding a releasing agent (e.g., lanthanum) to both samples and
standard.
Revised 4/84
-------
7080 / 2
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: single or dual channel,
single- or double-beam instrument, having a grating monochromator, photomul-
tiplier detector, adjustable slits, and provisions for background correction.
4.2 Barium hollow cathode lamp or electrodeless discharge lamp.
4.3 Strip chart recorder (optional).
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Barium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or^
dissolve 1.787 g barium chloride (BaCl2'2H2° (analytical reagent grade) in
Type II water and dilute to 1 liter.
5.4 Potassium chloride solution: Dissolve 95 g potassium chloride
(KC1) in Type II water and dilute to 1 liter.
5.5 Lanthanum chloride solution if needed: Dissolve 25 g reagent
grade La2®3 slowly in 250 ml concentrated HC1. (Reaction can be violent.)
Dilute to 500 ml with Type II water.
5.6 Barium working standards: Prepare dilutions of the stock barium
solution to be used as calibration standards. To each 100 ml of standard and
sample add 2.0 ml potassium chloride solution.
5.7 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.8 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
flame conditions by replacing the cylinder before the pressure has fallen to
50 psig.
-------
7080 / 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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3010; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases, or waxes may be prepared according
to Methods 3030 or 3040. 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 The 553.6-nm wavelength line shall be used.
7.3 A fuel-rich nitrous oxide/acetylene flame shall be used.
7.4 Follow the manufacturer's operating instructions for all other
instrument parameters.
7.5 Either (1) run a series of barium standards and construct a cali-
bration curve by plotting the concentrations of the standards against the
absorbances £r (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.6 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.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 The final calculated concentration should take into account all
dilution and concentration factors.
-------
7080 / 4
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are"being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7081
BARIUM (ATOMIC ABSORPTION, FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7081 is an atomic absorption procedure approved for deter-
mining the concentration of barium in wastes, mobility procedure extracts,
soils, and groundwater. 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 7081, samples must be prepared in order
to convert organic forms of barium 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 an acid digestion procedure (Method 3020).
Sludge samples are prepared using the procedure described in Method 3050.
For samples containing oils, greases, or waxes, the procedures described in
Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the barium concentra-
tion.
2.3 The typical detection limit for this method is 2 u.g/1.
3.0 Inferences
3.1 Barium is known to form a barium carbide in the graphite furnace.
This less volatile carbide can cause losses of sensitivity and memory effects.
3.2 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.
3.3 Because of possible chemical interaction, nitrogen should not be
used as a purge gas.
3.4 Halide acids should not be used.
-------
2 / INORGANIC ANALYTICAL METHODS
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument having a grating monochromator, photo-
multiplier detector, adjustable slits, a wavelength range of 190 to 800 nm,
and provisions for interfacing with a strip chart recorder.
4.2 Barium hollow cathode lamp or electrodeless discharge lamp.
4.3 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.4 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any prob-
lems with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
4.5 Pipets: Microliter with disposable tips. Sizes can range from
5 to 1000 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: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Barium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or_
dissolve 1.787 g barium chloride (BaCl2'2H20, analytical reagent grade)
in Type II water and dilute to 1 liter.
5.4 Potassium chloride solution: Dissolve 95 g potassium chloride
(KC1) in Type II water and dilute to 1 liter.
5.5 Barium working standards: Prepare dilution of the stock barium
solution to be used as calibration standards. To each 100 ml of standard
and sample add 2.0 ml potassium chloride solution.
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 Section One of this manual.
-------
7081 / 3
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3020; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 553.6-nm line is the analytical wavelength to be used for
barium analysis.
7.3 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.4 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,
7.5 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.
7.6 Either (1) run a series of barium standards and construct a cali-
bration curve by plotting the concentrations of the standards against the
absorbances or^ (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.7 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.
-------
4 / INORGANIC ANALYTICAL METHODS
7.8 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.9 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 or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7130
CADMIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7130 is an atomic absorption procedure approved for deter-
mining the concentration of cadmium in wastes, mobility procedure extracts,
soils, and groundwater. 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 7130, samples must be prepared for
direct aspiration. The method of sample preparation will vary according to
the sample matrix. Aqueous samples are subjected to acid digestion procedure
(Method 3010). Sludge samples are prepared using the procedure described in
Method 3050. For samples containing oils, greases, or waxes, the procedures
described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot is aspirated into an air/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the cadmium
concentration. Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.005 mg/1; typical
sensitivity is 0.025 mg/1.
3.0 Interferences
3.1 Nonspecific absorption and light scattering can be significant at
the analytical wavelength. Thus background correction is required.
3.2 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, photomul-
tiplier detector, adjustable slits, and provisions for background correction.
4.2 Cadmium hollow cathode lamp or electrodeless discharge lamp.
4.3 Strip chart recorder (optional).
-------
2 / INORGANIC ANALYTICAL METHODS
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Cadmium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or
dissolve 2.282 g cadmium sulfate (CdSO^Sh^O, analytical reagent grade)
and dissolve in Type II water or equivalent.
5.4 Cadmium working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
5.5 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.6 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
flame conditions, by replacing the cylinder before the pressure has fallen to
50 psig.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3010; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
-------
7130 / 3
to Methods 3030 or 3040. 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 The 228.8-nm wavelength line and background correction shall be
employed.
7.3 An oxidizing air/acetylene flame shall be used.
7.4 Follow the manufacturer's operating instructions for all other
instrument parameters.
7.5 Either (1) run a series of cadmium standards and construct a
calibration curve by plotting the concentrations of the standards against the
absorbances £r_ (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.6 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.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 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 or wet
samples must be appropriately qualified (e.g., 5 p.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
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4 / INORGANIC ANALYTICAL METHODS
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7131
CADMIUM (ATOMIC ABSORPTION, FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7131 is an atomic absorption procedure approved for deter-
mining the concentration of cadmium in wastes, mobility procedure extracts,
soils, and groundwater. 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 7131, samples must be prepared in order
to convert organic forms of cadmium 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 an acid digestion procedure (Method 3020).
Sludge samples are prepared using the procedure described in Method 3050.
For samples containing oils, greases, or waxes, the procedures described in
Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the cadmium concen-
tration.
2.3 The typical detection limit for this method is 0.1 ug/1.
3.0 Interferences
3.1 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result in severe
physical and chemical interferences. Furnace parameters must be optimized to
minimize these effects.
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 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.
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2 / INORGANIC ANALYTICAL METHODS
4.0 Apparatus and Materials
4.1 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
strip chart recorder.
4.2 Cadmium hollow cathode lamp or electrodeless discharge lamp.
4.3 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.4 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Ammonium phosphate solution (40%): Dissolve 40 g of ammonium
phosphate, (NH4)2HP04 (analytical reagent grade), in Type II water and
dilute to 100 ml.
5.4 Cadmium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or_
dissolve 2.282 g of cadmium sulfate (3 CdS04-8H20), analytical reagent grade),
in Type II water and dilute to 1 liter.
5.5 Cadmium working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
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7131 / 3
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedures
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3020; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 228.8-nm wavelength line and background correction shall be
used.
7.3 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.4 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,
7.5 Inject a measured u.1 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.
7.6 For certain sample types the addition of 2 ml of an ammonium
phosphate solution to 100 ml of standards and samples will elevate charring
(ashing) temperatures which may eliminate matrix interferences. Ammonium
sulfate, (NH4)2$04, has been reported to have a similar effect on these samples.
7.7 Either (1) run a series of cadmium 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 concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.8 Analyze, by the method of standard additions, all EP extracts, all
samples analyzed as part of a delisting petition, and all samples that suffer
om matrix interferences.
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4 / INORGANIC ANALYTICAL METHODS
7.9 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.10 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.11 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 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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process,
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7190
CHROMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7190 is an atomic absorption procedure approved for deter-
mining the concentration of chromium in wastes, mobility procedure extracts,
soils, and groundwater. 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 7190, samples must be prepared for
direct aspiration. The method of sample preparation will vary according
to the sample matrix. Aqueous samples are subjected to an acid digestion
procedure (Method 3010). Sludge samples are prepared using the procedure
described in Method 3050. For samples containing oils, greases, or waxes,
the procedures described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot is aspirated into an nitrous oxide/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the chromium
concentration.
2.3 The typical detection limit for this method is 0.05 mg/1; typical
sensitivity is 0.25 mg/1.
3.0 Interferences
3.1 The nitrous oxide/acetylene flame is the recommended flame since
chromium analysis in an air/acetylene flame suffers from matrix interferences
caused by nickel iron and other metals. If an air/acetylene flame must be
used it should be lean.
3.2 An ionization interference may occur in the nitrous oxide flame if
the samples have a significantly higher amount of alkali salts than the
standards. If this interference is encountered, an ionization suppressant
should be added to both samples and standards.
3.3 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, photomul-
tiplier detector, adjustable slits, and provisions for background correction.
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2 / INORGANIC ANALYTICAL METHODS
4.2 Chromium hollow cathode lamp or electrodeless discharge lamp.
4.3 Strip chart recorder (optional).
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Chromium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, 0£
dissolve 1.923 g of chromium trioxide (Cr03, reagent grade) in Type II
water, acidify with redistilled HN03 and dilute to 1 liter.
5.4 Chromium working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
5.5 Nitrous oxide cylinder.
5.6 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.7 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
flame conditions, by replacing the cylinder before the pressure has fallen to
50 psig.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
-------
7190 / 3
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3010; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 357.9-nm wavelength line and background correction shall be
employed.
7.3 A fuel-rich nitrous oxide/acetylene flame shall be used.
7.4 Follow the manufacturer's operating instructions for all other
instrument parameters.
7.5 Either (1) run a series of chromium 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 concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.6 Analyze, by the method of standard additions, all EP extracts, all
samples analyzed as part of a deli sting petition, and all samples that suffer
from matrix interferences.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 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 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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
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4 / INORGANIC ANALYTICAL METHODS
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7191
CHROMIUM (ATOMIC ABSORPTION, FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7191 is an atomic absorption procedure approved for deter-
mining the concentration of chromium in wastes, mobility procedure extracts,
soils, and groundwater. 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 7191, samples must be prepared in order
to convert organic forms of chromium 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 an acid digestion procedure (Method 3020).
Sludge samples are prepared using the procedure described in Method 3050.
For samples containing oils, greases, or waxes, the procedures described in
Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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 radiation
during atomization will be proportional to the chromium concentration.
2.3 The typical detection limit for this method is 1 ug/1.
3.0 Interferences
3.1 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result in severe
physical and chemical interferences. Furnace parameters must be optimized to
minimize these effects.
3.2 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.
3.3 Nitrogen should not be used as the purge gas because of a possible
CN band interference.
3.4 Low concentrations of calcium may cause interferences; at concen-
trations above 200 mg/1, calcium's effect is constant. Calcium nitrate (see
Section 5.4) is therefore added to ensure a known constant effect.
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2 / INORGANIC ANALYTICAL METHODS
4.0 Apparatus and Materials
4.1 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
strip chart recorder.
4.2 Chromium hollow cathode lamp or electrodeless discharge lamp.
4.3 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.4 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Hydrogen peroxide (30%).
5.4 Calcium nitrate solution: Dissolve 11.8 g of calcium nitrate,
Ca(N03)2*4H20 (analytical reagent grade), in Type II water and dilute
to 1 liter.
5.5 Chromium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or^
dissolve 1.923 g of chromium trioxide (Cr03, analytical reagent grade) in
Type II water and dilute to 1 liter.
5.6 Chromium working standards: These standards should be prepared
to contain 0.5% (v/v) HNOs; 1 ml of 30% H202 and 1 ml of the calcium
nitrate solution may be added to lessen interferences.
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 Section One of this manual.
-------
7191 / 3
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedures
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3020; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 357.9-nm wavelength line shall be used.
7.3 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.4 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Since temperature-sensing mechanisms and temperature control-
lers 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 sensi-
tivity due to less than optimum settings can be minimized. Similar verifica-
tion of furnace parameters may be required for complex sample matrices.
7.5 Inject a measured u,l 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.
7.6 Either (1) run a series of chromium 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 concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.7 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.
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4 / INORGANIC ANALYTICAL METHODS
7.8 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.9 Duplicates, spiked samples, and check standards should be routinely
analyzed.
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 or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7195
HEXAVALENT CHROMIUM: COPRECIPITATION METHOD
1.0 Scope and Application
1.1 Method 7195 is to be used to determine the concentration of dis-
solved hexavalent chromium Cr(VI) in Extraction Procedure toxicity character-
istic (EP) extracts and groundwaters. This method may also be applicable to
certain domestic and industrial wastes provided that no interfering substances
are present (see paragraph 3.1).
1.2 Method 7195 may be used to analyze samples containing more than
5 ug of Cr(VI) per liter using either flame or furnace atomic absorption
spectroscopy (Methods 7190 and 7191).
2.0 Summary of Method
2.1 Method 7195 is based on the separation of Cr(VI) from solution by
coprecipitation of lead chromate with lead sulfate in a solution of acetic
acid. After separation, the supernate (containing Cr(III)) is drawn off and
the precipitate is washed to remove occluded Cr(III). The Cr(VI) is then
reduced and resolubilized in nitric acid, and quantified as chromium Cr(III)
by either flame or furnace atomic absorption spectroscopy (Methods 7190 and
7191).
3.0 Interferences
3.1 Extracts containing either sulfate or chloride in concentrations
above 1000 mg/1 should be diluted prior to analysis.
4.0 Apparatus and Materials
4.1 Filtering flask: Heavy wall, 1-liter capacity.
4.2 Centrifuge tubes: Heavy duty, conical, graduated, glass-stoppered,
10-ml capacity.
4.3 Pasteur pipets: Borosilicate glass, 6.8 cm.
4.4 Centrifuge: Any centrifuge capable of reaching 2000 rpm and
accepting the centrifuge tubes described in Section 4.2 may be used.
4.5 pH meter: A wide variety of instruments are commercially available
and suitable for this work.
4.6 Test tube mixer: Any mixer capable of imparting a thorough vortex
is acceptable.
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2 / INORGANIC ANALYTICAL METHODS
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Lead nitrate solution: Dissolve 33.1 g of lead nitrate,
(analytical reagent grade), in Type II water and dilute to 100 ml.
5.3 Ammonium sulfate solution: Dissolve 2.7 g of ammonium sulfate,
(analytical reagent grade), in Type II water and dilute to
100 ml.
5.4 Calcium nitrate solution: Dissolve 11.8 g of calcium nitrate,
H20 (analytical reagent grade), in Type II water and dilute
to 100 ml (1 ml = 20 mg Ca).
5.5 Nitric acid: Concentrated, distilled reagent grade or spectrograde
quality.
5.6 Acetic acid, glacial, 10% (v/v): Dilute 10ml glacial acetic acid,
CH3COOH (ACS reagent grade), to 100 ml with Type II water.
5.7 Ammonium hydroxide, 10% (v/v): Dilute 10ml concentrated ammonium
hydroxide, NH40H (analytical reagent grade), to 100 ml with Type II water.
5.8 Hydrogen peroxide, 30%: ACS reagent grade.
5.9 Potassium dichromate standard solution: Dissolve 28.285 g of dried
potassium dichromate, I^C^O; (analytical reagent grade), in Type II
water and dilute to 1 liter (1 ml = 10 mg Cr).
5.10 Trivalent chromium working stock solution: To 50 ml of the
potassium dichromate standard solution, add 1 ml of 30% H202 and 1 ml
concentrated HN03 and dilute to 100 ml with Type II water (1 ml = 5.0 mg
trivalent chromium). Prepare fresh monthly or as needed.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 Since the stability of Cr(VI) in EP extracts is not completely
understood at this time, the analysis should be carried out as soon as possible,
6.3 To retard the chemical activity of hexavalent chromium, samples and
extracts should be stored at 4° C until analyzed.
-------
7195 / 3
7.0 Procedure
7.1 Transfer a 50-ml portion of the sample to a 100-ml Griffin beaker and
adjust to a pH of 3.5 _+ 0.3 by adding volumes of 10% acetic acid dropwise.
Proceed immediately to 7.2 taking no longer than 15 min between these steps.
NOTE: Care must be exercised not to take the pH below 3. If the pH is
inadvertently lowered to less than 3, 10% NH40H should be used to readjust
the pH to 3.5 + 0.3.
7.2 Pi pet a 10-ml aliquot of the adjusted sample into a centrifuge
tube. Add 100 [il of the lead nitrate solution, stopper the tube, mix the
sample and allow to stand for 3 min.
7.3 After the formation of lead chromate, to help retain Cr(III) complex
in solution, add 0.5 ml glacial acetic acid, stopper and mix.
7.4 To provide adequate lead sulfate for coprecipitation, add 100 ul of
ammonium sulfate solution, stopper and mix.
7.5 Place the stoppered centrifuge tube in the centrifuge, making sure
that the tube is properly counterbalanced. Start the centrifuge and slowly
increase the speed to 2000 rpm in small increments over a period of 5 min. Hold
at 2000 rpm for 1 min. NOTE: The speed of the centrifuge must be increased
slowly to ensure complete coprecipitation.
7.6 After centrifuging remove the tube and withdraw and discard the
supernate using either the apparatus detailed in Figure 1 or careful
decantation. If using the vacuum apparatus, the pasteur pipet is lowered
into the tube and the supernate is sucked over into the filtering flask.
With care the supernate can be withdrawn to within approximately 0.1 ml
above the precipitate. Wash the precipitate with 5 ml Type II water and
repeat steps 7.5 and 7.6; then proceed to 7.7.
7.7 To the remaining precipitate, add 0.5 ml concentrated HN03,
100 u.1 30% H202 and 100 ul calcium nitrate solution. Stopper the tube
and mix using a vortex mixer to disrupt the precipitate and solubilize
the lead chromate. Dilute to 10 ml, mix and analyze in the same manner as
the calibration standard.
7.8 Flame atomic absorption: At the time of analysis, prepare a blank
and a series of at least four calibration standards from the Cr(III) working
stock that will adequately bracket the sample and cover a concentration range
of 1 to 10 mg Cr/liter. Add to the blank and each standard, before diluting
to final volume, 1 ml 30% 1^2, 5 ml concentrated HN03, and 1 ml
calcium nitrate solution for each 100 ml of prepared solution. These
calibration standards should be prepared fresh weekly, or as needed. Refer
to Method 7090 for more detail.
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4 / INORGANIC ANALYTICAL METHODS
7.9 Furnace atomic absorption: At the time of analysis, prepare a
blank and a series of at least four calibration standards from the Cr(III)
working stock that will adequately bracket the sample and cover a concentra-
tion range of 5 to 100 u.g Cr/liter. Add to the blank and each standard
before diluting to final volume, 1 ml 30% \\2®2, 5 ml concentrated HN03,
and 1 ml calcium nitrate solution for each 100 ml of prepared solution.
These calibration standards should be prepared fresh weekly, or as needed.
Refer to Method 7191 for more detail.
7.10 Verification
7.10.1 For every sample matrix analyzed, verification is required to
ensure that neither a reducing condition nor chemical interference is
affecting precipitation. This must be accomplished by analyzing a second
10-ml aliquot of the pH-adjusted filtrate that has been spiked with Cr(VI).
The amount of spike added should double the concentration found in the
original aliquot. Under no circumstance should the increase be less than
30 ug Cr(VI)/liter. To verify the absence of an interference, the spike
recovery must be between 85% and 115%.
7.10.2 If addition of the spike extends the concentration beyond the
calibration curve, the analysis solution should be diluted with blank
solution, and the calculated results adjusted accordingly.
7.10.3 If the result of verification indicates a suppressive inter-
ference, the sample should be diluted and reanalyzed. If necessary use
furnace atomic absorption to achieve the optimal concentration range.
7.10.4 If the interference persists after sample dilution, an
alternative method (chelation/extraction or colorimetric) should be used.
7.11 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the low spike recovery is due to the presence of
residual reducing agent. This determination shall be made 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/liter Cr(VI), one can conclude that the analytical method has
been verified and the waste is not hazardous by reason of the Cr(VI) concen-
tration in the EP extract.
7.12 If none of the analytical methods approved for this analysis yield
valid results, and if the sample contains more total chromium than the
threshold amount of hexavalent chromium, the sample will be considered to
exhibit the characteristic of EP toxicity unless exempted according to the
provisions of 40 CFR 261.4(b)(6).
-------
7195 / 5
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7196
HEXAVALENT CHROMIUM: COLORIMETRIC METHOD
1.0 Scope and Application
1.1 Method 7196 is used to determine the concentration of dissolved
hexavalent chromium Cr(VI) in Extraction Procedure toxicity characteristic
(EP) extracts and groundwaters. This method may also be applicable to
certain domestic and industrial wastes provided that no interfering sub-
stances are present (See paragraph 3.1).
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 solu-
tion. A red-violet color of unknown composition is produced. The reaction
is very sensitive, the absorbancy index per gram atom of chromium being about
40,000 at 540 nm. Addition of an excess of diphenylcarbazide yields the
red-violet product and its absorbance is measured photometrically at 540 nm.
3.0 Interferences
3.1 The chromium reaction with diphenylcarbazide is usually free from
interferences. However, certain substances may interfere if the chromium
concentration is relatively low. Hexavalent molybdenum and mercury salts
also react to form color with the reagent; however, the red-violet intensi-
ties produced are much lower than those for chromium at the specified pH.
Concentrations of up to 200 mg/1 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/liter may produce a yellow
color but the ferric iron color is not strong and no difficulty is normally
encountered if the absorbance is measured photometrically at the appropriate
wavelength.
4.0 Apparatus and Materials
4.1 Colon'metric equipment. One of the following is required: Either
a spectrophotometer, for use at 540 nm, providing a light path of 1 cm or
longer, £r 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.
-------
7196 / 2
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Potassium dichromate stock solution: Dissolve 141.4 mg of dried
potassium dichromate, KgC^Oy (analytical reagent grade), in Type II water
and dilute to 1 liter (1 ml = 50 u,g Cr).
5.3 Potassium dichromate standard solution: Dilute 10.00 ml potassium
dichromate stock solution to 100 ml (1 ml =5 u.g 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 Type II water.
5.5 Diphenylcarbazide solution: Dissolve 250 mg 1,5-diphenylcarbazide
in 50 ml acetone. Store in a brown bottle. Discard when the solution
becomes discolored.
5.6 Acetone (analytical reagent grade): Avoid or redistill material
that comes in containers with metal or metal-lined caps.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 Since the stability of Cr(VI) in EP extracts is not completely
understood at this time, the analysis should be carried out as soon as
possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4* C until analyzed.
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 ^$04 solution to give a pH of 2 +_ 0.5, dilute to
100 ml with Type II water, and let stand 5 to 10 min for full color develop-
ment. Transfer an appropriate portion of the solution to a 1-cm absorption
cell and measure its absorbance at 540 nm. Use Type II water as a reference.
Correct the absorbance reading of the sample by subtracting the absorbance of
Revised 4/84
-------
7196 / 3
a blank carried through the method (see also note below). From the corrected
absorbance, determine the mg/1 of chromium present by reference to the
calibration curve. NOTE: If the solution is turbid after dilution to 100 ml
in 7.1 above, take an absorbance reading before adding the carbazide reagent
and correct the absorbance reading of the final colored solution by subtract-
ing 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/1 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 absorp-
tion cell, and measure the absorbance at 540 nm. As reference, use
distilled 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/1 of Cr(VI).
7.3 Verification
7.3.1 For every sample matrix analyzed, verification is required to
ensure that neither a reducing condition nor chemical interference is
affecting color development. This must be accomplished by analyzing a
second 10-ml aliquot of the pH-adjusted filtrate that has been spiked
with Cr(VI). The amount of spike added should double the concentration
found in the original aliquot. Under no circumstance should the increase
be less than 30 u.g Cr(VI)/liter. To verify the absence of an interfer-
ence, the spifce 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 inter-
ference, the sample should be diluted and reanalyzed.
7.3.4 If the interference persists after sample dilution, an
alternative method (coprecipitation or chelation/extraction) should be
used.
Revised 4/84
-------
7196 / 4
7.4 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the low spike recovery is due to the presence of
residual reducing agent. This determination shall be made 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/1 Cr(VI), one can conclude that the analytical method has been verified
and the waste is not hazardous by reason of the Cr(VI) concentration in the EP
extract.
7.5 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.
7.6 If none of the analytical methods approved for this analysis yield
valid results, and if the sample contains total chromium in excess of the
threshold concentration allowed for hexavalent chromium, the sample will be
considered to exhibit the characteristic of EP toxicity unless exempted
according to the provisions of 40 CFR 261.4(b)(6).
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
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 Analyze check standards after approximately every 15 samples.
8.5 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.6 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.7 The method of standard additions 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.
-------
METHOD 7197
HEXAVALENT CHROMIUM: CHELATIQN/EXTRACTION
1.0 Scope and Application
1.1 Method 7197 is approved for determining the concentration of
dissolved hexavalent chromium Cr(VI) in Extraction Procedure toxicity
characteristic (EP) extracts and groundwaters. This method may also be
applicable to certain domestic and industrial wastes provided that no
interfering substances are present (see paragraph 3.1).
1.2 Method 7197 may be used to analyze samples containing from 1.0 to
25 u,g of Cr(VI) per liter.
2.0 Summary of Method
2.1 Method 7197 is based on the chelation of hexavalent chromium with
ammonium pyrrolidine dithiocarbamate (APCD) and extraction with methyl
isobutyl ketone (MIBK). The extract is aspirated into the flame of an atomic
absorption spectrophotometer.
3.0 Interferences
3.1 High concentrations of other metals may interfere.
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, photo-
multiplier detector, adjustable slits, and provisions for background correc-
tion.
4.2 Chromium hollow cathode lamp.
4.3 Strip chart recorder (optional).
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Ammonium pyrrolidine dithiocarbamate (APDC) solution: Dissolve
1.0 g APDC in Type II water and dilute to 100 ml. Prepare fresh daily.
-------
7197 / 2
5.3 Bromphenol blue indicator solution: Dissolve 0.1 g bromphenol blue
in 100 ml 50% ethanol.
5.4 Potassium dichromate standard solution I (1.0 ml = 100 ng Cr):
Dissolve 0.2829 g pure, dried potassium dichromate, I^C^Oj, in Type II
water and dilute to 1000 ml.
5.5 Potassium dichromate standard solution II (1.0 ml = 10.0 u.g Cr):
Dilute 100 ml chromium standard solution I to 1 liter with Type II water.
5.6 Potassium dichromate standard solution III (1.0 ml = 0.10 u.g Cr):
Dilute 10.0 ml chromium standard solution II to 1 liter with Type II water.
5.7 Methyl isobutyl ketone (MIBK), analytical reagent grade: Avoid or
redistill material that comes in contact with metal or metal-lined caps.
5.8 Sodium hydroxide solution, 1 M: Dissolve 40 g sodium hydroxide,
NaOH (ASC reagent grade), in Type II water and dilute to 1 liter.
5.9 Sulfuric acid, 0.12 M: Slowly add 6.5 ml distilled reagent grade
or spectrograde quality sulfuric acid, H2S04, with Type II water and
dilute to 1 liter.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 Since the stability of Cr(VI) in EP extracts is not completely
understood at this time, the chelation and extraction should be carried out
as soon as possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4* C until analyzed.
7.0 Procedure
7.1 Pipet a volume of extract containing less than 2.5 u.g chromium
(100 ml maximum) into a 200-ml volumetric flask, and adjust the volume to
approximately 100 ml.
7.2 Prepare a blank and sufficient standards, and adjust the volume
of each to approximately 100 ml.
7.3 Add 2 drops of bromphenol blue indicator solution. (The pH
adjustment to 2.4 may also be made with a pH meter instead of using an
indicator.)
Revised 4/84
-------
METHOD 7420
LEAD (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7420 is an atomic absorption procedure approved for deter-
mining the concentration of lead in wastes, mobility procedure extracts,
and soils. 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 7420, samples must be prepared for
direct aspiration. The method of sample preparation will vary according
to the sample matrix. Aqueous samples are subjected to an acid digestion
procedure (Method 3010). Sludge samples are prepared using the procedure
described in Method 3050. For samples containing oils, greases, or waxes,
the procedures described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot is aspirated into an air/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the lead
concentration. Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.1 mg/1; typical
sensitivity is 0.5 mg/1.
3.0 Interferences
3.1 Background correction is required since nonspecific absorption and
light scattering can be significant at the analytical wavelength.
3.2 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, photomul-
tiplier detector, adjustable slits, and provisions for background correction.
4.2 Lead hollow cathode lamp or electrodeless discharge lamp.
4.3 Strip chart recorder (optional).
-------
2 / INORGANIC ANALYTICAL METHODS
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Lead standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or_
dissolve 1.599 g of lead nitrate, Pb(N03)2 (analytical reagent grade), and
dissolve in Type II water, acidify with 10 ml redistilled HN03, and dilute to
1 liter with Type II water.
5.4 Lead working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
5.5 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.6 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
flame conditions, by replacing the cylinder before the pressure has fallen to
50 psig.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3010; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
-------
7197 / 3
7.4 Adjust the pH by addition of 1 M NaOH solution dropwise until a
blue color persists. Add 0.12 M ^$04 dropwise until the blue color just
disappears in both the standards and sample. Then add 2.0 ml of 0.12 M
^$04 in excess. The pH at this point should be 2.4.
7.5 Add 5.0 ml APDC solution and mix. The pH should then be
approximately 2.8.
7.6 Add 10.0 ml MIBK and shake vigorously for 3 min.
7.7 Allow the layers to separate and add Type II water until the ketone
layer is completely in the neck of the flask.
7.8 Aspirate the ketone layer and record the scale reading for each
sample and standard against the blank. Repeat, and average the duplicate
results.
7.9 Determine the mg/liter of Cr(VI) in each sample from a plot of
scale readings of standards. A working curve must be prepared with each set
of samples.
7.10 Verification
7.10.1 For every sample matrix analyzed, verification is required to
ensure that neither a reducing condition nor chemical interference is
affecting chelation. This must be accomplished by analyzing a second
10-ml aliquot of the pH-adjusted filtrate that has been spiked with Cr(VI).
The amount of spike added should double the concentration found in the
original aliquot. Under no circumstance should the increase be less than
30 ug Cr(VI)/liter. To verify the absence of an interference, the spike
recovery must be between 85% and 115%.
7.10.2 If addition of the spike extends the concentration beyond the
calibration curve, the analysis solution should be diluted with blank
solution, and the calculated results adjusted accordingly.
7.10.3 If the result of verification indicates a suppressi.ve inter-
ference, the sample should be diluted and reanalyzed.
7.10.4 If the interference persists after sample dilution, an
alternative method (coprecipitation or colorimetric) should be used.
7.11 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the low spike recovery is due to the presence of
residual reducing agent. This determination shall be made 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
-------
7197 / 4
than 5 mg/1 Cr(VI), one can conclude that the analytical method has been verified
and the waste is not hazardous by reason of the Cr(VI) concentration in the EP
extract.
7.12 If none of the analytical methods approved for this analysis yield
valid results, and if total chromium concentrations are in excess of the
threshold limits allowed for hexavalent chromium, the sample will be considered
to exhibit the characteristic of EP toxicity unless exempted according to the
provisions of 40 CFR 261.4(b)(6).
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
7420 / 3
to Methods 3030 or 3040. 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 The 283.3-nm wavelength line and background correction shall be
used.
7.3 An oxidizing air/acetylene flame shall be used.
7.4 Follow the manufacturer's operating instructions for all other
instrument parameters.
7.5 Either (1) run a series of lead standards and construct a cali-
bration curve by plotting the concentrations of the standards against the
absorbances or_ (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.6 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.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 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 or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
-------
4 / INORGANIC ANALYTICAL METHODS
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7421
LEAD (ATOMIC ABSORPTION. FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7421 is an atomic absorption procedure approved for deter-
mining the concentration of lead in wastes, mobility procedure extracts,
soils, and groundwater. 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 7421, samples must be prepared in order
to convert organic forms of lead 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 an acid digestion procedure (Method 3020).
Sludge samples are prepared using the procedure described in Method 3050.
For samples containing oils, greases, or waxes, the procedures described in
Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the lead concentra-
tion.
2.3 The typical detection limit for this method is 1 u.g/1.
3.0 Interferences
3.1 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result in severe
physical and chemical interferences. Furnace parameters must be optimized to
minimize these effects.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, lead 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.
-------
2 / INORGANIC ANALYTICAL METHODS
3.4 Sulfate can suppress lead absorbance. This interference can be
eliminated or lessened by adding a lanthanum releasing agent (10 ml lanthanum
solution per 100 ml of solution).
4.0 Apparatus and Materials
4.1 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
strip chart recorder.
4.2 Lead hollow cathode lamp or electrodeless discharge lamp.
4.3 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.4 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Lanthanum nitrate solution: Dissolve 58.64 g of ACS reagent grade
La203 in 100 ml concentrated HN03 and dilute to 1000 ml with Type II water.
5.4 Lead standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or_
dissolve 1.599 g lead nitrate, Pb(N03)2 (analytical reagent grade), in
Type II water and acidify with 10 ml redistilled HN03. Dilute to 1 liter.
5.5 Lead working standards: These standards should be prepared
such that they contain 0.5% (v/v) HN03.
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 Section One of this manual.
-------
7421 / 3
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedures
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3020; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 283.3-nm wavelength line and background correction shall be
used.
7.3 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.4 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.
7.5 Inject a measured uT aliquot of sample into the furnace and atomize.
If the concentration found is greater than the highest standard, the sample
should be dilated in the same acid matrix and reanalyzed. The use of multiple
injections can improve accuracy and help detect furnace pipetting errors.
7.6 Either (1) run a series of lead standards and construct a calibration
curve by plotting the concentrations of the standards against the absorbances
or_ (2) for the method of standard additions, plot added concentration versus
absorbance. For instruments that read directly in concentration, set the
curve corrector to read out the proper concentration.
7.7 Analyze, 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.
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4 / INORGANIC ANALYTICAL METHODS
7.8 If sulfate interference is encountered, add 10 ml of lanthanum
solution to each 100 ml of solution.
7.9 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.10 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.11 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 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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7470
MERCURY (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 groundwaters. (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 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/1.
3.0 Interferences
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/1 of sulfide as sodium sulfide
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/1 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) since, during the oxida-
tion 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. Both inorganic and organic mercury spikes
have been quantitatively recovered from seawater using this technique.
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2 / INORGANIC ANALYTICAL METHODS
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
absoption unit having 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 having
quartz end windows may be used. Suitable cells may be constructed from
plexiglass tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to
the longitudinal axis and quartz windows (1 in. diameter x 1/16 in. thickness)
are cemented in place. The cell is strapped to a burner for support and
aligned in the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter
holes are cut in the middle of each card. The cards are then placed over
each end of the cell. The cell is then positioned and adjusted vertically
and horizontally to give the maximum transmittance.
4.5 Air pump: Any peristaltic pump capable of delivering 1 liter
air/min may be used. A Masterflex pump with electronic speed control has
been found to be satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 liter/min.
4.7 Aeration tubing: A straight glass frit having 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.
4.10 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.
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7470 / 3
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4 / INORGANIC ANALYTICAL METHODS
4.11 Because mercury vapor is toxic, precaution must be taken to avoid
its inhalation. Therefore, a bypass has been included in the system to
either vent the mercury vapor into an exhaust hood or pass the vapor through
some absorbing media, such as:
1. equal volumes of 0.1 M KMn04 and 10% ^$04
2. 0.25% iodine in a 3% KI solution
A specially treated charcoal that will adsorb mercury vapor is also available
from oarnebey and Cheney, E. 8th Ave. and N. Cassidy St., 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 Sulfuric acid, cone.: Reagent grade.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of cone, sulfuric acid to
1.0 liter.
5.4 Nitric acid, cone.: 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
sulfuric acid. 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 Type II water and dilute
to 100 ml. (Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.)
5.7 Potassium permanganate, 5% solution (w/v): Dissolve 5 g of potassium
permanganate in 100 ml of Type II water.
5.8 Potassium persulfate, 5% solution (w/v): Dissolve 5 g of potassium
persulfate in 100 ml of Type II water.
5.9 Stock mercury solution: Dissolve 0.1354 g of mercuric chloride
in 75 ml of Type II water. Add 10 ml of cone. HN03 and adjust the volume
to 100.0 ml (2 ml = 1 mg Hg).
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7470 / 5
5.10 Mercury working standard: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 u.g 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.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid. The suggested maximum holding times for these samples are
38 days in glass containers and 13 in 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 not more than 1.0 u.g of mercury, to a 300-ml BOD bottle.
Add 5 ml of sulfuric acid and 2.5 ml- of cone, nitric acid, mixing after
each addition. Add 15 ml of potassium permanganate solution to each sample
bottle. Sewage samples may require additional permanganate. 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 per-
sulfate 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 and immediately attach the bottle to the aeration apparatus and
continue as described in Section 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 to 1.0 u.g 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
cone, sulfuric acid and 2.5 ml of cone, nitric acid 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, and
immediately attach the bottle to the aeration apparatus and continue as
described in Section 7.3.
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6 / INORGANIC ANALYTICAL METHODS
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.
7.4 Construct a calibration curve by plotting the absorbance 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.
7.5 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.
7.6 Duplicates, spiked samples, and check standards should be routinely
analyzed.
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 multiphased or
wet samples must be appropriately qualified (e.g., 5 ^g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
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7470 / 7
8.8 The method of standard additions 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.
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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 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.
2.0 Summary of Method
2.1 Prior to analysis the 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 detection limit for this method is 0.0002 mg/1.
3.0 Interferences
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/1 of sulfide as sodium sulfide
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/1 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) since, during the oxi-
dation 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. Both inorganic and organic mercury spikes
have been quantitatively recovered from seawater 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.
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7471 / 2
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer or equivalent: Any atomic
absoption unit having 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 having
quartz end windows may be used. Suitable cells may be constructed from
plexiglass tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to
the longitudinal axis and quartz windows (1 in. diameter x 1/16 in. thickness)
are cemented in place. The cell is strapped to a burner for support and
aligned in the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter
holes are cut in the middle of each card. The cards are then placed over
each end of the cell. The cell is then positioned and adjusted vertically
and horizontally to give the maximum transmittance.
4.5 Air pump: Any peristaltic pump capable of delivering 1 liter
air/min may be used. A Masterflex pump with electronic speed control has
been found to be satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 liter/min.
4.7 Aeration tubing: A straight glass frit having a coarse porosity.
Tygon tubing is used for passage of the mercury vapor from the sample bottle
to the absorption cell and return.
4.8 Drying tube: 6-in. x 3/4-in.-diameter tube containing 20 g of
magnesium perch!orate or a small reading lamp with 60-W bulb which may be
used to prevent condensation of moisture inside the cell. The lamp should
be positioned to shine on the absorption cell so that the air temperature in
the cell is about 10* C above ambient.
4.9 The cold-vapor generator is assembled as shown in Figure 1.
4.10 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.
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7471 / 3
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7471 / 4
4.11 Because mercury vapor is toxic, precaution must be taken to avoid
its inhalation. Therefore, a bypass has been included in the system to
either vent the mercury vapor into an exhaust hood or pass the vapor through
some absorbing media, such as:
1. equal volumes of 0.1 M KMn04 and 10% H2S04
2. 0.25% iodine in a 3% KI solution
A specially treated charcoal that will adsorb mercury vapor is also available
from Barnebey and Cheney, E. 8th Ave. and N. Cassidy St., 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 Aqua regia: Prepare immediately before use by carefully adding
three volumes of cone. HC1 to one volume of cone.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of cone, 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 continu-
ously 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 Type II water and dilute
to 100 ml. Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.
5.6 Potassium permanganate, 5% solution (w/v): Dissolve 5 g of potassium
permanganate in 100 ml of Type II water.
5.7 Mercury stock solution: Dissolve 0.1354 g of mercuric chloride in
75 ml of distilled water. Add 10 ml of cone, 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 u.g/m1 • 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.
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7471 / 5
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 For solids or semi-solids, 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 dry sample
and place in the bottom of a BOD bottle. Add 5 ml of Type II water and 5 ml
of aqua regia. Heat 2 min in a water bath at 95" C. Cool, add 50 ml Type II
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 perman-
ganate. 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 7.4.
7.2 An alternate digestion procedure employing an autoclave may also
be used. In this method, 5 ml of cone. H2$04 and 2 ml of cone. 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
Type II 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 7.4.
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 to 1.0 ^g 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 regia and heat
2 min in a water bath at 95* C. Allow the sample to cool and add 50 ml Type
II 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 Type II water.
Treating each bottle individually, add 5 ml of stannous sulfate solution and
immediately attach to bottle to the aeration apparatus and continue as
described in Section 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 liter/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
Revised 4/84
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7471 / 6
levels off (approximately 1 min), open the bypass valve and continue the
aeration until the absorbance returns to its minimum value. Close the bypass
value, remove the fritted tubing from the BOD bottle, and continue the
aeration.
7.5 Construct a calibration curve by plotting the absorbance 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, 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.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 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 or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7520
NICKEL (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7520 is an atomic absorption procedure approved for deter-
mining the concentration of nickel in wastes, mobility procedure extracts,
soils, and groundwater. 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 7520, samples must be prepared for
direct aspiration. The method of sample preparation will vary according
to the sample matrix. Aqueous samples are subjected to an acid digestion
procedure (Method 3010). Sludge samples are prepared using the procedure
described in Method 3050. For samples containing oils, greases, or waxes,
the procedures described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a represen-
tative aliquot is aspirated into an air/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the nickel
concentration. Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.04 mg/1; typical
sensitivity is 0.15 mg/1.
3.0 Interferences
3.1 Background correction is required since nonspecific absorption
and light scattering can be significant at the analytical wavelength.
3.2 High concentrations of iron, cobalt and chromium can suppress nickel
absorbance. If this interference becomes measurable, either the method of
matrix matching or a nitrous oxide/acetylene flame should be employed.
3.3 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, photomul-
tiplier detector, adjustable slits, and provisions for background correction.
4.2 Nickel hollow cathode lamp.
4.3 Strip chart recorder (optional).
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2 / INORGANIC ANALYTICAL METHODS
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Nickel standard stock solution (1000 mg/1). Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products
or Fisher Scientific) and verify by comparison with a second standard, or_
dissolve 4.953 g of nickel nitrate, Ni(N03)2'6H20 (analytical reagent grade),
in Type II water. Add 10 ml of cone, nitric acid and dilute to 1 liter with
Type II water.
5.4 Nickel working standards: These standards should be prepared with
the same type and same concentration of acid that will be found in the
analytical solution.
5.5 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.6 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
flame conditions, by replacing the cylinder before the pressure has fallen to
50 psig.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3010; sludge-type samples should be prepared according to Method
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7520 / 3
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 The 232.0-nm wavelength line and background correction shall be
employed.
7.3 An oxidizing air/acetylene flame shall be used.
7.4 Follow the manufacturer's operating instructions for all other
instrument parameters.
7.5 Either (1) run a series of nickel standards and construct a calibra-
tion curve by plotting the concentrations of the standards against the
absorbances or_ (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.6 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.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 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 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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
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4 / INORGANIC ANALYTICAL METHODS
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7521
NICKEL (ATOMIC ABSORPTION. FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7521 is an atomic absorption procedure approved for deter-
mining the concentration of nickel in wastes, mobility procedure extracts,
soils, and groundwater. 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 7521, samples must be prepared in order
to convert organic forms of nickel 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 an acid digestion procedure (Method 3020).
Sludge samples are prepared using the procedure described in Method 3050.
For samples containing oils, greases, or waxes, the procedures described in
Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the nickel concentra-
tion.
2.3 The typical detection limit for this method is 1 u.g/1.
3.0 Interferences
3.1 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result in severe
physical and chemical interferences. Furnace parameters must be optimized to
minimize these effects.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, nickel analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization.
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.
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2 / INORGANIC ANALYTICAL METHODS
4.0 Apparatus and Materials
4.1 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 strip chart recorder.
4.2 Nickel hollow cathode lamp.
4.3 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.4 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Nickel standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products
or Fisher Scientific) and verify by comparison with a second standard, or_
dissolve 4.953 g of nickel nitrate, Ni(N03)2*6H20 (analytical reagent grade),
in Type II water.
5.4 Nickel working standards: These standards should be prepared
with the same type and same concentration of acid that will be found in the
analytical solution.
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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
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7521 / 3
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Method 3020; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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.
i
7.2 The 232.0-nm wavelength line and background correction shall be
used.
7.3 Follow the manufacturer's operating instructions for all other
spectrometer parameters.
7.4 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.
7.5 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.
7.6 Either (1) run a series of nickel standards and construct a cali-
bration curve by plotting the concentrations of the standards against the
absorbances or_ (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.6 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.
7.8 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.9 Duplicates, spiked samples, and check standards should be routinely
analyzed.
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4 / INORGANIC ANALYTICAL METHODS
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 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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION, FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7740 is an atomic absorption procedure approved for deter-
mining the concentration of selenium in wastes, mobility procedure extracts,
soils, and groundwater. All samples must be subjected to an appropriate
dissolution step prior to analysis.
2.0 Summary of Method
2.1 Prior to analysis by Method 7740, samples must be prepared in order
to convert organic forms of selenium to inorganic forms, to minimize organic
interferences, and to convert 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. For samples containing oils, greases, or waxes, the procedures
described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the selenium concen-
tration.
2.3 The typical detection limit for this method is 2 ng/1.
3.0 Interferences
3.1 Elemental selenium and many of its compounds are volatile and
therefore samples may be subject to losses of selenium during sample prepa-
ration. Spike samples and relevant standard reference materials should be
processed to determine if the chosen dissolution method is appropriate.
3.2 Likewise, caution must be employed during the selection of tem-
perature and times for the dry and char (ash) cycles. A nickel nitrate
solution must be added to all digestate prior to analysis to minimize vola-
tilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graph-
ite furnace analysis, selenium analysis can suffer from severe nonspecific
absorption and light scattering caused by matrix components during atomiza-
tion. Selenium analysis is particularly susceptible to these problems because
of its low analytical wavelength (196.0 nm). Simultaneous background correc-
tion must be employed to avoid erroneously high results.
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2 / INORGANIC ANALYTICAL METHODS
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, the tube should be cleaned by operating the furnace at full power
at regular intervals in the analytical scheme.
3.5 Selenium analysis suffers interference from chlorides (more than
800mg/l) and sulfate (more than 200 mg/1). The addition of nickel nitrate
such that the final concentration is 1% nickel will lessen this interference,
4.0 Apparatus and Materials
4.1 250-ml Griffin beaker.
4.2 10-ml volumetric flasks.
4.3 Atomic absorption 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 strip chart recorder.
4.4 Selenium hollow cathode lamp or electrodeless discharge lamp.
4.5 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.6 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any prob-
lems with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
4.7 Pipets: Micro!iter with disposable tips. Sizes can range from
5 to 1000 yl as required.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Hydrogen peroxide (30%): Oxidant should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
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7740 / 3
5.4 Selenium standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products,
or Fisher Scientific) and verify by comparison with a second standard, or^
dissolve 0.3453 g of selenious acid (actual assay 94.6% H2Se03, analytical
reagent grade) or equivalent in Type II water and dilute to 200 ml.
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent
grade Ni(N03)2*6H20 or equivalent in Type II water and dilute to 100 ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel
nitrate to 100 ml with Type II water.
5.7 Selenium working standards: Prepare dilutions of the stock solu-
tion to be used as calibration standards at the time of analysis. Withdraw
appropriate aliquots of the stock solution, add 1 ml of cone. HN03, 2 ml of
30% H202, and 2 ml of the 5% nickel nitrate solution. Dilute to 100 ml with
Type II water.
5.8 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.9 Hydrogen: Suitable for instrumental analysis.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile selenium compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.5 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared in the
manner described in Sections 7.1.1 to 7.1.3. Sludge-type samples should be
prepared according to Method 3050, and samples containing oils, greases, or
waxes may be prepared according to Methods 3030 or 3040. The applicability
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4 / INORGANIC ANALYTICAL METHODS
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% ^0? and sufficient cone. HNOs to result
in an acid concentration of 1% (v/v). Heat for 1 hr at 95* C or until
the volume is slightly less than 50 ml.
7.1.2 Cool and bring back to 50 ml with Type II water.
7.1.3 Pipet 5 ml of this digested solution into a 10-ml volumetric
flask, add 1 ml of the 1% nickel nitrate solution and dilute to 10 ml
with Type II water. The sample is now ready for injection into the
furnace.
7.2 The 196.0-nm wavelength line and a background correction system
must be employed. Follow the manufacturer's suggestions for all other
instrument parameters.
7.3 Furnace parameters suggested by the manufacturer should be em-
ployed 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.
7.4 Inject a measured u.1 aliquot of sample into the furnace and
atomize. If the concentration found is greater than the highest stand-
ard, the sample should be diluted in the same acid matrix and reanalyzed.
The use of multiple injections can improve accuracy and help detect furnace
pipetting errors.
7.5 Analyze, 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.
7.6 Run a check standard after approximately every 10 sample injec-
tions. Standards are run in part to monitor the life and performance of the
graphite tube. Lack of reproducibility or significant change in the signal
for the standard indicates that the tube should be replaced.
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 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
-------
7740 / 5
must be taken into account. Concentrations reported for multiphased or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7741
SELENIUM (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
1.0 Scope and Application
1.1 Method 7741 is an atomic absorption procedure which is approved for
determining the concentration of selenium in wastes, mobility procedure
extracts, soils, and groundwater, 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.
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 the +4 form using tin chloride. The +4 selenium is then converted
to a volatile hydride with hydrogen produced from a zinc/HCl reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located
in the optical path of an atomic absorption spectrophotometer, and the
resulting absorbance is proportional to the selenium concentration.
2.3 The typical detection limit for this method is 0.002 mg/1.
3.0 Interferences
3.1 High concentrations of chromium, cobalt, copper, mercury, molybdenun
nickel, and silver can cause analytical interferences.
3.2 Traces of nitric acid left following the sample workup can result
in analytical interferences. Nitric acid must be distilled off by heating
the sample until fumes of 503 are observed.
3.3 Elemental selenium and many of its compounds are volatile and
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.
4.3 A commercially available zinc slurry hydride generator or a
generator constructed from the following material (see Figure 1).
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7741 / 2
Flow Meter
JM-3325
Medicine
Dropper in
Size "0"
Rubber
Stopper
(Auxiliary Air)
Argon (Nebulizer Air)
Figure 1. Zinc slurry hydride generator apparatus set-up and AAS sample introduction system.
-------
7741 / 3
4.3.1 Medicine dropper fitted into a size "0" rubber stopper
capable of delivering 1.5 ml.
4.3.2 A 50-ml pear-shaped reaction flask 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 A 10-cm polyethylene drying tube filled with glass 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 having a grating monochromator, photomulti-
plier detector, adjustable slits, a wavelength range of 190 to 800 nm, and
provisions for interfacing with a strip chart recorder and simultaneous
background correction.
4.5 Burner recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Selenium hollow cathode lamp or electrodeless discharge lamp.
4.7 Strip chart recorder.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored
for impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Concentrated sulfuric acid: Acid should be analyzed to determine
levels of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.4 Concentrated hydrochloric acid: Acid should be analyzed to
determine levels of impurities. If impurities are detected all analyses
should be blank-corrected.
5.5 Diluent: Add 100 ml 18 N H2$04 and 400 ml concentrated HC1 to
400 ml Type II water and dilute to a final volume of 1 liter with Type II
water.
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7741 / 4
5.6 Potassium iodide solution: Dissolve 20 g KI in 100 ml Type II
water.
5.7 Stannous chloride solution: Dissolve 100 g SnClg in 10° ml of
cone. HC1.
5.8 Selenium standard stock solution: 1000 nig/liter solution may be
purchased, or prepared as follows. Dissolve 0.3453 g of selenious acid
(assay 94.6% of H2Se03) in Type II 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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile selenium compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.5 Nonaqueous samples shall be refrigerated where 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 EP
extracts a 50-ml sample) add 10 ml cone. HN03 and 12 ml of 18 N H2S04.
Evaporate the sample on a hot plate until white 503 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.
7.1.2 Cool the sample, add about 25 ml distilled deionized water
and again evaporate to S03 fumes just to expel oxides of nitrogen.
Cool. Add 40 ml cone. HC1 and bring to a volume of 100 ml with distilled
deionized water.
Revised 4/84
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7741 / 5
7.2 Prepare working standards from the standard stock solutions. The
following procedure provides standards in the optimum working range.
7.2.1 Pipet 1 ml stock solution into a 1-liter volumetric flask.
Bring to volume with Type II water containing 1.5 ml cone. HN03/liter.
The concentration of this solution is 1 mg Se/liter (1 ml =1 ng Se).
7.2.2 Prepare six working standards by transferring 0, 0.5, 1.0,
1.5, 2.0 and 2.5 ml of the selenium stock standard (see Section 5.8)
into a 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/liter.
7.3 Standard additions
7.3.1 Take the 15-, 20-, and 25-ug standards and transfer quanti-
tatively 25 ml from each into separate 50-ml volumetric flasks. Add
10 ml of the prepared sample to each. Bring to volume with Type II
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 Type II water containing 1.5 ml HN03 per liter.
This is the blank.
7.4 Follow the manufacturer's instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame is colorless so 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 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. When the recorder pen returns partway to the
base line, remove the reaction vessel.
7.7 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.
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
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7741 / 6
7.9 Calculate metal concentrations by (1) the method of standard
additions, or (2) from a calibration curve, or (3) directly from the instru-
ment's concentration readout. All dilution or concentration factors must
be taken into account. For example, if the method of standard additions was
employed, the analytical value will be one-tenth the concentration of the
original sample due to dilution during preparation. Concentrations reported
for multiphased or wet samples must be appropriately qualified (e.g., "5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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METHOD 7760
SILVER (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
1.0 Scope and Application
1.1 Method 7760 is an atomic absorption procedure approved for deter-
mining the concentration of silver in wastes, mobility procedure extracts,
soils, and groundwater. 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. Sludge samples are prepared using the
procedure described in Method 3050. For samples containing oils, greases, or
waxes, the procedures described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a repre-
sentative 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/1; typical
sensitivity is 0.06 mg/1.
3.0 Interferences
3.1 Background correction should be employed since 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 so hydrochloric acid should be avoided
unless the silver is already in solution as a chloride complex.
3.4 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 Apparatus and Materials
4.1 Atomic absorption spectrophotometer: Single or dual channel,
single- or double-beam instrument, having a grating monochromator, photomul-
tiplier detector, adjustable slits, and provisions for background correction.
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7760 / 2
4.2 Silver hollow cathode lamp.
4.3 Strip chart recorder (optional).
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Concentrated ammonium hydroxide (NH^OH): Base should be analyzed
to determine levels of impurities. If impurities are detected, all analyses
should be blank-corrected.
5.4 Silver standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products
or Fisher Scientific) and verify by comparison with a second standard, _or_
dissolve 0.7874 g anhydrous silver nitrate (AgNOi), analytical reagent
grade, in Type II water. Add 5 ml cone. HN03 and bring to volume in a
500-ml volumetric flask (1 ml = 1 mg Ag).
5.5 Silver working standards: These standards should be prepared with
nitric acid and at the same concentrations as the analytical solution.
5.6 Iodine solution, IN: Dissolve 20 g potassium iodide (KI),
analytical reagent grade, in 50 ml Type II water. Add 12.7 g iodine
analytical reagent grade, and dilute to 100 ml. Place in a brown bottle.
5.7 Cyanogen iodide solution: To 50 ml deionized distilled water
add 4.0 ml cone. NfyOH, 6.5 g KCN, and 5.0 ml of iodine solution. Mix and
dilute to 100 ml with deionized distilled water. Do not keep longer than
2 weeks. CAUTION: This reagent cannot be mixed with any acid solutions
since toxic hydrogen cyanide will be produced.
5.8 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of industrial-grade compressed air.
5.9 Acetylene: Should be of high purity. Acetone, which is usually
present in acetylene cylinders, can be prevented from entering and affecting
flame conditions by replacing the cylinder before the pressure has fallen to
50 psig.
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7760 / 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 Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids,
and Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 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 Sections 7.2 and 7.3; sludge-type samples should be prepared according to
Method 3050; and samples containing oils, greases or waxes may be prepared
according to Methods 3030 or 3040. 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 Griffin beaker and add 3 ml of cone. HN03- Cover the beaker with
a 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 cone. HNO^.
Re-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 type 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 distilled
water and, when necessary, filter the sample to remove silicates and
other insoluble material that could clog the nebulizer. Adjust the
Revised 4/84
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7760 / 4
volume to some predetermined value based on the expected metal concen-
trations. The sample is now ready for analysis.
7.3 If plating out of AgCl is suspected, the precipitate can be
rediss-olved by adding cyanogen iodide to the sample. CAUTION: This can only
be done after digestion to prevent formation of toxic hydrogen cyanide under
acid conditions. If cyanogen iodide addition to the sample is necessary,
then the standards must be treated in the same manner. CAUTION: cyanogen
iodide,must not be added to the acidified silver standards. New standards
must be made as directed in Sections 5.4 and 5.5 except that the acid addition
step must be omitted. Transfer 10 ml of stock solution to a small beaker.
Add Type II water to make about 80 ml. Make the solution basic (pH above 7)
with ammonium hydroxide. Rinse the pH meter electrodes into the solution
with Type II water. Add 1 ml cyanogen iodide and allow to stand 1 hr.
Transfer quantitatively to a 100 ml volumetric flask and bring to volume
with Type II water.
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.
7.7 Either (1) run a series of silver standards and construct a cali-
bration curve by plotting the concentrations of the standards against the
absorbances or. (2) for the method of standard additions, plot added concentra-
tion versus absorbance. For instruments that read directly in concentration,
set the curve corrector to read out the proper concentration.
7.8 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.
7.9 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.10 Calculate metal concentrations by (1) the method of standard
additions, or (2) from a calibration curve, or (3) directly from the instru-
ment's concentration readout. All dilution or concentration factors must be
taken into account. Concentrations reported for multiphased or wet samples
must be appropriately qualified (e.g., 5 u.g/g dry weight).
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
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7760 / 5
8,2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8,5 Analyze check standards after approximately every 15 samples.
8,6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8,8 The method of standard additions 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.
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METHOD 7761
SILVER (ATOMIC ABSORPTION, FURNACE METHOD)
1.0 Scope and Application
1.1 Method 7761 is an atomic absorption procedure approved for deter-
mining the concentration of silver in wastes, mobility procedure extracts,
soils, and groundwater. 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 7761, samples must be prepared in order
to convert organic forms of silver 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. For samples containing oils, greases, or waxes, the procedures
described in Methods 3030 and 3040 may be applicable.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 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
radiation during atomization will be proportional to the silver concen-
tration.
2.3 The typical detection limit for this method is 0.2 ug/1.
3.0 Interferences
3.1 The long residence time and high concentrations of the atomized
sample in the optical path of the graphite furnace can result in severe
physical and chemical interferences. Furnace parameters must be optimized
to minimize these effects.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, silver analysis can suffer from severe nonspecific absorp-
tion 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.
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7761 / 2
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.
4.0 Apparatus and Materials
4.1 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
strip chart recorder.
4.2 Silver hollow cathode lamp.
4.3 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.4 Strip chart recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during
charring, changes in sensitivity, etc., can easily be recognized.
5.0 Reagents
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
level of impurities. If impurities are detected, all analyses should be
blank-corrected.
5.3 Lead standard stock solution (1000 mg/1): Either procure a
certified aqueous standard from a supplier (Spex Industries, Alpha Products
or Fisher Scientific) and verify by comparison with a second standard, or
dissolve 0.7874 g anhydrous silver nitrate (AgN03), analytical reagent
grade, in Type II water. Add 5 ml concentrated HNOs and bring to volume
in a 500-ml volumetric flask.
5.4 Silver working standards: These standards should be be prepared with
nitric acid such that the final acid concentration is 0.5% (v/v) HN03.
5.5 Concentrated ammonium hydroxide (NfyOH): Base should be analyzed
to determine levels of impurities. If impurities are detected, all analyses
should be blank-corrected.
5.6 Iodine solution (IN): Dissolve 20 g potassium iodide (KI),
analytical reagent grade, in 50 ml Type II water. Add 12.7 g iodine
analytical reagent grade, and dilute to 100 ml. Place in a brown bottle.
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7761 / 3
5.7 Cyanogen iodide solution: To 50 ml deionized distilled water add
4.0 ml concentrated-NfyOH, 6.5 g KCN, and 5.0 ml of iodine solution. Mix
and dilute to 100 ml with deionized distilled 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 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Section One of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH of less than 2 with
nitric acid.
6.4 Nonaqueous samples shall be refrigerated when possible, and analyzed
as soon as possible.
7.0 Procedure
7.1 Sample preparation: Aqueous samples should be prepared according
to Section 7.2; sludge-type samples should be prepared according to Method
3050; and samples containing oils, greases or waxes may be prepared according
to Methods 3030 or 3040. 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 Griffin beaker and add 3 ml of cone. HN03« Cover the beaker with
a 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 cone. HNO^.
Re-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 type samples.
7.2.1 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.
Revised 4/84
-------
7761 / 4
7.2.3 Wash down the beaker walls and watch glass with distilled
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 concen-
trations. The sample is now ready for analysis.
7.3 If plating out of AgCl is suspected, the precipitate can be
redissolved by adding cyanogen iodide to the sample. CAUTION: This can only
be done after digestion to prevent formation of toxic hydrogen cyanide under
acid conditions. If cyanogen iodide addition to the sample is necessary,
then the standards must be treated in the same manner. CAUTION: cyanogen
iodide must not be added to the acidified silver standards. New standards
must be made as directed in Sections 5.4 and 5.5 except that the acid addition
step must be omitted. Transfer 10 ml of stock solution to a small beaker.
Add Type II water to make about 80 ml. Make the solution basic (pH above 7)
with ammonium hydroxide. Rinse the pH meter electrodes into the solution
with Type II water. Add 1 ml cyanogen iodide and allow to stand 1 hr.
Transfer quantitatively to a 100-ml volumetric flask and bring to volume
with Type II water.
7.4 The 328.1-nm wavelength line and background correction shall be
used.
7.5 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7.6 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Since temperature-sensing mechanisms and temperature
controllers can vary between instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering
the furnace parameters while analyzing a standard. In this manner, losses of
analyte due to higher than necessary temperature settings or losses in
sensitivity due to less than optimum settings can be minimized. Similar
verification of furnace parameters may be required for complex sample matrices.
7.7 Inject a measured pil 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 cali-
bration curve by plotting the concentrations of the standards against the
absorbances or_ (2) for the method of standard additions, plot added concentra-
tion versus absorbance. 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.
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7761 / 5
7.10 Run a check standard after approximately every 10 sample Injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.11 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.12 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 or wet
samples must be appropriately qualified (e.g., 5 u.g/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 if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
8.8 The method of standard additions 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.
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SECTION EIGHT
ORGANIC ANALYTICAL METHODS
8.1 Gas Chromatographic Methods (8000-8190)
Methods appropriate for organic analysis of samples by gas chromatography
are included on the following pages.
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METHOD 8010
HALOGENATED VOLATILE ORGANICS
1.0 Scope and Application
1.1 Method 8010 is used to determine the concentration of various halo-
genated volatile organic compounds in groundwater, liquid, and solid matrices.
Specifically, Method 8010 may be used to detect the following substances:
Benzyl chloride
Bis (2-chloroethoxy)methane
Bis (2-chloroisopropyl)ether
Bromobenzene
Bromodi chloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chloracetaldehyde
Chloral
Chlorobenzene
Chloroethane
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chloromethane
Chloromethyl methyl ether
Chlorotoluene
Di bromochloromethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene (Vinylidene chloride)
trans-1,2-Dichloroethylene
Dichloromethane
1,2-Dichloropropane
1,3-Di chloropropylene
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethylene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Tri chlorof1uoromethane
Trichloropropane
Vinyl chloride
1.2 This method is recommended for use by, or under the supervision
of, analysts experienced in the operation of gas chromatographs and in the
interpretation of chromatograms.
2.0 Summary of Method
2.1 Method 8010 provides chromatographic conditions for the detection
of halogenated volatile organic compounds. Waste samples can be analyzed
using direct injection, the headspace method (Method 5020) or the purge-
and-trap method (Method 5030). Groundwater samples should be determined
using Method 5030. A temperature program is used in the gas chromatograph to
separate the organic compounds. Detection is achieved by a halide-specific
detector (HSD).
2.2 If interferences are encountered, the method provides an optional
gas chromatographic column that may be helpful in resolving the compounds of
interest from the interferences.
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2 / ORGANIC ANALYTICAL METHODS - GC
3.0 Interferences
3.1 Samples can be contaminated by diffusion of volatile organics
{particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe or purging device must be rinsed out between samples with reagent
water. Whenever an unusually concentrated sample is encountered, it should
be followed by an analysis of reagent water to check for cross contamination.
For samples containing large amounts of water-soluble materials, suspended
solids, high boiling compounds or high organohalide levels, it may be neces-
sary to wash out the syringe or purging device with a detergent solution,
rinse it with distilled water, and then dry it in a 105" C oven between
analyses.
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.4 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 uxj/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 (below) when
analyzing groundwater samples.
4.0 Apparatus and Materials
4.1 Vial with cap: 40-ml capacity screw cap (Pierce #13075 or equiv-
alent). Detergent wash, rinse with tap and distilled deionized water, and
dry at 105" C before use.
4.2 Septum: Teflon-faced silicone (Pierce #12722 or equivalent).
Detergent wash, rinse with tap and distilled deionized water, and dry at
-------
8010 / 3
105° C for 30 min before use. NOTE: Do not heat the TFE seals for extended
periods of time (i.e., more than 1 hr) because the silicone layer slowly
degrades at 105° C.
4.3 Sample introduction apparatus for Methods 5020 and 5030.
4.4 Gas chromatograph: Analytical system complete with programmable
gas chromatograph suitable for on-column injection or purge-and-trap sample
introduction and all required accessories, including HSD or FID, column
supplies, recorder, and gases. A data system for measuring peak area is
recommended.
4.5 GC columns:
Column 1: 8-ft x 0.1-in. I.D. stainless steel or glass column packed
with 1% SP-1000 on Carbopac B 60/80 mesh.
Column 2: 6-ft x 0.1-in. I.D. stainless steel or glass column packed
with n-octane on Porasil-L 100/120 mesh.
4.6 Detector: Electrolytic conductivity (HSD).
4.7 Syringes: 5-ml glass hypodermic with Luerlok top (2 each).
4.8 Microsyringes: 10, 25, 100 ul.
4.9 Two-way syringe valve with Luer ends (3 each).
4.10 Syringe: 5 ml, gas-tight with shutoff valve.
4.11 Bottle: 15-ml screw-cap, with teflon cap liner.
5.0 Reagents
5.1 Activated carbon: Filtrasorb 200 (Calgon Corp.) or equivalent.
5.2 Organic-free water: Generated by passing tap water through a
carbon filter bed containing about 1 Ib of activated carbon. A water pur-
ification system (Millipore Super-Q or equivalent) may be used to generate
organic-free deionized water. Organic-free water may also be prepared by
boiling water for 15 min. Subsequently, while maintaining the temperature
at 90" C, bubble a contaminant-free inert gas through the water for 1 hr.
5.3 Stock standard solutions: Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions. Prepare
stock standard solutions in methyl alcohol using assayed liquids or gas
cylinders as appropriate. Because of the toxicity of many of the compounds
-------
4 / ORGANIC ANALYTICAL METHODS - GC
being analyzed, primary dilutions of these materials should be prepared in
a hood. A NIOSH/MESA-approved toxic gas respirator should be used when the
analyst handles high concentrations of such materials.
5.3.1 Place about 9 ml of methyl alcohol into a 10-ml ground-
glass-stoppered volumetric flask. Allow to stand about 10 min or until
all alcohol-wetted surfaces have dried. Weigh the flask to the nearest
0.1 mg.
5.3.2 Add the assayed reference material
5.3.2.1 Liquids: Using a 100-ul syringe, immediately add an
amount of assayed reference material to the flask, then reweigh.
Be sure that the reference material falls directly into the alcohol
without contacting the neck of the flask.
5.3.2.2 Gases: To prepare standards from any of the organic
compounds that boil below 30° C, fill a 5-ml valved gas-tight
syringe with the reference standard to the 5-ml mark. Lower the
needle to 5 mm above the methyl alcohol meniscus. Slowly inject
the reference standard above the surface of the liquid (the heavy
gas will rapidly dissolve into the methyl alcohol).
5.3.3 Reweigh, dilute to volume, stopper, then mix by inverting
the flask several times. Calculate the concentration in u.g/u.1 from
the net gain in weight. When compound purity is certified at 96%
or greater, the weight can be used without correction to calculate
the concentration of the stock standard. Commercially prepared stock
standards can be used at any concentration if they are certified by the
manufacturer or by an independent source.
5.3.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store at 4° C and protect from light.
5.3.5 Prepare fresh standards weekly for those co/npounds whose
boiling point is less than or equal to 30° C and for the 2-chloroethyl-
vinyl ether. All other standards must be replaced after 1 month, or
sooner if comparison with check standards indicate a problem.
5.4 Secondary dilution standards: Using stock standard solutions,
prepare secondary dilution standards in methyl alcohol that contain the
compounds of interest, either singly or mixed together. The secondary dilu-
tion standards should be prepared at concentrations such that the prepared
aqueous calibration standards will completely bracket the working range of
the analytical system. Secondary dilution standards must be stored with
zero headspace and should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them. Quality control check standards, available from the EPA's Environmental
Monitoring and Support Laboratory in Cincinnati, can be used to determine the
accuracy of calibration standards.
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8010 / 5
5.5 Calibration standards: In order to prepare accurate aqueous
standard solutions, the following precautions must be observed.
5.5.1 Do not inject more than 20 u.1 of alcoholic standards into
100 ml of reagent water.
5.5.2 Use a 25-u.l Hamilton 702N microsyringe or equivalent.
(Variations in needle geometry will adversely affect the ability
to deliver reproducible volumes of methanolic standards into water.)
5.5.3 Rapidly inject the alcoholic standard into the filled volu-
metric flask. Remove the needle as fast as possible after injection.
5.5.4 Mix aqueous standards by inverting the flask three times
only.
5.5.5 Discard the contents contained in the neck of the flask.
Fill the sample syringe from the standard solution contained in the
expanded area of the flask.
5.5.6 Never use pi pets to dilute or transfer samples or aqueous
standards.
5.5.7 Aqueous standards are not stable and should be discarded
after 1 hr unless preserved, stored, and sealed according to 6.1
and 6.3.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers (see Apparatus,
Sections 4.1 and 4.2) having a total volume of at least 25 ml. Fill the
sample bottles in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles are
entrapped in it. Solid and semisolid samples are to be taken in the same
way. Assure that no solid material interferes with sealing of the glass
vial. Maintain the hermetic seal on the sample bottle until time of analysis.
6.2 Sample transfer implements: Implements are required to transfer
portions of solid, semisolid, and liquid wastes from sample containers to
laboratory glassware. The transfer must be accomplished rapidly to avoid
loss of volatile components during the transfer step. Liquids may be trans-
ferred using a hypodermic syringe with a wide-bore needle attached or with no
needle. Solids may be transferred using a conventional laboratory spatula,
spoon, or coring device. A coring device that is suitable for handling some
samples can be made by using a glass tubing saw to cut away the enclosed end
of the barrel of a glass hypodermic syringe.
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6 / ORGANIC ANALYTICAL METHODS - GC
6.3 The samples must be iced or refrigerated fro.n the time of collec-
tion until extraction. If the sample may contain free or combined chlorine,
add sodium thiosulfate preservative (10 mg/40 ml will suffice for up to 5 ppm
Cl2) to the empty sample bottles just prior to shipping to the sampling site,
fill with sample just to overflowing, seal the bottle, and shake vigorously
for 1 min.
6.4 All samples must be analyzed within 14 days of collection.
7.0 Procedures
7.1 The recommended gas chromatographic columns and operating conditions
for the instrument are:
Column 1: Set helium gas flow at 40 ml /min flow rate. Set column
temperature at 45" C for 3 min, then program an 8° C/min temperature
rise to 220° C and hold for 15 min.
Column 2: Set helium gas flow at 40 ml /min flow rate. Set column
temperature at 50° C for 3 min, then program a 6* C/min temperature
rise to 170° C and hold for 4 min.
7.2 Calibration
7.2.1 By injecting secondary standards, adjust the sensitivity of
the analytical system for each compound being analyzed so as to detect
quantities of less than or equal to 1 u.g for waste samples. Detection
limits to be used for groundwater analysis are given in Table 1. Cali-
brate the chromatographic system using either the external standard tech-
nique (Section 7.2.2) or the internal standard technique (Section 7.2.3).
7.2.2 External standard calibration procedure
7.2.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0 u.1
of one or more secondary dilution standards to 100, 500, or 1,000
ml of reagent water or the matrix under study. A 25-u.l syringe
should 'be used for this operation. One of the external standards
should be at a concentration near, but above, the method detection
limit and the other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector. These aqueous standards must be
prepared fresh daily.
-------
8010 / 7
7.2.2.2 Analyze each calibration standard according to the
procedure being used (direct aqueous injection, headspace, or
purge-and-trap) and tabulate peak height or area responses against
the concentration in the standard. The results can be used to
prepare a calibration curve for each compound. Alternatively, if
the ratio of response to concentration (calibration factor) is a
constant over the working range (less than 10% relative standard
deviation), linearity through the origin can be assumed and the
average ratio or calibration factor can be used in place of a
calibration curve.
7.2.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than +10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that compound.
7.2.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the internal
standards is not affected by method or matrix interferences. Because of
these limitations, no internal standard that would be applicable to all
samples can be suggested. The compounds recommended for use as surrogate
spikes have been used successfully as internal standards, because of
their generally unique retention times.
7*2.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described
in Section 7.2.2.1.
7.2.3.2 Prepare a spiking solution containing each of the
internal standards using the procedures described in Sections 5.3
and 5.4.
7.2.3.3 Analyze each calibration standard according to
appropriate methods (direct injection, 5020, 5030), adding the
internal standard spiking solution directly to an aliquot of the
sample or, in the case of purge-and-trap, to the syringe. Tabu-
late peak height or area responses against concentration for each
compound and internal standard, and calculate response factors (RF)
for each compound as follows:
RF = (AsCis)/(AisCs)
-------
8 / ORGANIC ANALYTICAL METHODS - GC
where:
As = Response for the parameter to be measured
AJS = Response for the internal standard
Cis = Concentration of the internal standard
Cs = Concentration of the parameter to be measured
If the RF value over the working range is a constant (less than
10% relative standard deviation), the RF can be assumed to be
invariant and the average RF can be used for calculations. Alter-
natively, the results can be used to plot a calibration curve of
response ratios, As/AjS against RF.
7.2.3.4 The working calibration curve or RF must be verified
on each working day by measuring one or more calibration standards.
If the response for any parameter varies from the predicted response
by more than +1Q%, either the test must be repeated using a fresh
calibration standard, or a new calibration curve must be prepared
for that compound.
7.3 Gas chromatographic analysis
7.3.1 Introduce volatile compounds to the gas chromatograph using
direct injection, headspace (Method 5020), or purge-and-trap (Method
5030).
7.3.2 Table 1 summarizes the estimated retention times for a
number of organic compounds analyzable using this method. An example
of the separation achieved by Column 1 is shown in Figure 1.
7.3.3 Calibrate the system immediately prior to conducting any
analysis and recheck for each type of waste. Calibration should be
done no less frequently than at the beginning and end of each analysis
session.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
-------
8010 / 9
TABLE 1. ESTIMATED RETENTION TIMES FOR SOME HALOGENATED VOLATILE ORGANICS
Retention time Estimated
(min) detection
limit3
Compound Col. 1 Col. 2 ([ig/1)
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl)ether
Bromobenzene
Bromodichloromethane 13.7 14.6 0.10
Bromoform 19.2 19.2 0.20
Carbon tetrachloride 13.0 14.4 0.12
Chloroacetaldehyde
Chlorobenzene 24.2 18.8 0.25
Chloroethane 3.33 8.68 0.52
Chloroform 10.7 12.1 0.05
1-Chlorohexane
2-Chloroethyl vinyl ether 18.0 0.13
Chlorornethane 1.50 5.28 0.08
Chlorotoluene
Dibromochloromethane 16.5 16.6 0.09
Dibromomethane
1,2-Dichlorobenzene 34.9 23.5 0.15
1,3-Dichlorobenzene 34.0 22.4 0.32
1,4-Dichlorobenzene 35.4 22.3 0.24
Di chlorodi f1uoromethane
1,1-Dichloroethane 9.30 12.6 0.07
1,2-Dichloroethane 11.4 15.4 0.03
1,1-Dichloroethylene 8.0 7.72 0.13
trans-l,2-Dichloroethylene 10.1 9.38 0.10
Dichloromethane 6.5
1,2-Dichloropropane 14.9 16.6 0.04
trans-l,3-Dichloropropylene 15.2 16.6 0.34
1,1,2,2-Tetrachloroethane 21.6 0.03
1,1,1,2-Tetrachloroethane
Tetrachloroethylene 21.7 15.0 0.03
1,1,1-Trichloroethane 12.6 13.1 0.03
1,1,2-Trichloroethane 16.5 18.1 0.02
Trichloroethylene 15.8 13.1 0.12
Trichlorofluoromethane 7.18
Trichloropropane
Vinyl chloride 2.67 5.28 0.18
aUsing purge-and-trap method (5030). See also Section 8.3.
-------
10 / ORGANIC ANALYTICAL METHODS - GC
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8010 / 11
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed to
validate the sensitivity and accuracy of the analysis. If the fortified waste
samples do not indicate sufficient sensitivity to detect less than or equal
to 1 ug/g of sample, then the sensitivity of the instrument should be increased
or the extract subjected to additional cleanup. Detection limits to be used
for groundwater samples are indicated in Table 1. Where doubt exists over
the identification of a peak on the chrornatograph, confirmatory techniques
such as mass spectroscopy should be used.
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 2
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 2.
9.0 References
1. Bellar, T.A., and J.J.
Assoc. 66(12):739-744.
Lichtenberg. 1974. J. Amer. Water Works
2. Bellar, T.A., and J.J. Lichtenberg. 1979. Semi-automated headspace
and industrial waters for purgeable
In: Van Hall (ed.), Measurement of
and wastewater. ASTM STP 686, pp. 108-129.
analysis of drinking waters
volatile organic compounds.
organic pollutants in water
3. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 11 - Purgeables and
Category 12 - Acrolein, Acrylonitrile, and Dichlorodifluoromethane.
Report for EPA Contract 68-03-2635 (in preparation).
-------
12 / ORGANIC ANALYTICAL METHODS - GC
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION
/
f
Parameter r
Bromodi chl oromethane
Bromoform
Carbon tetrachloride
Chlorobenzene
Chl oroethane
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Di brornochl oromethane
1,2-Di chlorobenzene
1,3-Di chlorobenzene
1 ,4-Di chl orobenzene
1,1-Dichloroethane
1,2-Di chloroethane
1, 1-Di chl oroethylene
trans -1,2-Di chl oroethylene
1,2-Di chl oropropane
trans -1,3-Di chl orop ropy lene
1,1, 2, 2-Tetrachl oroethane
Tetrachl oroethylene
1,1,1-Tri chl oroethane
1,1,2-Tri chl oroethane
Tri chl oroethylene
Vinyl chloride
We rage
jercent
^ecovery
100.9
89.5
82.5
93.9
91.5
96.3
101.7
91.4
98.3
102.0
91.6
97.5
.102.3
97.8
101.1
91.0
97.7
73.5
91.9
94.1
75.1
91.0
106.1
101.9
Standard
deviatio
f w \
\ /o I
5.0
9.0
25.6
8.9
22.4
9.9
20.6
13.4
6.5
2.0
4.3
9.3
5.5
4.8
21.7
19.3
8.8
17.2
15.0
18.1
12.5
25.1
7.4
11.4
Spike
n range
(^9/1)
0.43-46.7
1.45-50
0.55-50
2.21-50
3.95-50
4.39-133
0.44-50
0.55-23.9
0.75-93.0
4.89-154
2.94-46.7
2.99-51.6
0.44-46.7
0.44-46.7
0.37-50
0.44-98.0
0.29-39.0
0.43-50
0.46-46.7
0.50-35.0
0.37-29.0
0.45-50
0.38-46.7
0.82-32.3
Number
of
analyses
21
20
19
20
21
20
20
21
21
21
21
21
21
21
19
20
21
20
21
21
21
21
21
21
Matrix
types
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
-------
METHOD 8015
NONHALOGENATED VOLATILE OR6ANICS
1.0 Scope and Application
1.1 Method 8015 is used to determine the concentration of nonhalogen-
ated volatile organic compounds in groundwater, liquid, and solid matrices.
Specifically, Method 8015 is used to detect the following substances:
Aery1 amide
Carbon disulfide
Diethyl ether
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Paraldehyde (trimer of acetaldehyde)
1.2 This method is recommended for use by, or under the supervision
of, analysts experienced in the operation of gas chromatographs and in the
interpretation of chromatograms.
2.0 Summary of Method
2.1 Method 8015 provides chromatographic conditions for the detection
of certain nonhalogenated volatile organic compounds. Waste samples can be
analyzed using direct injection, the headspace method (Method 5020) or the
purge-and-trap method (Method 5030). Groundwater samples can be analyzed by
Method 5030. A temperature program is used in the gas chromatograph to separate
the organic compounds. Detection is achieved by a flame ionization detector
(FID).
2.2 If interferences are encountered, the method provides an optional
gas chromatographic column that may be helpful in resolving the compounds of
interest from the interferences.
3.0 Interferences
3.1 Samples can be contaminated by diffusion of volatile organics
through the sample container septum during shipment and storage. A field
sample blank prepared from reagent water and carried through sampling and
subsequent storage and handling can serve as a check on such contamination.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe or purging device must be rinsed out between samples with reagent
water. Whenever an unusually concentrated sample is encountered, it should
-------
2 / ORGANIC ANALYTICAL METHODS - GC
be followed by an analysis of reagent water to check for cross contamination.
For samples containing large amounts of water-soluble materials, suspended
solids, high boiling compounds or high organohalide levels, it may be neces-
sary to wash out the syringe or purging device with a detergent solution,
rinse it with distilled water, and then dry it in a 105" C oven between
analyses.
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.4 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 jig/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower; they should be
less than 1 u.g/1.
4.0 Apparatus and Materials
4.1 Vial with cap: 40-ml capacity screw cap vial (Pierce #13075 or
equivalent). Detergent wash, rinse with tap and distilled deionized water,
and dry at 105" C before use.
4.2 Septum: Teflon-faced silicone (Pierce #12722 or equivalent).
Detergent wash, rinse with tap and distilled deionized water, and dry at
105* C for 30 min before use. NOTE: Do not heat the TFE seals for extended
periods of time (i.e., more than 1 hr) because the silicone layer slowly
degrades at 105" C.
4.3 Sample introduction apparatus for Methods 5020 and 5030.
4.4 Gas chromatograph: Analytical system complete with programmable
gas chromatograph suitable for on-column injection or purge-and-trap sample
introduction and all required accessories, including .FID, column supplies,
recorder, and gases. A data system for measuring peak area is recommended.
-------
8015 / 3
4.5 GC columns:
Column 1: 8-ft x 0.1-in. I.D. stainless steel or glass column
packed with 1% SP-1000 on Carbopac B 60/80 mesh.
Column 2: 6-ft x 0.1-in. I.D. stainless steel or glass column
packed with n-octane on Porasil-L 100/120 mesh.
4.6 Detector: Flame ionization (FID).
4.7 Syringes: 5-ml glass hypodermic with Luerlok top (2 each).
4.8 Microsyringes: 10, 25, 100 ul.
4.9 Two-way syringe valve with Luer ends (3 each).
4.10 Syringe: 5-ml, gas-tight with shutoff valve.
4.11 Bottle: 15-ml screw-cap, with teflon cap liner.
5.0 Reagents
5.1 Activated carbon: Filtrasorb 200 (Calgon Corp.) or equivalent.
5.2 Organic-free water: Generated by passing tap water through a
carbon filter bed containing about 1 Ib of activated carbon. A water pur-
ification system (Millipore Super-Q or equivalent) may be used to generate
organic-free deionized water. Organic-free water may also be prepared by
boiling water for 15 min. Subsequently, while maintaining the temperature
at 90° C, bubble a contaminant-free inert gas through the water for 1 hr.
5.3 Stock standard solutions: Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions. Prepare
stock standard solutions in methyl alcohol using assayed liquids. Because of
the toxicity of many of the compounds being analyzed, primary dilutions of
these materials should be prepared in a hood. A NIOSH/MESA-approved toxic
gas respirator should be used when the analyst handles high concentrations of
such materials.
5.3.1 Place about 9 ml of methyl alcohol into a 10-ml ground-
glass-stoppered volumetric flask. Allow to stand about 10 min or until
all alcohol-wetted surfaces have dried. Weigh the flask to the nearest
0.1 mg.
5.3.2 Using a 100-ul syringe, immediately add an amount of assayed
reference material to the flask, then reweigh. Be sure that the reference
material falls directly into the methyl alcohol without contacting the
neck of the flask.
-------
4 / ORGANIC ANALYTICAL METHODS - GC
5.3.3 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store at 4" C and protect from light.
5.3.4 Prepare fresh standards weekly for those compounds whose
boiling point is less than or equal to 30' C. All other standards must
be replaced after 1 month, or sooner if comparison with check standards
indicate a problem.
5.4 Secondary dilution standards: Using stock standard solutions,
prepare secondary dilution standards in methyl alcohol that contain the
compounds of interest, either singly or mixed together. The secondary dilu-
tion standards should be prepared at concentrations such that the prepared
aqueous calibration standards will completely bracket the working range of
the analytical system. Secondary dilution standards must be stored with
zero headspace and should be checked frequently for signs, of degradation or
evaporation, especially just prior to preparing calibration standards from
them. Quality control check standards, available from the EPA's Environmental
Monitoring and Support Laboratory in Cincinnati, can be used to determine the
accuracy of calibration standards.
5.5 Calibration standards: In order to prepare accurate aqueous standard
solutions, the following precautions must be observed.
5.5.1 Do not inject more than 20 ul of methanolic standards into
100 ml of reagent water.
5.5.2 Use a 25-ul Hamilton 702N microliter syringe or equivalent.
(Variations in needle geometry will adversely affect the ability
to deliver reproducible volumes of methanolic standards into water.)
5.5.3 Rapidly inject the methanolic standard into the filled volu-
metric flask below the neck. Remove the needle as fast as possible
after injection.
5.5.4 Mix aqueous standards by inverting the flask three times
only.
5.5.5 Discard the contents contained in the neck of the flask.
Fill the sample syringe from the standard solution contained in the
expanded area of the flask.
5.5.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.5.7 Aqueous standards are not stable and should be discarded
unless stored and sealed as stipulated in Sections 6.1 and 6.3.
-------
8015 / 5
(see Apparatus,
Fill the
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers
Sections 4.1 and 4.2) having a total volume of at least 25 ml.
sample bottles in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles are
entrapped in it. Solid and semisolid samples are to be taken in the same
way. Assure that no solid material interferes with sealing of the glass
vial. Maintain the hermetic seal on the sample bottle until time of analysis.
6.2 Sample transfer implements: Implements are required to transfer
portions of solid, semisolid, and liquid wastes from sample containers to
laboratory glassware. The transfer must be accomplished rapidly to avoid
loss of volatile components during the transfer step. Liquids may be trans-
ferred using a hypodermic syringe with a wide-bore needle attached or with no
needle. Solids may be transferred using a conventional laboratory spatula,
spoon, or coring device. A coring device that is suitable for handling some
samples can be made by using a glass tubing saw to cut away the enclosed end
of the barrel of a glass hypodermic syringe.
6.3 The samples must be iced or refrigerated from the time of collec-
tion until extraction. If the sample contains free or combined chlorine,
add sodium thiosulfate preservative (10 mg/40 ml will suffice for up to 5 ppm
Cl2) to the empty sample bottles just prior to shipping to the sampling
site, fill with sample just to overflowing, seal the bottle, and shake
vigorously for 1 min.
6.4 All samples must be analyzed within 14 days of collection.
7.0 Procedures
7.1 The recommended gas chromatographic column and operating conditions
for the instrument are:
Column 1: Set helium gas flow at 40 ml/min flow rate. Set column
temperature at 45° C for 3 min, then program an 8° C/min temperature
rise to 220° C and hold for 15 min.
Column 2: Set helium gas flow at 40 ml/min flow rate. Set column
temperature at 50° C for 3 min, then program a 6° C/min temperature
rise to 170° C and hold for 4 min.
7.2 Calibration
7.2.1 By injecting secondary standards, adjust the sensitivity of
the analytical system for each compound being analyzed so as to detect
quantities of less than or equal to 1 u.g for waste samples.
-------
6 / ORGANIC ANALYTICAL METHODS - GC
Calibrate the chromatographic system using either the external standard
technique (Section 7.2.2) or the internal standard technique (Section 7.2.3),
7.2.2 External standard calibration procedure
7.2.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0 jil
of one or more secondary dilution standards to 100, bOO, or 1,000
ml of reagent water or the matrix under study. A 25-u/l syringe
limit and the other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range ot the detector. These aqueous standards must be
prepared fresh daily.
7.2.2.2 Analyze each calibration standard according to the
procedure being used (direct aqueous injection, headspace, or
purge-and-trap) and tabulate peak height or area responses against
the concentration in the standard. The results can be used to
prepare a calibration curve for each compound. Alternatively, it
the ratio of response to concentration (calibration factor) is a
constant over the working range (less than 10% relative standard
deviation), linearity through the origin can be assumed and the
average ratio or calibration factor can be used in place of a
calibration curve.
7.2.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement ot one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than +10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that compound.
7.2.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the internal
standards is not affected by method or matrix interferences. Because
of these limitations, no internal standard that would be applicable to
all samples can be suggested.
7.2.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described
in Section 7.2.2.1.
7.2.3.2 Prepare a spiking solution containing each of the
internal standards using the procedures described in Sections 5.3
and 5.4.
-------
8015 / 7
7.2.3.3 Analyze each calibration standard according to
appropriate methods (direct injection, 5020, 5030), adding the
internal standard spiking solution directly to an aliquot of the
sample or, in the case of purge-and-trap, to the syringe. Tabu-
late peak height or area responses against concentration for each
compound and internal standard, and calculate response factors (RF)
for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured
AiS = Response for the internal standard
C-jS = Concentration of the internal standard
Cs = Concentration of the parameter to be measured
If the RF value over the working range is a constant (less than
10% relative standard deviation), the RF can be assumed to be
invariant and the average RF can be used for calculations. Alter-
natively, the results can be used to plot a calibration curve of
response ratios, As/A-jS against RF.
7.2.3.4 The working calibration curve or RF must be verified
on each working day by measuring one or more calibration standards.
If the response for any parameter varies from the predicted response
by more than +10%, either the test must be repeated using a fresh
calibration standard, or a new calibration curve must be prepared
for that compound.
7.3 Gas chromatographic analysis
7.3.1 Introduce volatile compounds to the gas chromatograph using
direct injection, headspace (Method 5020), or purge-and-trap (Method
5030).
7.3.2 Calibrate the system immediately prior to conducting any
analysis and recheck for each type of waste. Calibration should be
done no less frequently than at the beginning and end of each analysis
session.
-------
8 / ORGANIC ANALYTICAL METHODS - GC
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed to
validate the sensitivity and accuracy of the analysis. If the fortified
samples do not indicate sufficient sensitivity to detect less than or equal
to 1 u.g/g of sample, then the sensitivity of the instrument should be increased.
Where doubt exists over the identification of a peak on the chromatograph,
confirmatory techniques such as mass spectroscopy should be used.
9.0 References
1. Bellar, T.A., and J.J. Lichtenberg. 1974. J. Amer. Water Works
Assoc. 66(12):739-744.
2. Bellar, T.A., and J.J. Lichtenberg. 1979. Semi-automated headspace
analysis of drinking waters and industrial waters for purgeable vola-
tile organic compounds. In: Van Hall (ed.), Measurement of organic
pollutants in water and wastewater. ASTM STP 686, pp. 108-129.
3. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 11 - Purgeables and
Category 12 - Acrolein, Acrylonitrile, and Dichlorodifluoromethane.
Report for EPA Contract 68-03-2635 (in preparation).
-------
METHOD 8020
AROMATIC VOLATILE ORGANICS
1.0 Scope and Application
1.1 Method 8020 is used to determine the concentration of various
aromatic volatile organic compounds in groundwater, liquid, and solid
matrices. Specifically, Method 8020 may be used to detect the following
substances:
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
Ethyl benzene
Toluene
Xylenes (Dimethyl benzenes)
1.2 This method is recommended for use by, or under the supervision
of, analysts experienced in the operation of gas chromatographs and in the
interpretation of chromatograms.
2.0 Summary of Method
2.1 Method 8020 provides chromatographic conditions for the detection
of aromatic volatile organic compounds. Waste samples can be analyzed
using direct injection, the headspace method (Method 5020) or the purge-
and-trap method (Method 5030). Groundwater samples should be determined
using Method 5030. A temperature program is used in the gas chromatograph to
separate the organic compounds. Detection is achieved by a photo-ionization
detector (PID).
2.2 If interferences are encountered, the method provides an optional
gas chromatographic column that may be helpful in resolving the compounds of
interest from the interferences.
3.0 Interferences
3.1 Samples can be contaminated by diffusion of volatile organics
through the sample container septum during shipment and storage. A field
sample blank prepared from reagent water and carried through sampling and
subsequent storage and handling can serve as a check on such contamination.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
-------
2 / ORGANIC ANALYTICAL METHODS - GC
syringe or purging device must be rinsed out between samples with reagent
water. Whenever an unusually concentrated sample is encountered, it should
be followed by an analysis of reagent water to check for cross contamination.
For samples containing large amounts of water-soluble materials, suspended
solids, high boiling compounds or high levels of volatile organics, it may be
necessary to wash out the syringe or purging device with a detergent solution,
rinse it with distilled water, and then dry it in a 105* C oven between
analyses.
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.4 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 uxj/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 (below) when
analyzing groundwater samples.
4.0 Apparatus and Materials
4.1 Vial with cap: 40-ml capacity screw cap vial (Pierce #13075 or
equivalent). Detergent wash, rinse with tap and distilled deionized water,
and dry at 105* C before use.
4.2 Septum: Teflon-faced silicone (Pierce #12722 or equivalent).
Detergent wash, rinse with tap and distilled deionized water, and dry at
105* C for 30 min before use. NOTE: Do not heat the TFE seals for extended
periods of time (i.e., more than 1 hour) because the silicone layer slowly
degrades at 105* C.
4.3 Sample introduction apparatus for Methods 5020 and 5030.
4.4 Gas chromatograph: Analytical system complete with programmable
gas chromatograph suitable for on-column injection or purge-and-trap sample
introduction and all required accessories, including PID, column supplies,
recorder, and gases. A data system for measuring peak area is recommended.
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8020 / 3
4.5 GC columns:
Column 1: 6-ft x 0.082-in. I.D. #304 stainless steel or glass
tubing. Packed with 5% SP-1200 + 1.75% Bentone 34 on 100/120 mesh
Supelcoport.
Column 2: 6-ft x 0.1-in. I.D. #304 stainless steel or glass tubing
packed with 5% l,2,3-tris(2-cyanoethoxy)propane on 60/80 mesh
Chromosorb W-AW.
4.6 Detector: Photoionization (PID).
4.7 Syringes: 5-ml glass hypodermic with Luerlok top (2 each).
4.8 Microsyringes: 10, 25, 100 ul.
4.9 Two-way syringe valve with Luer ends (3 each).
4.10 Syringe: 5-ml, gas-tight with shutoff valve.
4.11 Bottle: 15-ml screw-cap, with teflon cap liner.
5.0 Reagents
5.1 Activated carbon: Filtrasorb 200 (Calgon Corp.) or equivalent.
5.2 Organic-free water: Generated by passing tap water through a
carbon filter bed containing about 1 Ib of activated carbon. A water pur-
ification system (Millipore Super-Q or equivalent) may be used to generate
organic-free deionized water. Organic-free water may also be prepared by
boiling water for 15 min. Subsequently, while maintaining the temperature
at 90° C, bubble a contaminant-free inert gas through the water for 1 hr.
5.3 Stock standard solutions: Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions. Prepare
stock standard solutions in methyl alcohol using assayed liquids. Because of
the toxicity of many of the compounds being analyzed, primary dilutions of
these materials should be prepared in a hood. A NIOSH/MESA-approved toxic
gas respirator should be used when the analyst handles high concentrations of
such materials.
5.3.1 Place about 9 ml of methyl alcohol into a 10-ml ground-
glass-stoppered volumetric flask. Allow to stand about 10 min or until
all alcohol-wetted surfaces have dried. Weigh the flask to the nearest
0.1 mg.
5.3.2 Using a 100-u.l syringe, immediately add an amount of assayed
reference material to the flask, then reweigh. Be sure that the reference
-------
4 / ORGANIC ANALYTICAL METHODS - GC
material falls directly into the alcohol without contacting the neck of
the flask.
5.3.3 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store at 4" C and protect from light.
5.3.4 Prepare fresh standards weekly for those compounds whose
boiling point is less than or equal to 30° C. All other standards must
be replaced after 1 month, or sooner if comparison with check standards
indicates a problem.
5.4 Secondary dilution standards: Using stock standard solutions,
prepare secondary dilution standards in methyl alcohol that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the pre-
pared aqueous calibration standards will completely bracket the working range
of the analytical system. Secondary dilution standards must be stored with
zero headspace and should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them. Quality control check standards, available from the EPA's Environmental
Monitoring and Support Laboratory in Cincinnati, can be used to determine the
accuracy of calibration standards.
5.5 Calibration standards: In order to prepare accurate aqueous standard
solutions, the following precautions must be observed.
5.5.1 Do not inject more than 20 u.1 of alcoholic standards into
100 ml of reagent water.
5.5.2 Use a 25-jil Hamilton 702N microsyringe or equivalent.
(Variations in needle geometry will adversely affect the ability
to deliver reproducible volumes of methanolic standards into water.)
5.5.3 Rapidly inject the alcoholic standard into the filled volu-
metric flask. Remove the needle as fast as possible after injection.
5.5.4 Mix aqueous standards by inverting the flask three times
only.
5.5.5 Discard the contents contained in the neck of the flask.
Fill the sample syringe from the standard solution contained in the
expanded area of the flask.
5.5.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.5.7 Aqueous standards are not stable and should be discarded
after one hour unless preserved, stored, and sealed according to 6.1
and 6.3.
-------
8020 / 5
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers (see Apparatus,
Sections 4.1 and 4.2) having a total volume of at least 25 ml. Fill the
sample bottles in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles are
entrapped in it. Solid and semisolid samples are to be taken in the same
way. Assure that no solid material interferes with sealing of the glass
vial. Maintain the hermetic seal on the sample bottle until time of analysis.
6.2 Sample transfer implements: Implements are required to transfer
portions of solid, semisolid, and liquid wastes from sample containers to
laboratory glassware. The transfer must be accomplished rapidly to avoid
loss of volatile components during the transfer step. Liquids may be trans-
ferred using a hypodermic syringe with a wide-bore needle attached or with no
needle. Solids may be transferred using a conventional laboratory spatula,
spoon, or coring device. A coring device that is suitable for handling some
samples can be made by using a glass tubing saw to cut away the enclosed end
of the barrel of a glass hypodermic syringe.
6.3 The samples must be iced or refrigerated from the time of collec-
tion until extraction. If the sample may contain free or combined chlorine,
add sodium thiosulfate preservative (10 mg/40 ml will suffice for up to 5 ppm
013) to the empty sample bottles just prior to shipping to the sampling
site, fill with sample just to overflowing, seal the bottle, and shake
vigorously for 1 min.
6.4 Sample preservation: Non-sterile samples containing aromatic
hydrocarbons cannot be stored longer than 4 hr because of biological
degradation.^ Samples can be stabilized by adding free chlorine or by
adjusting the pH to less than 2 with 1:1 hydrochloric acid. However, free
chlorine will react with styrene and 2,3-benzofuran. Therefore, if styrene
or 2,3-benzofuran are to be determined in chlorinated water, the sample must
be dechlorinated with sodium thiosulfate at the rate of 1 mg/ppm of free
chlorine. Once dechlorinated, the sample pH must be adjusted to less than 2
with 1:1 hydrochloric acid. If chemical preservation is employed, the pre-
servative is also added to the blanks.
6.5 All samples must be analyzed within 14 days of collection.
7.0 Procedures
7.1 The recommended gas chromatographic columns and operating conditions
for the instrument are:
Column 1: The carrier gas is helium at a flow rate of 30 ml/min. The
temperature program sequences are as follows: for lower boiling compounds,
operate at 50° C isothermal for 2 min, then program at 6" C/min to 90* C
-------
6 / ORGANIC ANALYTICAL METHODS - GC
and hold until all compounds have eluted. For a higher boiling range of
compounds, operate at 50' C isothermal for 2 min, then program at S'/min
to 110" C and hold until all compounds have eluted. Column 1 provides
outstanding separations for a wide variety of aromatic hydrocarbons.
Column 1 should be used as the primary analytical column because of its
unique ability to resolve para, meta, and ortho aromatic isomers.
Column 2: The carrier gas is helium at a flow rate of 30 ml/min. The
temperature program sequence is as follows: 40° C isothermal for 2 min,
then 2*/min to 100* C and hold until all compounds have eluted. Col-
umn 2, an extremely high polarity column, has been used for a number of
years to resolve aromatic hydrocarbons from alkanes in complex samples.
However, since the resolution between some of the aromatics is not as
efficient as with Column 1, Column 2 should be used as a confirmatory
column.
7.2 Calibration. Assemble necessary gas chromatographic apparatus and
establish operating parameters equivalent to those indicated in Section 7.1.
7.2.1 By injecting secondary standards, adjust the sensitivity of
the analytical system for each compound being analyzed so as to detect
quantities of less than or equal to 1 u,g for waste samples. Detection
limits to be used for groundwater analysis are given in Table 1.
Calibrate the chromatographic system using either the external
standard technique (Section 7.2.2) or the internal standard technique
(Section 7.2.3).
7.2.2 External standard calibration procedure
7.2.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0 u.1
of one or more secondary dilution standards to 100, 500, or 1,000
ml of reagent water or the matrix under study. A 25-u.l syringe
should be used for this operation. One of the external standards
should be at a concentration near, but above, the method detection
limit and the other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector. These aqueous standards must be
prepared fresh daily.
7.2.2.2 Analyze each calibration standard according to the
procedure being used (direct aqueous injection, headspace, or
purge-and-trap) and tabulate peak height or area responses against
the concentration in the standard. The results can be used to
prepare a calibration curve for each compound. Alternatively, if
the ratio of response to concentration (calibration factor) is a
constant over the working range (less than 10% relative standard
deviation), linearity through the origin can be assumed and the
-------
8020 / 7
average ratio or calibration factor can be used in place of a
calibration curve.
7.2.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than +10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that compound.
7.2.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the internal
standards is not affected by method or matrix interferences. Because
of these limitations, no internal standard that would be applicable to
all samples can be suggested. The compounds recommended for use as
surrogate spikes have been used successfully as internal standards,
because of their generally unique retention times.
7.2.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described
in Section 7.2.2.1.
7.2.3.2 Prepare a spiking solution containing each of the
internal standards using the procedures described in Sections 5.3
and 5.4.
7.2.3.3 Analyze each calibration standard according to
appropriate methods (direct injection, 5020, 5030), adding the
internal standard spiking solution directly to an aliquot of the
sample or, in the case of purge-and-trap, to the syringe. Tabu-
late peak height or area responses against concentration for each
compound and internal standard, and calculate response factors (RF)
for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured
A1S = Response for the internal standard
Cis = Concentration of the internal standard
Cs = Concentration of the parameter to be measured
-------
8 / ORGANIC ANALYTICAL METHODS - GC
If the RF value over the working range is a constant (less than
10% relative standard deviation), the RF can be assumed to be
invariant and the average RF can be used for calculations. Alter-
natively, the results can be used to plot a calibration curve of
response ratios, As/AjS against RF.
7.2.3.4 The working calibration curve or RF must be verified
on each working day by measuring one or more calibration standards.
If the response for any parameter varies from the predicted response
by more than +10%, either the test must be repeated using a fresh
calibration standard, or a new calibration curve must be prepared
for that compound.
7.3 Gas chromatographic analysis
7.3.1 Introduce volatile compounds to the gas chromatograph using
direct injection, headspace (Method 5020), or purge-and-trap (Method
5030).
7.3.2 Table 1 summarizes the estimated retention times and detec-
tion limits for a number of organic compounds analyzable using this
method. An example of the separation achieved by Column 1 is shown in
Figure 1. An example of the separation achieved by Column 2 is shown in
Figure 2.
7.3.3 Calibrate the system immediately prior to conducting any
analysis and recheck for each type of waste. Calibration should be
done no less frequently than at the beginning and end of each analysis
session.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed
to validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 u,g/g of sample, then the sensitivity of the instrument should be
-------
8020 / 9
TABLE 1. RETENTION TIMES FOR SOME AROMATIC VOLATILE ORGANICS
Compound
Benzene
Chlorobenzene
1,4-Di chlorobenzene
1,3-Di Chlorobenzene
1,2-Di chlorobenzene
Toluene
Ethyl Benzene
Xylenes
Retention
time (min)
3.33
9.17
16.8
18.2
25.9
5.75
8.25
Method detection
limit3 (ug/1)
0.2
0.2
0.3
0.4
0.4
0.2
0.2
Column: 6-ft x 1/8-in. column packed with 1.75%
Bentone 34 and 5% SP-2100 on Supelcoport 100/200.
aUsing purge-and-trap Method 5030. See also
Section 8.3.
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION
Parameter
Benzene
Chlorobenzene
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlcrobenzene
Ethyl benzene
Toluene
Average
percent
recovery
91
97
104
97
120
98
77
Standard
deviation
(%)
10.0
9.4
27.7
20.0
20.4
12.4
12.1
Spike
range
(H9/1 )
0.5-9.7
0.5-100
0.5-10.0
0.5-4.8
0.5-10.0
0.5-9.9
0.5-100
Number
of
analyses
21
21
21
21
21
21
21
Matrix
types
3
3
3
3
3
3
3
-------
10 / ORGANIC ANALYTICAL METHODS - GC
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8020 / 11
Column: 5% 1,2,3-Tris (2-Cyanoethoxy)
Propane on Chromosorb—W
Program: 40°C-2 Minutes 2°C/Min. to 100°C
Detector: Photoionization
Sample: 2.0 pg/l Standard Mixture
8 12 16
RETENTION TIME (MINUTES)
24
Figure 2. Chromatogram of aromatic volatile organics (column 2 conditions).
-------
12 / ORGANIC ANALYTICAL METHODS - GC
increased. Detection limits to be used for groundwater samples are indicated
in Table 1. Where doubt exists over the identification of a peak on the
chromatograph, confirmatory techniques such as mass spectroscopy should be
used.
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 2
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 2.
9.0 References
1. Bellar, T.A., and J.J. Lichtenberg.
Assoc. 66(12):739-744.
1974. J. Amer. Water Works
2. Bellar, T.A., and J.J. Lichtenberg. 1979. Semi-automated headspace
analysis of drinking waters and industrial waters for purgeable vola-
tile organic compounds. In: Van Hall (ed.), Measurement of organic
pollutants in water and wastewater. ASTM STP 686, pp. 108-129.
3. Dowty, B.J., S.R. Antoine, and J.L. Laseter. 1979. Quantitative
and qualitative analysis of purgeable organics by high resolution gas
chromatography and flame ionization detection. In: Van Hall (ed.),
Measurement of Organic Pollutants in Water and Wastewater. ASTM STP
686, pp. 24-35.
4. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 11 - Purgeables and
Category 12 - Acrolein, Acrylonitrile, and Dichlorodifluoromethane.
Report for EPA Contract 68-03-2635 (in preparation).
-------
METHOD 8030
ACROLEIN. ACRYLONITRILE. ACETONITRILE
1.0 Scope and App1i cati on
1.1 Method 8030 is used to determine the concentration of three
volatile organic compounds' in groundwater, liquid, and solid matrices.
Specifically, Method 8030 is used to detect the following substances:
Acrolein (Propenal)
Acrylonitrile
Acetonitrile
1.2 This method is recommended for use by, or under the supervision
of, analysts experienced in the operation of gas chromatographs and in the
interpretation of chromatograms.
2.0 Summary of Method
2.1 Method 8030 provides chromatographic conditions for the detection
of certain halogenated volatile organic compounds. Waste samples can be
analyzed using direct injection, the headspace method (Method 5020) or the
purge-and-trap method (Method 5030). Groundwater samples should be analyzed
using Method 5030. A temperature program is used in the gas chromatograph to
separate the organic compounds. Detection is achieved by a flame ionization
detector (FID).
3.0 Interferences
3.1 Samples can be contaminated by diffusion of volatile organics
through the sample container septum during shipment and storage. A field
sample blank prepared from reagent water and carried through sampling and
subsequent storage and handling can serve as a check on such contamination.
3.2 Contamination by carryover can occur whenever high-level and low-
level samples are sequentially analyzed. To reduce carryover, the sample
syringe or purging device must be rinsed out between samples with reagent
water. Whenever an unusually concentrated sample is encountered, it should
be followed by an analysis of reagent water to check for cross contamination.
For samples containing large amounts of water-soluble materials, suspended
solids, high boiling compounds or high organohalide levels, it may be neces-
sary to wash out the syringe or purging device with a detergent solution,
rinse it with distilled water, and then dry it in a 105° C oven between
analyses.
-------
2 / ORGANIC ANALYTICAL METHODS - GC
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.4 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 u.g/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table I (below) when
analyzing groundwater samples.
4.0 Apparatus and Materials
4.1 Vial with cap: 40-ml capacity screw cap (Pierce #13075 or equiv-
alent). Detergent wash, rinse with tap and distilled deionized water, and
dry at 105* C before use.
4.2 Septum: Teflon-faced silicone (Pierce #12722 or equivalent).
Detergent wash, rinse with tap and distilled deionized water, and dry at
105* C for 30 min before use. NOTE: Do not heat the TFE seals for extended
periods of time (i.e., more than 1 hr) because the silicone layer slowly
degrades at 105* C.
4.3 Sample introduction apparatus for Methods 5020 and 5030.
4.4 Gas chromatograph: Analytical system complete with programmable
gas chromatograph suitable for on-column injection or purge-and-trap sample
introduction and all required accessories, including FID, column supplies,
recorder, and gases. A data system for measuring peak area is recommended.
4.5 GC column: 6-ft x 1/8-in. stainless steel.or 6-ft x 1/4-in. glass
column packed with Chromosorb 101 (60/80 mesh) or equivalent.
4.6 Detector: Flame ionization (FID).
4.7 Syringes: 5-ml glass hypodermic with Luerlok top (2 each).
4.8 Microsyringes: 10, 25, 100 \i].
-------
8030 / 3
4.9 Two-way syringe valve with Luer ends (3 each).
4.10 Syringe: 5-ml, gas-tight with shutoff valve.
4.11 Bottle: 15-ml screw-cap, with teflon cap liner.
5.0 Reagents
5.1 Activated carbon: Filtrasorb 200 (Calgon Corp.) or equivalent.
5.2 Organic-free water: Generated by passing tap water through a
carbon filter bed containing about 1 Ib of activated carbon. A water pur-
ification system (Millipore Super-Q or equivalent) may be used to generate
organic-free deionized water. Organic-free water may also be prepared by
boiling water for 15 min. Subsequently, while maintaining the temperature
at 90° C, bubble a contaminant-free inert gas through the water for 1 hr.
5.3 Stock standard solutions: Stock standard solutions can be prepared
from pure standard materials or purchased as certified solutions. Prepare
stock standard solutions in methyl alcohol using assayed liquids or gas
cylinders as appropriate. Because of the toxicity of many of the compounds
being analyzed, primary dilutions of these materials should be prepared in
a hood. A NIOSH/MESA-approved toxic gas respirator should be used when the
analyst handles high concentrations of such materials.
5.3.1 Place about 8 ml of methyl alcohol into a 10-ml ground-
glass-stoppered volumetric flask. Allow to stand about 10 min or until
all alcohol-wetted surfaces have dried. Weigh the flask to the nearest
0.1 mg.
5.3.2 Using a 100-u.l syringe, immediately add an amount of assayed
reference material to the flask, then reweigh. Be sure that the reference
material falls directly into the alcohol without contacting the neck of
the flask.
5.3.3 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store at 4° C and protect from light.
5.3.4 Prepare fresh standards weekly for those compounds whose
boiling point is less than or equal to 30° C and for the 2-chloroethyl-
vinyl ether. All other standards must be replaced after 1 month, or
sooner if comparison with check standards indicate a problem.
5.4 Secondary dilution standards: Using stock standard solutions,
prepare secondary dilution standards in methyl alcohol that contain the
compounds of interest, either singly or mixed together. The secondary dilu-
tion standards should be prepared at concentrations such that the prepared
aqueous calibration standards will completely bracket the working range of
-------
4 / ORGANIC ANALYTICAL METHODS - GC
the analytical system. Secondary dilution standards must be stored with
zero headspace and should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them. Quality control check standards, available from the EPA's Environmental
Monitoring and Support Laboratory in Cincinnati, can be used to determine the
accuracy of calibration standards.
5.5 Calibration standards: In order to prepare accurate aqueous
standard solutions, the following precautions must be observed.
5.5.1 Do not inject more than 20 u.1 of alcoholic standards into
100 ml of reagent water.
5.5.2 Use a 25-u.l Hamilton 702N microsyringe or equivalent.
(Variations in needle geometry will adversely affect the ability
to deliver reproducible volumes of methanolic standards into water.)
5.5.3 Rapidly inject the alcoholic standard into the filled volu-
metric flask. Remove the needle as fast as possible after injection.
5.5.4 Mix aqueous standards by inverting the flask three times
only.
5.5.5 For standards prepared in 500- or 1,000-ml flasks, discard
the contents contained in the neck of the flask. Fill the sample
syringe from the standard solution contained in the expanded area of
the flask.
5.5.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.5.7 Aqueous standards are not stable and should be discarded
after 1 hr unless stored and sealed as stipulated in Sections 6.1
and 6.3.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers (see Apparatus,
Sections 4.1 and 4.2) having a total volume of at least 25 ml. Fill the
sample bottles in such a manner that no air bubbles pass through the sample
as the bottle is being filled. Seal the bottle so that no air bubbles are
entrapped in it. Solid and semisolid samples are to be taken in the same
way. Assure that no solid material interferes with sealing of the glass
vial. Maintain the hermetic seal on the sample bottle until time of analysis.
6.2 Sample transfer implements: Implements are required to transfer
portions of solid, semisolid, and liquid wastes from sample containers to
-------
8030 / 5
laboratory glassware. The transfer must be accomplished rapidly to avoid
loss of volatile components during the transfer step. Liquids may be trans-
ferred using a hypodermic syringe with a wide-bore needle attached or with no
needle. Solids may be transferred using a conventional laboratory spatula,
spoon, or coring device. A coring device that is suitable for handling some
samples can be made by using a glass tubing saw to cut away the enclosed end
of the barrel of a glass hypodermic syringe.
6.3 The samples must be iced or refrigerated from the time of collec-
tion until extraction. If the sample may contain free or combined chlorine,
add sodium thiosulfate preservative (10 mg/40 ml will suffice for up to 5 ppm
Cl2) to the empty sample bottles just prior to shipping to the sampling
site, fill with sample just to overflowing, seal the bottle, and shake
vigorously for 1 min.
6.4 All samples must be analyzed within 14 days of collection.
7.0 Procedures
7.1 The recommended gas chromatographic column and operating conditions
for the instrument are: Set helium gas flow at 45 ml/min flow rate. Set
column temperature at 80° C for 5 min, then program an 8° C/min temperature
rise to 150' C and until all compounds elute.
7.2 Calibration
7.2.1 By injecting secondary standards, adjust the sensitivity of
the analytical system for each compound being analyzed so as to detect
quantities of less than or equal to 1 ng for waste samples. Detection
limits to be used for groundwater analysis are given in Table 1. Cali-
brate the chromatographic system using either the external standard tech-
nique (Section 7.2.2) or the internal standard technique (Section 7.2.3).
7.2.2 External standard calibration procedure
7.2.2.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter by carefully adding 20.0 ul
Of one or more secondary dilution standards to 100, 500, or 1,000
ml of reagent water or the matrix under study. A 25-ul syringe
should be used for this operation. One of the external standards
should be at a concentration near, but above, the method detection
limit and the other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector. These aqueous standards must be
prepared fresh daily.
7.2.2.2 Analyze each calibration standard according to the
procedure being used (direct aqueous injection, headspace, or
-------
6 / ORGANIC ANALYTICAL METHODS - GC
purge-and-trap) and tabulate peak height or area responses against
the concentration in the standard. The results can be used to
prepare a calibration curve for each compound. Alternatively, if
the ratio of response to concentration (calibration factor) is a
constant over the working range (less than 10% relative standard
deviation), linearity through the origin can be assumed and the
average ratio or calibration factor can be used in place of a
calibration curve.
7.2.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than _+10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that compound.
7.2.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the internal
standards is not affected by method or matrix interferences. Because
of these limitations, no internal standard that would be applicable to
all samples can be suggested. The compounds recommended for use as
surrogate spikes have been used successfully as internal standards,
because of their generally unique retention times.
7.2.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest as described
in Section 7.2.2.1.
7.2.3.2 Prepare a spiking solution containing each of the
internal standards using the procedures described in Sections 5.3
and 5.4.
7.2.3.3 Analyze each calibration standard according to
appropriate methods (direct injection, 5020, 5030), adding the
internal standard spiking solution directly to an aliquot of the
sample or, in the case of purge-and-trap, to the syringe. Tabu-
late peak height or area responses against concentration for each
compound and internal standard, and calculate response factors (RF)
for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured
-------
8030 / 7
A-JS = Response for the internal standard
C-js = Concentration of the internal standard
Cs = Concentration of the parameter to be measured
If the RF value over the working range is a constant (less than
10% relative standard deviation), the RF can be assumed to be
invariant and the average RF can be used for calculations. Alter-
natively, the results can be used to plot a calibration curve of
response ratios, As/A-js against RF.
7.2.3.4 The working calibration curve or RF must be verified
on each working day by measuring one or more calibration standards.
If the response for any parameter varies from the predicted response
by more than +10%, either the test must be repeated using a fresh
calibration standard, or a new calibration curve must be prepared
for that compound.
7.3 Gas chromatographic analysis
7.3.1 Introduce volatile compounds to the gas chromatograph using
direct injection, headspace (Method 5020), or purge-and-trap (Method
5030).
7.3.2 Calibrate the system immediately prior to conducting any
analysis and recheck for each type of waste. Calibration should be
done no less frequently than at the beginning and end of each analysis
session.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed
to validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 ug/g of sample, then the sensitivity of the instrument should be
-------
8 / ORGANIC ANALYTICAL METHODS - GC
increased or the extract subjected to additional cleanup. Detection limits
to be used for groundwater samples are indicated in Table 1. Where doubt
exists over the identification of a peak on the chromatograph, confirmatory
techniques such as mass spectroscopy should be used.
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Parameter
Acrolein
Acrylom'trile
Retention time
(min)
8.2
9.8
Method detection limit3
(ug/1)
0.6
0.5
aMethod detection limit is based upon recovery of 5.0 ug/1
dose into tap water.
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 2
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 2.
TABLE 2. SINGLE OPERATOR ACCORACY AND PRECISION
Parameter
Acrolein
AeryIonitrile
Average
percent
recovery
96
107
Standard
deviation
(%)
11.6
5.6
Spike
range
(ug/1)
20
20
Number
of
analyses
7
7
Matrix
types
1
1
-------
8030 / 9
9.0 References
1.
2.
Bellar, T.A., and O.J.
Assoc. 66(12):739-744.
Lichtenberg. 1974. J. Amer. Water Works
Bellar, T.A., and J.J. Lichtenberg. 1979. Semi-automated headspace
analysis of drinking waters and industrial waters for purgeable vola-
tile organic compounds. In: Van Hall (ed.), Measurement of organic
pollutants in water and wastewater. ASTM STP 686, pp. 108-129.
3. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 11 - Purgeables and
Category 12 - Acrolein, Acrylonitrile, and Dichlorodifluoromethane.
Report for EPA Contract 68-03-2635 (in preparation).
4. Going, John, et al. 1979. Environmental monitoring near industrial
sites - Acrylonitrile. EPA Report No. 560/6-79-003.
-------
METHOD 8040
PHENOLS
1.0 Scope and Application
1.1 Method 8040 is used to determine the concentration of various
phenolic compounds in groundwater, liquid, and solid matrices. Specifically,
Method 8040 may be used to detect the following substances:
Phenol 4-Chloro-3-methylphenol
2-Chlorophenol 2,4-Dimethyl phenol
2,4-Dichlorophenol 2-Nitrophenol
2,6-Dichlorophenol 4-Nitrophenol
Trichlorophenols 2,4-Dinitrophenol
Tetrachlorophenols 2-sec-Butyl-4,6-dinitrophenol (DNBP)
Pentachlorophenol 2-Cyclohexyl-4,6-dinitrophenol
Cresol (methyl phenols) 2-Methyl-4,6-dinitrophenol
4,6-Dinitro-o-cresol
1.2 Method 8040 is recommended for use only by, or under the close
supervision of, experienced residue analysts.
2.0 Summary of Method
2.1 Method 8040 provides chromatographic conditions for the detection
of phenolic compounds. Prior to analysis, samples must be extracted using
appropriate techniques. Water and groundwater samples are extracted at a
pH of less than or equal to 2 with methylene chloride as a solvent using a
separatory funnel (Method 3510) or a continuous liquid-liquid extractor
(Method 3520). Both neat and diluted organic liquids may be analyzed by
direct injection. Solid samples are extracted at a pH of less than or equal
to 2 with methylene chloride using either the Soxhlet extraction (Method 3540)
or sonication (Method 3550) procedures. A 2- to 5-ul sample is injected into
a gas chromatograph (GC) using the solvent flush technique, and compounds
in the GC effluent are detected by a flame ionization detector (FID). An
aliquot of each sample must be spiked with standards to determine the spike
recovery and the limits of detection for that particular sample.
2.2 Method 8040 also provides for the preparation of pentafluorobenzyl-
bromide (PFB) derivatives with additional cleanup procedures for electron
capture gas chromatography to aid the analyst in the elimination of
interferences.
2.3 The sensitivity of Method 8040 usually depends on the level of
interferences rather than on instrumental limitations. The detection limits
listed in Table 1 for some phenols represent sensitivities that can be
achieved in wastewaters in the absence of interferences. However, in typical
waste samples, detection limits would be higher. The use of derivatization
cleanup, if necessary, will also increase detection limits.
-------
2 / ORGANIC ANALYTICAL METHODS - GC
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample-processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of gas chromatograms. All these materials must be demonstrated to be
free from interferences under the conditions of the analysis by running
method blanks. Specific selection of reagents and purification of solvents
by distillation in all-glass systems may be required.
3.2 Interferences coextracted from samples will vary considerably from
source to source depending upon the waste being sampled. While general
cleanup techniques are provided as part of this method, unique samples may
require additional cleanup.
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
TABLE 1. FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS9
Compound
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4-Dimethyl phenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chl oro-3-methyl phenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
Pentachlorophenol
4-Nitrophenol
Retention
time
1.70
2.00
3.01
4.03
4.30
6.05
7.50
10.00
10.24
12.42
24.25
Detection
limit (ug/l)b
0.31
0.45
0.14
0.32
0.39
0.64
0.36
13.0
16.0
7.4
2.8
aTaken from Reference 1.
Detection limit is calculated from the minimum detectable GC response
being equal to 5 times the GC background noise, assuming a 10-ml final
extract volume of the 1-liter sample extract, assuming a GC injection of 5 ml
-------
8040 / 3
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.4 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 uxj/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 when analyzing
groundwater samples.
4.0 Apparatus and Materials
4.1 Drying column: 20-mm I.D. Pyrex chromatographic column with coarse
frit.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube: 10ml, graduated (Kontes K-570050-1025
or equivalent). Calibration must be checked. Ground-glass stopper
(size 19/22 joint) is used to prevent evaporation of extracts.
4.2.2 Evaporative flask: 500 ml. Attach to concentrator tube
with springs (Kontes K-662750-0012).
4.2.3 Snyder column: Three-ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Boiling chips: Solvent extracted, approximately 10/40 mesh.
4.3 Water bath: Heated, with concentric ring cover, capable of
temperature control (+2° C). The bath should be used in a hood.
4.4 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injections and all required accessories including
flame ionization and electron capture detector, column supplies, recorder,
gases, syringes. A data system for measuring peak areas is recommended.
4.5 Chromatographic column: 10-mm I.D. by 100-mm length, with Teflon
stopcock.
-------
4 / ORGANIC ANALYTICAL METHODS - GC
4.6 Reaction vial: 20-ml, with Teflon-lined cap.
5.0 Reagents
5.1 Preservatives
5.1.1 Sodium hydroxide: (ACS) 10 N in distilled or distilled,
deionized water.
5.1.2 Sulfuric acid: (1:1) Mix equal volumes of cone. ^04
(ACS) with distilled or distilled, deionized water.
5.1.3 Sodium thiosulfate: (ACS) Granular.
5.2 Methylene chloride, acetone, 2-propanol, hexane, toluene: Pesticide
quality or equivalent.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400" C for 4 hr in a shallow tray).
5.4 Stock standards: Prepare stock standard solutions at a concentra-
tion of 1.00 u.g/[il by dissolving 0.100 g of assayed reference material in
pesticide quality 2-propanol and diluting to volume in a 100-ml ground-
glass-stoppered volumetric flask. The stock solution is transferred to
ground-glass-stoppered reagent bottles, stored in a refrigerator, and checked
frequently for signs of degradation or evaporation, especially just prior to
preparing working standards.
5.5 Sulfuric acid: (ACS) 1 N in distilled water.
5.6 Potassium carbonate: (ACS) powdered.
5.7 Pentafluorobenzyl bromide (a-Bromopentafluorotoluene): 97% minimum
purity.
5.8 1,4,7,10,13,16-Hexaoxacyclooctadecane (18-crown-6): 98% minimum
purity.
5.9 Derivatization reagent: Add 1 ml pentafluorobenzyl bromide and
1 g 18-crown-6 to a 50-ml volumetric flask and dilute to volume with 2-propanol
Prepare fresh weekly.
5.10 Silica gel: (ACS) 100/200 mesh, grade 923; activated at 130* C and
stored in a desiccator.
-------
8040 / 5
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not be
prewashed with sample before collection. Composite samples should be collected
in refrigerated glass containers in accordance with the requirements of the
program. Automatic sampling equipment must be free of tygon and other
potential sources of contamination.
6.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. At the sampling location fill the glass container
with sample. Add 35 mg of sodium thiosulfate per ppm free chlorine per
liter. Adjust the sample pH to approximately 2, as measured by pH paper,
using appropriate sulfuric acid solution or 10 N sodium hydroxide. Record
the volume of acid used on the sample identification tag so the sample
volume can be corrected later.
6.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
7.0 Procedures
7.1 Sample preparation
7.1.1 Extraction
Extract water samples at a pH of less than or equal to 2 with
methylene chloride as a solvent using a separatory funnel (Method 3510)
or a continuous liquid-liquid extractor (Method 3520). Solid samples
are extracted at a pH of less than or equal to 2 with methylene chloride
using either the Soxhlet extraction (Method 3540) or sonication (Method
3550) procedures. An aliquot of each sample must be spiked with standards
to determine the percent recovery and the limits of detection for that
sample.
7.1.2 Derivatization
If interferences prevent measurement of the peak area during
analysis of the extract by flame ionization gas chromatography, the
phenols must be derivatized and analyzed by electron capture gas
chromatography.
7.1.2.1 Pipet a 1.0-ml aliquot of the 2-propanol solution
of standard or sample extract into a glass reaction vial. Add
1.0 ml derivatization reagent. This is a sufficient amount of
reagent to derivatize a solution whose total phenolic content does
not exceed 0.3 mg/ml.
-------
6 / ORGANIC ANALYTICAL METHODS - GC
7.1.2.2 Add about 3 mg of potassium carbonate to the solu-
tion and shake gently.
7.1.2.3 Cap the mixture and heat it for 4 hr at 80* C in a
hot water bath.
7.1.2.4 Remove the solution from the hot water bath and
allow it to cool.
7.1.2.5 Add 10 ml hexane to the reaction vial and shake
vigorously for 1 min. Add 3.0 ml distilled, deionized water
to the reaction vial and shake for 2 min.
7.1.2.6 Decant organic layer into a concentrator tube and
cap with a glass stopper.
7.1.2.7 Pack a 10-mm I.D. chromatographic column with 4.0 g
of activated silica gel. After settling the silica gel by
tapping the column, add about 2 g of anhydrous sodium sulfate to
the top.
7.1.2.8 Pre-elute the column with 6 ml hexane. Discard the
eluate and just prior to exposure of the sulfate layer to air,
pipet onto the column 2.0 ml of the hexane solution that
contains the derivatized sample of standard. Elute the column
with 10.0 ml of hexane (Fraction 1) and discard this fraction.
Elute the column, in order, with: 10.0 ml 15% toluene in hexane
(Fraction 2); 10.0 ml 40% toluene in hexane (Fraction 3); 10.0 ml
75% toluene in hexane (Fraction 4); and 10.0 ml 15% 2-propanol in
toluene (Fraction 5). Elution patterns for some phenolic deriva-
tives are shown in Table 2. Fractions may be combined as desired,
depending upon the specific phenols of interest or level of
interferences.
7.2 The recommended gas chromatographic columns and operating conditions
for the instruments are:
Column 1 conditions: Supelcoport 80/100 mesh coated with 1%
SP-1240 DA in 6-ft long x 2-mm I.D. glass column with nitrogen
carrier gas at 30 ml/min flow rate. Column temperature is 80' C at
injection, and then programmed immediately at 8" C/min to a 150" C
final temperature.
Column 2 conditions: Chromosorb W-AW-DMCS 80/100 mesh coated
with 5% OV-17 packed in a 1.8-m long x 2.0-mm I.D. glass column
with 5% methane/95% argon carrier gas at 30 ml/min flow rate.
Column temperature is 200" C.
-------
8040 / 7
TABLE 2. ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES9
Method
detection
Parent compound limit (ug/1 )
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethylphenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-2-methyl phenol
Pentachlorophenol
4-Nitrophenol
(2,4-Dinitrophenol )
(2-Methyl-
4,6-dinitrophenol )
0.58
0.77
2.2
0.63
0.68
0.58
1.8
0.59
0.70
Retention
time
(min)b
3.3
9.1
1.8
2.9
5.8
7.0
4.8
28.8
14.0
46.9
36.6
Percent recovery by fraction
1 2 3
90
90
95
95
50 50
84
75 20
4
over 1
9
10
7
over 1
14
over 1
5
90
90
aTaken from Reference 1.
^Retention times included for qualitative information only. The lack
of accuracy and precision of the derivatization reaction precludes the use of
this approach for quantitative purposes.
7.3 Calibration
7.3.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.2. By injecting secondary standards,
adjust the sensitivity of the analytical system for each compound
being analyzed so as to detect quantities of less than or equal to 1 ug
for waste samples. Detection limits to be used for groundwater analysis
are given in Table 1. Calibrate the chromatographic system using either
the external standard technique (Section 7.3.2) or the internal standard
technique (Section 7.3.3).
7.3.2 External standard calibration procedure
7.3.2.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with isooctane. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
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8 / ORGANIC ANALYTICAL METHODS - GC
7.3.2.2 Using injections of 2 to 5 u,l of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
the mass injected, defined as the calibration factor (CF), can be
calculated for each parameter at each standard concentration. If
the relative standard deviation of the calibration factor is less
than 10% over the working range, linearity through the origin can
be assumed and the average calibration factor can be used in place
of a calibration curve.
7.3.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than ^10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that parameter.
7.3.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is
not affected by method or matrix interferences. Due to these limita-
tions, no internal standard applicable to all samples can be suggested.
7.3.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
volumes of one or more stock standards to a volumetric flask. To
each calibration standard, add a known constant amount of one or
more internal standards, and dilute to volume with isooctane. One
of the standards should be at a concentration near, but above, the
method detection limit. The other concentrations should correspond
to the expected range of concentrations found in real samples, or
should define the working range of the detector.
7.3.3.2 Using injections of 2 to 5 uJ of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
A-JS = Response for the internal standard.
-------
8040 / 9
Cis = Concentration of the internal standard in ug/1 .
Cs = Concentration of the parameter to be measured in ug/1.
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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 aga^st RF.
7.3.3.3 The working calibration curve or RF must be verified
on each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than +10%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibra-
tion curve must be prepared for that compound.
7.4 Gas chromatographic analysis
7.4.1 Phenols are to be analyzed on a gas chromatograph equipped
with a flame ionization detector according to column 1 conditions
(Section 7.2). Table 1 summarizes estimated retention times and sensi-
tivities that should be achieved by this method for clean water samples.
Detection limits for a typical waste sample would be significantly
higher. If peak detection is prevented by interferences, PFB deriva-
tives of the phenols should be analyzed on a gas chromatograph equipped
with an electron capture detector according to column 2 conditions
(Section 7.2). Table 2 summarizes estimated retention times as well as
percent recoveries for the fractionation procedure.
7.4.2 Inject 2 to 5 ul of the sample extract using the solvent
flush technique. Smaller (1.0 ul ) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 ul , and the resulting peak size, in area units.
7.4.3 If the peak areas exceed the linear range of the system,
dilute the extract and reanalyze.
7.4.4 An example of a GC/FID chromatogram for certain phenols is
shown in Figure 1. Figure 2 shows a GC/ECD chromatogram of PFB deriva-
tives of certain phenols.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware and
-------
10 / ORGANIC ANALYTICAL METHODS - GC
reagents are interference-free. Each time a set of samples is extracted or
there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision
of the sampling technique. Laboratory replicates should be analyzed to
validate the precision of the analysis. Fortified samples should be analyzed
to validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 ug/g of sample, then the sensitivity of the instrument should be
increased or the extract subjected to additional cleanup. Detection limits
to be used for groundwater samples are indicated in Table 1. The fortified
samples should be carried through all stages of sample preparation and
measurement. Where doubt exists over the identification of a peak on the
chromatograph, confirmatory techniques such as mass spectroscopy should be
used.
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 3
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 3.
9.0 References
1. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 3 - Chlorinated Hydro-
carbons and Category 8 - Phenols. Report for EPA Contract 68-03-2625.
(In preparation.)
-------
8040 / 11
TABLE 3. SINGLE OPERATOR ACCURACY AND PRECISION
Average
percent
Parameter recovery
4-Chloro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitropheno1
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
82
67
74
51
74
86
67
45
79
41
71
Standard Spike
deviation range
(%) (H9/1 )
15.0
14.8
11.4
14.0
16.5
12.4
12.9
7.9
8.8
8.4
14.5
0.70-3.5
0.74-3.7
1.03-5.2
0.82-4.1
28.7
34.6
0.80-4.0
15.9
21.0
0.76-3.8
1.20-6.0
Number
of
analyses
21
21
21
21
14
21
21
21
21
21
21
Matrix
types
3
3
3
3
2
3
3
3
3
3
3
-------
12 / ORGANIC ANALYTICAL METHODS - GC
o
c
0)
a
o
o
c
E
o
c
CD
.C
a
o
CN
Column: 1% SP-1240DA on Supelcoport
Program: 80°C 0 Minutes 8°/Minute to 150°C
Detector: Flame lonization
0
V
o
0)
> _ "-H
£ o co
QJ t— •»
o
CD
O
^
1
•4-*
C
8 12 16 20
RETENTION TIME (MINUTES)
24
28
Figure 1. Gas chromatogram of phenols.
-------
8040 / 13
o
g
0)
5 §
-'!i
2! ,
0> _. C
Column: 5% OV-17 on Chromosorb W-AW
Temperature: 200°C
Detector: Electron Capture
co «
2
S5«
111
JU
Q <6
CM CN
•5
91
8 12 16 20 24
RETENTION TIME (MINUTES)
28
32
Figure 2. Gas chromatogram of PFB derivatives of phenols.
-------
METHOD 8060
PHTHALATE ESTERS
1.0 Scope and Application
1.1 Method 8060 is used to determine the concentration of phthalate
esters in groundwater, liquid, and solid sample matrices. Specifically,
Method 8060 may be used to detect the following substances:
Benzyl butyl phthalate
Bis(2-ethylhexyl )phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate
1.2 The applicability of Method 8060 to other phthalate compounds can be
determined by means of a spike recovery study.
1.3 Method 8060 is recommended for use only by, or under the close
supervision of, experienced residue analysts.
2.0 Summary of Method
2.1 Method 8060 provides cleanup and gas chromatographic conditions for
the detection of ppb levels of phthalate esters. Prior to use of this
method, appropriate sample extraction techniques must be used. Water samples
are extracted at a neutral pH with methylene chloride as a solvent using a
separatory funnel (Method 3510) or a continuous liquid-liquid extractor
(Method 3520). Both neat and diluted organic liquids may be analyzed by
direct injection. Solid samples are extracted at a neutral pH with methylene
chloride using either the Soxhlet extraction (Method 3540) or sonication
(Method 3550) procedures. A 2- to 5-ul aliquot of the extract is injected
into a gas chromatograph (GC) using the solvent flush technique, and com-
pounds in the GC effluent are detected by an electron capture detector (ECD)
or a flame ionization detector (FID). Groundwater samples should be deter-
mined by ECD. An aliquot of each sample will be spiked with standards to
determine percent recovery and the limits of detection for that sample.
2.2 The sensitivity of Method 8060 usually depends on the level of
interferences rather than on instrumental limitations. Table 1 lists the
limits of detection that can be obtained in wastewaters in the absence of
interferences. Detection limits in groundwater should be approximately the
same. Detection limits for a typical waste sample would be significantly
higher.
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield discrete artifacts and/or elevated baselines causing
-------
2 / ORGANIC ANALYTICAL METHODS - GC
misinterpretation of gas chromatograms. All these materials must therefore
be demonstrated to be free from interferences under the conditions of the
analysis by running method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are provided as part
of this method, unique samples may require additional cleanup approaches to
achieve desired sensitivities.
3.3 Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This should be
followed by detergent washing in hot water. Rinse with tap water, distilled
water, acetone, and finally pesticide-quality hexane. Heavily contaminated
glassware may require treatment in a muffle furnace at 400' C for 15 to 30
min. Some high boiling materials, such as PCB's, may not be eliminated by
this treatment. Volumetric ware should not be heated in a muffle furnace.
Glassware should be sealed/stored in a clean environment immediately after
drying or cooling to prevent any accumulation of dust or other contaminants.
Store inverted or capped with aluminum foil.
3.4 Phthalate esters contaminate many types of products commonly found
in the laboratory. The analyst must demonstrate that no phthalate residues
contaminate the sample or solvent extract under the conditions of analysis.
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 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as. mass spectroscopy should be
used.
3.6 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 uxj/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 when analyzing
groundwater samples.
-------
8060 / 3
TABLE 1. GAS CHROMATOGRAPHY OF PHTHALATE ESTERS3
Retention time (min) Detection limit (u.g/1)
Compound
Dimethyl phthalate
Diethyl phthalate
Di-n-butyl phthalate
Benzyl butyl phthalate
Bis(2-ethylhexyl )
Col.
2.03
2.82
8.65
*6.94
*8.92
lb Col. 2C
0.95
1.27
3.50
**5.11
**10.5
ECD
0.29
0.49
0.36
0.34
2.0
FID
19
31
14
15
20
phthalate
Di-n-octyl phthalate *16.2 **8.0 3.0 31
aTaken from Reference 1.
bColumn 1: Supelcoport 100/120 mesh coated with 1.5% SP-2250/1.95%
SP-2401 packed in a 180-cm long x 4-mm I.D. glass column with carrier
gas at 60 ml/min flow rate. Column temperature is 180° C except where *
indicates 220° C. Under these conditions retention time of Aldrin is
5.49 min at 180° C and 1.84 min at 220° C.
cColumn 2: Supelcoport 100/120 mesh with 3% OV-1 in a 180-cm long x
4-mm I.D. glass column with carrier gas at 60 ml/min flow rate. Column
temperature is 200° C except where ** indicates 220° C. Under these
conditions retention time of Aldrin is 3.18 min at 200° C and 1.46 min at
220° C.
4.0 Apparatus and Materials
4.1 2000-ml separatory funnel with Teflon stopcock.
4.2 Drying column: 20-mm I.D. pyrex chromatographic column with coarse
frit.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube: 10ml, graduated (Kontes K-570050-1025
or equivalent). Calibration must be checked. Ground-glass stopper
(size 19/22 joint) is used to prevent evaporation of extracts.
4.3.2 Evaporative flask: 500 ml. Attach to concentrator tube
with springs (Kontes K-662756-0012).
4.3.3 Snyder column: Three-ball macro (Kontes K503000-0121 or
equivalent).
-------
4 / ORGANIC ANALYTICAL METHODS - GC
4.3.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Boiling chips: Solvent extracted, approximately 10/40 mesh.
4.4 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+2° C). The bath should be used in a hood.
4.5 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection and all required accessories including
electron-capture or flame ionization detector, column supplies, recorder,
gases, syringes. A data system for measuring peak areas is recommended.
4.6 Chromatography column: 300-mm long x 10-mm I.D., with coarse
disc at bottom and Teflon stopcock (Kontes K-420540-0213 or equivalent).
5.0 Reagents
5.1 Preservatives
5.1.1 Sodium hydroxide: (ACS) 10 N in distilled water.
5.1.2 Sulfuric acid: (ACS) Mix equal volumes of cone.
with distilled water.
5.2 Methylene chloride: Pesticide quality or equivalent.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Stock standards: Prepare stock standard solutions at a concen-
tration of 1.00 u.g/u.1 by dissolving 0.100 g of assayed reference material
in pesticide quality isooctane or other appropriate solvent and diluting
to volume in a 100-ml ground-glass-stoppered volumetric flask. The stock
solution is transferred to ground-glass-stoppered reagent bottles, stored in
a refrigerator, and checked frequently for signs of degradation or evaporation,
especially just prior to preparing working standards from them.
5.5 Diethyl ether: Nanograde, redistilled in glass if necessary.
5.5.1 Must be free of peroxides as indicated by EM Quant test
strips. (Test strips are available from EM Laboratories, Inc., 500
Executive Blvd., Elmsford, NY 10523.)
5.6 Florisil: PR grade (60/100 mesh); purchase-activated at 1250* F;
store in glass containers with ground-glass stoppers or foil-lined screw
caps.
-------
8060 / 5
5.7 Alumina: Activity Super I, Neutral, W200 series (ICN Life
Sciences Group, No. 404583).
5.8 Hexane: Pesticide quality.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not be
prewashed with sample before collection. Composite samples should be collected
in refrigerated glass containers in accordance with the requirements of the
program. Automatic sampling equipment must be free of tygon and other
potential sources of contamination.
6.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. Chemical preservatives should not be used in the
field unless more than 24 hr will elapse before delivery to the laboratory.
If the samples will not be extracted within 48 hr of collection, the sample
should be adjusted to a pH range of 6.0-8.0 with sodium hydroxide or sulfuric
acid.
6.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
7.0 Procedures
7.1 Extraction. Extract water samples at a neutral pH with methylene
chloride as a solvent using a separatory funnel (Method 3510) or a continuous
liquid-liquid extractor (Method 3520). Extract solid samples with methylene
chloride using either the Soxhlet extraction (Method 3540) or sonication
(Method 3550) procedures. Spiked samples are used to verify the applicability
of the chosen extraction technique to each new sample type. An aliquot of
each sample should be spiked with standards to determine the percent recovery
and the limit of detection for that sample.
7.2 Cleanup and separation
7.2.1 If the entire extract is to be cleaned up by one of the
following two procedures, it must be concentrated to about 2 ml. To the
concentrator tube add a clean boiling chip and attach a two-ball micro-
Snyder column. Prewet the column by adding about 0.5 ml hexane through
the top. Place the K-D apparatus in a hot water bath (80° 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 min. At the proper rate
of distillation, the balls of the column will actively chatter but the
chambers will not flood. When the apparent volume of liquid reaches
-------
6 / ORGANIC ANALYTICAL METHODS - GC
about 0.5 ml, remove the K-D apparatus and allow it to drain for at
least 10 min while cooling. Remove the micro-Snyder column and rinse
its lower joint into the concentrator tube with 0.2 ml of hexane.
Proceed with one of the following cleanup procedures.
7.2.2 Florisil column cleanup for phthalate esters
7.2.2.1 Place 100 g of Florisil 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 distilled water which is free
of phthalates and interferences. Mix thoroughly by shaking or
rolling for 10 min and let it stand for at least 2 hr. Keep the
bottle sealed tightly.
7.2.2.2 Place 10 g of this Florisil preparation into
a 10-mm I.D. chromatography column and tap the column to settle the
Florisil. Add 1 cm of anhydrous sodium sulfate to the top of the
Florisil.
7.2.2.3 Preelute the column with 40 ml of hexane. Discard
this eluate and, just prior to exposure of the sodium sulfate layer
to the air, transfer the 2-ml sample extract onto the column, using
an additional 2 ml of hexane to complete the transfer.
7.2.2.4 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.
7.2.2.5 Next elute the phthalate esters with 100 ml of
20 percent ethyl ether/80 percent hexane (v/v) into a 500-ml K-D
flask equipped with a 10-ml concentrator tube. Elute the column at
a rate of about 2 ml/min for all fractions. Concentrate the
collected fraction by standard K-D technique. No solvent exchange
is necessary. After concentration and cooling, adjust the volume
of the cleaned-up extract to 10 ml in the concentrator tube and
analyze by gas chromatography.
7.2.3 Alumina column cleanup for phthalate esters
7.2.3.1 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 distilled water which is free from phthalates
and interferences. Mix thoroughly by shaking or rolling for 10 min
and let it stand for at least 2 hr. Keep the bottle sealed tightly,
7.2.3.2 Place 10 g of this alumina preparation into a 10-mr
I.D. chromatography column and tap the column to settle the
Add 1 cm of anhydrous sodium sulfate to the top of the alumina,
-------
8060 / 7
7.2.3.3 Preelute the column with 40 ml of hexane. Discard
this eluate and, just prior to exposure of the sodium sulfate layer
to the air, transfer the 2-ml sample extract onto the column, using
an additional 2 ml of hexane to complete the transfer.
7.2.3.4 Just prior to exposure of the sodium sulfate layer
to the air, add 35 ml hexane and continue to elution of the column.
Discard this hexane eluate.
7.2.3.5 Next elute the column with 140 ml of 20 percent
ethyl ether/80 percent hexane (v/v) into a 500-ml K-D flask equipped
with a 10-ml concentrator tube. Elute the column at a rate of
about 2 ml/min for all fractions. Concentrate the collected
fraction by standard K-D technique. No solvent exchange is neces-
sary. After concentration and cooling adjust the volume of the
cleaned-up extract to 10 ml in the concentrator tube and analyze by
gas chromatography.
7.3 The recommended gas chromatographic columns and operating condi-
tions for the instrument are:
Column 1 conditions: Supelcoport 100/120 mesh coated with 1.5%
SP-2250/1.95% SP-2401 packed in a 180-cm-long x 4-mm I.D. glass
column with carrier gas at 60 ml/min flow rate. Column temperature
is 180* C.
Column 2 conditions: Supelcoport 100/120 mesh coated with 3% OV-1
in a 180-cm-long x 4-mm I.D. glass column with carrier gas at 60
ml/min flow rate. Column temperature is 200° C.
7.4 Calibration
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.3. By injecting secondary standards,
adjust the sensitivity of the analytical system for each compound
being analyzed so as to detect quantities of less than or equal to 1 n
-------
8 / ORGANIC ANALYTICAL METHODS - GC
range of concentrations found in real samples or should define the
working range of the detector.
7.4.2.2 Using injections of 2 to 5 u.1 of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
the mass injected, defined as the calibration factor (CF), can be
calculated for each parameter at each standard concentration. If
the relative standard deviation of the calibration factor is less
than 10% over the working range, linearity through the origin can
be assumed and the average calibration factor can be used in place
of a calibration curve.
7.4.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than +10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that parameter.
7.4.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Due to these limitations,
no internal standard applicable to all samples can be suggested.
7.4.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
volumes of one or more stock standards to a volumetric flask. To
each calibration standard, add a known constant amount of one or
more internal standards, and dilute to volume with isooctane. One
of the standards should be at a concentration near, but above, the
method detection limit. The other concentrations should correspond
to the expected range of concentrations found in real samples, or
should define the working range of the detector.
7.4.3.2 Using injections .of 2 to 5 u,l of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsC1s)/(A1sCs)
where:
-------
8060 / 9
As = Response for the parameter to be measured.
A-JS = Response for the internal standard.
C-js = Concentration of the internal standard in ng/1.
Cs = Concentration of the parameter to be measured in u.g/1 •
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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 against RF.
7.4.3.3 The working calibration curve or RF must be verified
on each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than +10%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibration
curve must be prepared for that compound.
7.5 Gas chromatographic analysis
7.5.1 Either a flame ionization or electron capture detector may
be used; however, the electron capture detector provides substantially
better sensitivity.
7.5.2 Inject 2 to 5 u.1 of the sample extract using the solvent
flush technique. Smaller (1.0 u.1) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 u.1, and the resulting peak size, in area units.
7.5.3 If the peak areas exceed the linear range of the system,
dilute the extract and reanalyze.
7.5.4 If peak detection is prevented by the presence of interfer-
ences, further cleanup is required. Before using any cleanup procedure,
the analyst must process a series of calibration standards through the
procedure to validate elution patterns and the absence of interferences
from the reagents.
7.5.5 Examples of chromatograms for phthalate esters detected with
an electron capture detector are shown in Figures 1 and 2.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank, that all glassware
-------
10 / ORGANIC ANALYTICAL METHODS - GC
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 18CK>C
Detector: Electron Capture
&
JS
03
0 2 4 6 8 10 12
RETENTION TIME (MINUTES)
Figure 1. Gas chromatogram of phthalates (example 1).
-------
8060 / 11
Column: 1.5%SP-2250+
1.95% SP-2401 on Supelcoport
Temperature: 180°C
Detector: Electron Capture
4 8 12 16
RETENTION TIME (MINUTES)
18
Figure 2. Gas chromatogram of phthalates (example 2).
-------
12 - ORGANIC ANALYTICAL METHODS / GC
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.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified waste samples should be analyzed
to validate the accuracy of the analysis. Detection limits to be used for
groundwater samples are indicated in Table 1. Where doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques such as
mass spectroscopy should be used.
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 2
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 2.
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION
Parameter
Bis(2-ethylhexyl)
Average
percent
recovery
85
Standard
deviation
(*)
4.2
Spike
range
(u.g/1 )
24-1000
Number
of
analyses
24
Matrix
types
4
phthalate
Butyl benzyl phthalate
Di-n-butyl-phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl-phthalate
82
80
94
94
86
6.5
6.2
1.3
3.4
4.9
3-100
20-1500
15-50
15-50
40-150
24
24
18
18
24
4
4
3
3
4
-------
8060 / 13
9.0 References
1. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 1 - phthalates. Report
for EPA Contract 68-03-2606 (in preparation).
-------
METHOD 8080
ORGANOCHLORINE PESTICIDES AND RGB'S
1.0 Scope and Application
1.1 Method 8080 is used to determine the concentration of certain
organochlorine pesticides and polychlorinated biphenyls (RGB's) in ground-
water, liquid, and solid sample matrices. Specifically, Method 8080 may be
used to detect the following substances:
Aldrin
a_-BHC
6-BHC
w_-BHC
q-BHC (Lindane)
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Kepone
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
1.2 Method 8080 is recommended for use only by, or under the close
supervision of, experienced residue analysts.
2.0 Summary of Method
2.1 Method 8080 provides cleanup and chromatographic conditions for
the detection of ppb levels of organochlorine pesticides and RGB's. Prior
to the use of this method, appropriate sample extraction techniques must be
used. Groundwater and other aqueous samples are extracted at a neutral pH
with methylene chloride as a solvent using a separatory funnel (Method 3510)
or a continuous liquid-liquid extractor (Method 3520). Both neat and diluted
organic liquids may be analyzed by direct injection. Solid samples are
extracted with hexane:acetone (1:1) using either the Soxhlet extraction
(Method 3540) or sonication (Method 3550) procedures. A 2- to 5-u.l sample is
injected into a gas chromatograph (GC) using the solvent flush technique, and
compounds in the GC effluent are detected by an electron capture detector
(ECD) or another halogen-specific detector. An aliquot of each sample will
be spiked with standards to determine the spike recovery and the limits of
detection for that particular sample. It is recommended that the analyst
carefully select the compounds used in sample spiking to avoid coelution
under the GC conditions given in Table 1. Aroclor 1221 will give minimal
interference with the single component pesticides listed in Table 1. Chlor-
dane and toxaphene may require individual spiked sample analysis to yield
valid recovery data.
-------
8080 / 2
TABLE 1. GAS CHROMATOGRAPHY OF PESTICIDES AND PCB's3
Retention time (min)
Detection limitb
Parameter • Column lc Column 2d (ng/1)
Aldrin
a-BHC
B-BHC
w-BHC
£-BHC (Lindane)
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
2.40
1.35
1.90
2.15
0.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
0.004
0.004
0.006
0.009
0.004
0.014
0.012
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.004
0.083
0.176
ND
ND
ND
0.065
ND
ND
ND
ND = not determined.
aTaken from reference 6.
^Detection limit is calculated from the minimum detectable GC response
being equal to five times the GC background noise, assuming a 10-ml final
volume of a 1-liter liquid extract, and assuming a GC injection of 5 ul.
cColumn 1 conditions: Supelcoport 100/120 mesh coated with 1.5%
SP-2250/1.95% SP-2401 packed in a 180-cm long x 4-mm I.D. glass column with
5% Methane/95% Argon carrier gas at 60 ml/min flow rate. Column temperature
is 200' C.
dColumn 2 conditions: Supelcoport 100/200 mesh coated with 3% OV-1 in
a 180-cm long x 4-mm I.D. glass column with 5% Methane/95% Argon carrier gas
at 60 ml/min flow rate. Column temperature is 200* C.
eMultiple peak response.
-------
8080 / 3
2.2 The sensitivity of Method 8080 usually depends on the level of
interferences rather than on instrumental limitations. Table 1 lists the
limits of detection that can be obtained in wastewaters in the absence of
interferences. Detection limits for a typical waste sample may be signifi-
cantly higher.
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of gas chromatograms. All these materials must therefore be demonstrated
to be free from interferences under the conditions of the analysis by
running method blanks. Specific selection of reagents and purification of
solvents by distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are provided as part of
this method, unique samples may require additional cleanup approaches to
achieve desired sensitivities.
3.3 Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This should be
followed by detergent washing in hot water. Rinse with tap water, distilled
water, acetone, and finally pesticide-quality hexane. Heavily contaminated
glassware may require treatment in a muffle furnace at 400" C for 15 to 30
min. Some high boiling materials, such as PCB's, may not be eliminated by
this treatment. Volumetric ware should not be heated in a muffle furnace.
Glassware should be sealed/stored in a clean environment immediately after
drying or cooling to prevent any accumulation of dust or other contaminants.
Store inverted or capped with aluminum foil.
3.4 Interferences by phthalate esters can pose a major problem in
pesticide analysis. These materials elute in the 15% and 50% fractions of
the Florisil cleanup. They usually can be minimized by avoiding contact
with any plastic materials. The contamination from phthalate esters can be
completely eliminated with a microcoulometric or electrolytic conductivity
detector.
3.5 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should
-------
8080 / 4
be used. Detection limits for groundwater and EP extracts are given in
Table 1. Detection limits for these compounds in wastes should be set at
1
4.0 Apparatus and Materials
4.1 Drying column: 20-mm I.D. pyrex chromatographic column with coarse
frit.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube: 10 ml, graduated. Calibration must be
checked at 1.0- and 10.0-ml level. Ground glass stopper (size 19/22
joint) is used to prevent evaporation of extracts.
4.2.2 Evaporative flask: 500 ml. Attach to concentrator tube with
springs.
4.2.3 Snyder column: Three-ball macro (Kontes K503000-0121 or
equivalent).
4.2.4 Boiling chips: Extracted, approximately 10/40 mesh.
4.3 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+_2* C). The bath should be used in a hood.
4.4 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection and all required accessories including
electron-capture or halogen-specific detector, column supplies, recorder,
gases, syringes. A data system for measuring peak areas is recommended.
4.5 Chromatographic column: Pyrex, 400 mm x 25 mm O.D., with coarse
fritted plate and Teflon stopcock (Kontes K-42054-213 or equivalent).
5.0 Reagents
5.1 Preservatives
5.1.1 Sodium hydroxide: (ACS) 10 N in distilled water.
5.1.2 Sulfuric acid (1+1): (ACS) Mix equal volumes of cone.
H2S04 with distilled water.
5.2 Methylene chloride: Pesticide quality or equivalent.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400* C for 4 hr in a shallow tray).
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8080 / 5
5.4 Stock standards: Prepare stock standard solutions at a concen-
tration of 1.00 u.g/u.1 by dissolving 0.100 g of assayed reference material
in pesticide quality isooctane or other appropriate solvent and diluting
to volume in a 100-ml ground-glass-stoppered volumetric flask. The stock
solution is transferred to ground-glass-stoppered reagent bottles, stored in
a refrigerator, and checked frequently for signs of degradation or evaporation,
especially just prior to preparing working standards from them.
5.5 Mercury: Triple distilled.
5.6 Hexane: Pesticide residue analysis grade.
5.7 Isooctane (2,2,4-trimethyl pentane): Pesticide residue analysis
grade.
5.8 Acetone: Pesticide residue analysis grade.
5.9 Diethyl ether: Nanograde, redistilled in glass if necessary.
5.9.1 Must be free of peroxides as indicated by EM Quant test
strips (Test strips are available from EM Laboratories, Inc., 500
Executive Blvd., Elmsford, N.Y. 10523).
5.9.2 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.
5.10 Florisil: PR grade (60/100 mesh); purchase activated at 1250* F;
store in glass containers with glass stoppers or foil-lined screw caps.
Before use, activate each batch at least 16 hr at 130" C in a foil-covered
glass container.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in appropriately cleaned glass
containers and the sampling bottle must not be prewashed with the sample
before collection. Composite samples should be collected in refriger-
ated glass containers in accordance with the requirements of the program.
Automatic sampling equipment must be free of tygon and other potential
sources of contamination.
6.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. Chemical preservatives should not be used in the
field unless more than 24 hr will elapse before delivery to the laboratory.
If the samples will not be extracted within 48 hours of collection, the
sample should be adjusted to a pH range of 6.0-8.0 with sodium hydroxide or
sulfuric acid.
-------
8080 / 6
6.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
7.0 Procedures
7.1 Sample preparation
7.1.1 Extraction. Extract water samples at a neutral pH with
methylene chloride as a solvent using a separatory funnel (Method 3510)
or a continuous liquid-liquid extractor (3520). Extract solid samples
with hexane:acetone (1:1) using either the Soxhlet extraction (Method
3540) or sonication procedures (Method 3550). Spiked samples are used
to verify the applicability of the chosen extraction technique to each
new sample type. Each sample must be spiked to determine the % recovery
and the limit of detection for that sample.
7.1.2 Florisil column cleanup
7.1.2.1: Add a weight of Florisil .(nominally 21 g), pre-
determined by calibration (Section 7.3) to a chromatographic
column. Settle the Florisil by tapping the column. Add sodium
sulfate to the top of the Florisil to form a layer 1-2 cm deep.
Add 60 ml of hexane to wet and rinse the sodium sulfate and Florisil
Packing the Florisil in a hexane slurry is an alternative method
which has proven effective. Just prior to exposure of the sodium
sulfate to air, stop the elution of the hexane by closing the
stopcock on the chromatography column. Discard the eluate. Adjust
the sample extract volume to 10 ml 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.
7.1.2.2 Place a 500-ml K-D flask and clean concentrator tube
under the chromatography 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 (Fraction 1) using a drip
rate of about 5 ml/min. Remove the K-D flask and set aside for
later concentration. Elute the column again, using 200 ml of 15%
ethyl ether in hexane (Fraction 2), into a second K-D flask.
Perform the third elution using 200 ml of 50% ethyl ether in hexane
(Fraction 3). The elution patterns for the pesticides and PCB's
are shown in Table 2.
7.1.2.3 Concentrate the eluates by standard K-D techniques,
as described in the referenced extraction procedures, substituting
hexane for the glassware rinses and using the water bath at about
85" C. Adjust final volume to 10 ml with hexane. Analyze by gas
chromatography.
-------
8080 / 7
TABLE 2. DISTRIBUTION AND RECOVERY OF CHLORINATED PESTICIDES
AND PCB's USING FLORISIL COLUMN CHROMATOGRAPHY3
Parameter
Aldrin
a-BHC
S-BHC
w-BHC
£-BHC (Lindane)
Chlordane
4, 4 '-ODD
4, 4 '-DDE
4, 4 '-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
P.CB-1248
PCB-1254
PCB-1260
Percent
1(6%)
100
100
97
98
100
100
99
98
100
0
37
0
0
4
0
100
100
100
96
97
97
95
97
103
90
95
recovery by fractionb
2(15%) 3(50%)
100
64
7 91
0 106
96
68 26
4
aTaken from reference 1.
fluting solvent composition given in Section 7.1.2.2.
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8080 / 8
7.2 Gas chromatography conditions. The recommended gas chromatographic
columns and operating conditions for the instrument are:
Column 1 conditions: Supelcoport 100/120 mesh coated with 1.5% SP-2250/
1.95% SP-2401 packed in a 180-cm long x 4-mm I.D. glass column with
5% Methane/95% Argon carrier gas at 60 ml/min flow rate. Column
temperature is 200" C.
Column 2 conditions: Supelcoport 100/120 mesh coated with 3% OV-1 in
a 180-cm long x 4-mm I.D. glass column with 5% Methane/95% Argon carrier
gas at 60 ml/min flow rate. Column temperature is 200* C.
7.3 Calibration
7.3.1 Establish gas chromatographic operating parameters equiva-
lent to those indicated in Table 1. The gas chromatographic system can
be calibrated using the external standard technique (Section 7.3.2) or
the internal standard technique (Section 7.3.3).
7.3.2 External standard calibration procedure
7.3.2.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with isooctane. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
7.3.2.2 Using injections of 2 to 5 ul of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
the mass injected, defined as the calibration factor (CF), can be
calculated for each parameter at each standard concentration. If
the relative standard deviation of the calibration factor is less
than 10% over the working range, linearity through the origin can
be assumed and the average calibration factor can be used in place
of a calibration curve.
7.3.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than _+10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor may be prepared for
that parameter.
-------
8080 / 9
7.3.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is
not affected by method or matrix interferences. Due to these limita-
tions, no internal standard applicable to all samples can be suggested.
7.3.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
volumes of one or more stock standards to a volumetric flask. To
each calibration standard, add a known constant amount of one or
more internal standards, and dilute to volume with isooctane. One
of the standards should be at a concentration near, but above, the
method detection limit. The other concentrations should correspond
to the expected range of concentrations found in real samples, or
should define the working range of the detector.
7.3.3.2 Using injections of 2 to 5 u.1 of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
AJS = Response for the internal standard.
C.js = Concentration of the internal standard in u.g/1.
Cs = Concentration of the parameter to be measured in u.g/1.
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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 against RF.
7.3.3.3 The working calibration curve or RF must be verified
on each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than +10%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibra-
tion curve must be prepared for that compound.
7.3.4 Florisil standardization. The cleanup procedure described
in Section 7.1.2 utilizes Florisil chromatography. Florisil from
-------
8080 / 10
different batches or sources may vary in absorption capacity. To
determine the amount of Florisil to be used, the absorption capacity of
each separate batch of Florisil is measured using lauric acid values
(2). The referenced procedure determines the adsorption from hexane
solution of lauric acid (mg) per g Florisil. The amount of Florisil to
be used for each column is calculated by dividing this factor into 110
and multiplying by 20 g.
7.4 Gas chromatographic analysis
7.4.1 Inject 2-5 ul of the sample extract using the solvent flush
technique. Smaller (1.0 ul) volumes can be injected if automatic devices
are employed. Record the volume injected to the nearest 0.05 (il, and
the resulting peak size, in area units.
7.4.2 If the peak areas exceed the linear range of the system,
dilute the extract and reanalyze.
7.4.3 If peak detection is prevented by the presence of inter-
ferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of calibration standards
through the procedure to validate elution patterns and the absence of
interferences from the reagents.
7.4.4 Examples of chromatograms for organochlorine pesticides are
shown in Figures 1-5.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware and
reagents are interference-free. Each time a set of samples is extracted or
there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement steps.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision
of the sampling technique. Laboratory replicates should be analyzed to
validate the precision of the analysis. Fortified samples should be analyzed
to validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 ug/g of sample, then the sensitivity of the instrument should be
increased or the extract subjected to additional cleanup. Detection limits
to be used for groundwater samples are indicated in Table 1. The fortified
samples should be carried through all stages of the sample preparation and
measurement steps. Where doubt exists over the identification of a peak on
the chromatograph, confirmatory techniques such as mass spectroscopy should
be used.
J
-------
8080 / 11
Column: 1.5% SP-2250+
1.95% SP-2401 on Supeicoport
Temperature: 200°C
Detector: Electron Capture
48 12 16
RETENTION TIME (MINUTES)
Figure 1. Gas chromatogram of pesticides.
-------
8080 / 12
Column: 1.5% SP-2250+
1.95% SP 2401 on Supelcopon
Temperature 20C°C
Detector: Electron Capture
4 8 12
RETENTION TIME (MINUTES)
Figure 2. Gas chromatogram of chlordane.
-------
8080 / 13
Column: 1.5* SP-2250+
1.95% SP-2401 on Supelcoport
Temperature. 200°C
Detector. Electron Capture
10 14 18
RETENTION TIME (MINUTES)
22
26
Figure 3. Gas chromatogram of toxaphene.
-------
8080 / 14
Column: 1.5% SP-2250+
1.95% SP-2401 on Supelcoport
Ttmperature: 200°C
Detector: Electron Capture
6 10 14 18
RETENTION TIME (MINUTES)
22
Figure 4. Gas chromatogram of PC8-1254.
-------
8080 / 15
Column: t.5% SP-2250+
1.95% SP-2401 on Supelcopon
Temperature: 200°C
Detector: Electron Capture
10 14 18
RETENTION TIME (MINUTES)
22
26
Figure 5. Gas chromatogram of PC8-1260.
-------
8080 / 16
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked at
or near background levels, the average recoveries presented in Table 3 were
obtained. The standard deviation of the measurement in percent recovery is
also included in Table 3.
TABLE 3. SINGLE OPERATOR ACCURACY AND PRECISION
Parameter
Average
percent
recovery
Standard
deviation
Spike
range
(ug/1)
Number
of
analyses
Matrix
types
Aldrin
a-BHC
T5-BHC
w-BHC
c[-BHC (Lindane)
Chlordane
4,4'-ODD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endn'n
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
89
89
88
86
97
93
92
89
92
95
96
97
99
95
87
88
93
95
94
96
88
92
90
92
91
2.5
2.0
1.3
3.4
3.3
4.1
1.9
2.2
3.2
2.8
2.9
2.4
4.1
2.1
2.1
3.3
1.4
3.8
1.8
4.2
2.4
2.0
1.6
3.3
5.5
2.
1.
2,
2.
1.
20
6,
3.
8.0
5.0
15
5.0
12
1.0
2.0
200
25
55-100
110
28-56
40
40
80
15
15
15
15
15
21
15
15
15
15
12
14
15
12
11
12
15
18
12
12
12
12
12
18
18
3
3
3
3
3
4
3
3
3
2
2
3
3
2
2
2
3
3
2
2
2
2
2
3
3
-------
8080 / 17
9.0 References
1. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 10 - Pesticides and PCB's.
Report for EPA Contract 68-03-2606.
2. Mills, P.A. 1968. Variation of florisil activity: simple method for
measuring absorbent capacity and its use in standardizing florisil
columns. J. Assoc. Official Anal. Chem. 51 (29).
3. U.S. EPA. 1980. Interim methods for the sampling and analysis of
priority pollutants in sediments and fish tissue. October 1980.
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio.
4. Bellar, T., J. Lichtenburg, and S. Lonnesman. 1980. Recovery of
organic compounds from environmentally contaminated bottom mate-
rials. _In Contaminants and sediments, Volume 2, ed. R. Baker, Ann
Arbor Science Publ., Inc., Ann Arbor, Michigan.
5. Rodriguez, C., W. McMahon, and K. Thomas. 1980. Method development
for determination of polychlorinated hydrocarbons in municipal
sludge. EPA Report-600/2-80-029.
6. U.S. EPA. Method 617. Organochlorine pesticides and PCB's.
Environmental Monitoring and Support Laboratory, Cincinnati, OH.
-------
METHOD 8090
NITROAROMATICS AND CYCLIC KETONES
1.0 Scope and Application
1.1 Method 8090 is used to determine the concentration of certain
nitroaromatic and cyclic ketone compounds in groundwater, liquid, and
solid sample matrices. Specifically Method 8090 may be used to detect the
following substances:
Nitrobenzene
Di nitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isophorone
Naphthoquinone
1.2 Method 8090 is recommended for use only by, or under the close
supervision of, experienced residue analysts.
2.0 Summary of Method
2.1 Method 8090 provides cleanup and gas chromatographic conditions for
the detection of ppb levels of nitroaromatic and cyclic ketone compounds.
Prior to use of this method, the sample must be extracted using appropriate
extraction techniques. Groundwater and other aqueous samples are extracted
at a neutral pH with methylene chloride as a solvent using a separatory
funnel (Method 3510) or a continuous liquid-liquid extractor (Method 3520).
Both neat and diluted organic liquids may be analyzed by direct injection.
Solid samples are extracted with methylene chloride using either the Soxhlet
extraction (Method 3540) or sonication (Method 3550) procedures. A 2- to
5-u.l aliquot of the extract is injected into a gas chromatograph (GC) using
the solvent flush technique, and compounds in the GC effluent are detected by
an electron capture detector (ECD) or a flame ionization detector (FID). An
aliquot of each sample will be spiked with standards to determine percent
recovery and the limits of detection for that sample.
2.2 The sensitivity of Method 8090 usually depends on the level of
interferences rather than on instrumental limitations. Table 1 lists the
limits of detection for some of the compounds that can be obtained in waste-
waters in the absence of interferences. Detection limits for a typical waste
sample would be significantly higher.
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of gas chromatograms. All these materials must therefore be demonstrated
-------
2 / ORGANIC ANALYTICAL METHODS - GC
to be free from interferences under the conditions of the analysis by
running method blanks. Specific selection of reagents and purification of
solvents by distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are provided as part
of this method, unique samples may require additional cleanup approaches to
achieve desired sensitivities.
3.3 Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This should be
followed by detergent washing in hot water. Rinse with tap water, distilled
water, acetone, and finally pesticide-quality hexane. Heavily contaminated
glassware may require treatment in a muffle furnace at 400° C for 15 to 30
min. Some high boiling materials, such as PCB's, may not be eliminated by
this treatment. Volumetric ware should not be heated in a muffle furnace.
Glassware should be sealed/stored in a clean environment immediately after
drying or cooling to prevent any accumulation of dust or other contaminants.
Store inverted or capped with aluminum foil.
3.4 Phthalate esters contaminate many types of products commonly found
in the laboratory. The analyst must demonstrate that no phthalate residues
contaminate the sample or solvent extract under the conditions of the analy-
sis. 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 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.6 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 u.g/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 (below) when
analyzing groundwater samples.
-------
8090 / 3
TABLE 1. GAS CHROMATOGRAPHY OF NITROAROMATICS AND ISOPHORONE
Retention time (min)
Compound
Isophorone
Nitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Col. la
4.49
3.31
5.35
3.52
Col. 2b
5.72
4.31
6.54
4.75
Detection limit (u.g/1 )
ECD FID
5
5
0.06
0.06
aGas-Chrom Q 80/100 mesh coated with 1.95% OF-1/1.5% OV-17 packed in a
4' x 1/4" O.D. glass column. FID analysis for IP and NB requires nitrogen
carrier gas at 44 ml/min and 85° C column temperature. ECD analysis for the
DNT's requires 10% methane/90% argon carrier gas at 44 ml/min flow rate and
145' column temperature.
bGas-Chrom Q 80/100 mesh coated with 3% OV-101 packed in a 10' x 1/4"
O.D. glass column. FID analyis of IP and NB requires nitrogen carrier gas
at 44 ml/min flow rate and 100* C column temperature. ECD analysis for the
DNT's requires 10% methane/90% argon carrier gas at 44 ml/min flow rate and
150' C column temperature.
4.0 Apparatus and Materials
4.1 Drying column: 20-mm I.D. pyrex chromatographic column with coarse
frit.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube: 10ml, graduated (Kontes K-570050-1025
or equivalent). Calibration must be checked. Ground-glass stopper
(size 19/22 joint) is used to prevent evaporation of extracts.
4.2.2 Evaporative flask: 500 ml (Kontes K-57001-0500 or equiva-
lent). Attach to concentrator tube with springs (Kontes K-662750-0012).
4.2.3 Synder column: Three-ball macro (Kontes K503000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Boiling chips: Solvent extracted, approximately 10/40 mesh.
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4 / ORGANIC ANALYTICAL METHODS - GC
4.3 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+_2° C). The bath should be used in a hood.
4.4 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection and all required accessories including
electron capture or flame ionization detectors, column supplies, recorder,
gases, syringes. A data system for measuring peak areas is recommended.
4.5 Chromatography column: 400-mm long x 10-mm I.D., with coarse-
fritted plate on bottom and Teflon stopcock.
5.0 Reagents
5.1 Sodium hydroxide: (ACS) 10 N in distilled water.
5.2 Sulfuric acid (1+1): (ACS) Mix equal volumes of cone. H2S04 with
distil led water.
5.3 Methylene chloride: Pesticide quality or equivalent.
5.4 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.5 Stock standards: Prepare stock standard solutions at a concen-
tration of 1.00 u.g/u.1 by dissolving 0.100 g of assayed reference material
in pesticide quality isooctane or other appropriate solvent and diluting
to volume in a 100-ml ground-glass-stoppered volumetric flask. The stock
solution is transferred to ground-glass-stoppered reagent bottles, stored in
a refrigerator, and checked frequently for signs of degradation or evaporation,
especially just prior to preparing working standards from them.
5.6 Acetone, hexane, methanol, toluene: Pesticide quality or equivalent.
5.7 Florisil: PR grade (60/100 mesh); purchase-activated at 1250° F
and store in glass containers with glass stoppers or foil-lined screw
caps. Before use, activate each batch overnight at 130" C in glass con-
tainers loosely covered with foil.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not be
prewashed with sample before collection. Composite samples should be collected
in refrigerated glass containers in accordance with the requirements of the
program. Automatic sampling equipment must be free of tygon and other
potential sources of contamination.
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8090 / 5
6.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. Chemical preservatives should not be used in the
field unless more than 24 hr will elapse before delivery to the laboratory.
If the samples will not be extracted within 48 hr of collection, the sample
should be adjusted to a pH range of 6.0-8.0 with sodium hydroxide or sulfuric
acid.
6.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
7.0 Procedures
7.1 Extraction. Extract water samples at a neutral pH with methylene
chloride as a solvent using a separatory funnel (Method 3510) or a continuous
liquid-liquid extractor (Method 3520). Extract solid samples with methylene
chloride using either the Soxhlet extraction (Method 3540) or sonication
(Method 3550) procedures. Spiked samples are used to verify the applicability
of the chosen extraction technique to each new sample type. An aliquot of
each sample should be spiked with standards to determine the percent recovery
and the limit of detection for that sample.
7.2 Cleanup and separation. If interferences prevent measurement of
these compounds by GC, the following column cleanup procedure can be used to
remove the interferences.
7.2.1 Prepare a slurry of 10 g of activated Florisil in 10%
methylene chloride in hexane (v/v). Use it to pack a 10-mm I.D. chroma-
tography column, gently tapping the column to settle the Florisil. Add
1 cm anhydrous sodium sulfate to the top of the Florisil.
7.2.2 Just prior to exposure of the sodium sulfate layer to the
air, transfer the 1-ml sample extract onto the column, using an addi-
tional 2 ml of toluene to complete the transfer.
7.2.3 Just prior to exposure of the sodium sulfate layer to the
air, add 30 ml 10% methylene chloride in hexane and continue the elution
of the column. Elution of the column should be at a rate of about 2 ml/
min. Discard the eluate from this fraction.
7.2.4 Next elute the column with 30 ml of 10% acetone/90% methyl-
ene chloride (v/v) into a 500-ml K-D flask equipped with a 10-ml concen-
trator tube.
7.2.5 Concentrate the collected fraction by the following K-D
technique.
7.2.5.1 Add 1 or 2 clean boiling chips to the flask and
attach a three-ball Snyder column. Prewet the Snyder column by
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6 / ORGANIC ANALYTICAL METHODS - GC
adding about 1 ml methylene chloride to the top. Place the K-D
apparatus on a hot water bath (60-65° C) so that the concentrator
tube is partially immersed in the hot water, and the entire lower
rounded surface of the flask is bathed in vapor. Adjust the
vertical position of the apparatus and the water temperature as
required to complete the concentration in 15-20 min. At the proper
rate of distillation, the balls of the column will actively chatter
but the chambers will not flood.
7.2.5.2 When the apparent volume of liquid reaches 1 ml,
remove the K-D apparatus and allow it to drain for at least 10 min
while cooling. Remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1-2 ml of methylene
chloride. A 5-ml syringe is recommended for this operation.
7.2.5.3 Add 1.0 ml toluene to the concentrator tube, and a
clean boiling chip. Attach a two-ball micro-Snyder column. Prewet
the Snyder column by adding about 0.5 ml of methylene chloride to
the top. Place this KD apparatus on a water bath (60-65* C) so
that the concentrator tube is partially immersed in the hot water.
Adjust the vertical position of the apparatus and the water tem-
perature as required to complete the concentration in 5-10 min.
At the proper rate of distillation, the balls of the column will
actively chatter but the chambers will not flood.
7.2.5.4 When the apparent volume of liquid reaches 0.5 ml,
remove the K-D apparatus and allow it to drain for at least 10 min
while cooling. Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with a small volume of toluene.
7.2.5.5 Adjust the final volume to 1.0 ml, stopper the con-
centrator tube, and store refrigerated if further processing will
not be performed immediately.
7.3 The recommended gas chromatographic columns and operating conditions
are:
Column 1: Gas-Chrom Q, 80/100 mesh, coated with 1.95% OF-1/1.5% OV-17
packed in a 4' x 1/4" O.D. glass column. FID analysis requires nitrogen
gas at 44 ml/minute and 85° C column temperature. EDC analysis requires
10% methane/90% argon carrier gas at 44 ml/minute flow rate and 145 C
column temperature.
Column 2: Gas-Chrom Q, 80/100 mesh, coated with 3% OV-101 packed in a
10' x 1/4" O.D. glass column. FID analysis requires nitrogen carrier
gas at 44 ml/minute flow rate and 100° C column temperature. ECD
analysis requires 10% methane/ 90% argon carrier gas at 44 ml/minute
flow rate and 150° C column temperature.
-------
8090 / 7
7.4 Calibration
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.3. By injecting secondary standards,
adjust the sensitivity of the analytical system for each compound
being analyzed so as to detect quantities of less than or equal to 1 u.g
for waste samples. Detection limits to be used for groundwater analysis
are given in Table 1. Calibrate the chromatographic system using either
the external standard technique (Section 7.4.2) or the internal standard
technique (Section 7.4.3).
7.4.2 External standard calibration procedure
7.4.2.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with isooctane. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
7.4.2.2 Using injections of 2 to 5 u,l of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
the mass injected, defined as the calibration factor (CF), can be
calculated for each parameter at each standard concentration. If
the relative standard deviation of the calibration factor is less
than 10% over the working range, linearity through the origin can
be assumed and the average calibration factor can be used in place
of a calibration curve.
7.4.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than _+10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that parameter.
7.4.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards similar
in* analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Due to these limitations,
no internal standard applicable to all samples can be suggested.
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8 / ORGANIC ANALYTICAL METHODS - GC
7.4.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
volumes of one or more stock standards to a volumetric flask. To
each calibration standard, add a known constant amount of one or
more internal standards, and dilute to volume with isooctane. One
of the standards should be at a concentration near, but above, the
method detection limit. The other concentrations should correspond
to the expected range of concentrations found in real samples, or
should define the working range of the detector.
7.4.3.2 Using injections of 2 to 5 u.1 of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
Ais = Response for the internal standard.
Cis = Concentration of the internal standard in ug/1.
Cs = Concentration of the parameter to be measured in ug/1.
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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/A-js against RF.
7.4.3.3 The working calibration curve or RF must be verified
on each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than _+10%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibration
curve must be prepared for that compound.
7.5 Gas chromatographic analysis
7.5.1 Dinitrotoluenes can be analyzed on a gas chromatograph
equipped with an electron capture detector. The other compounds covered
by Method 8090 are to be analyzed on a gas chromatograph equipped with
a flame ionization detector. Chromatography conditions are given in
-------
8090 / 9
Section 7.3. Table 1 summarizes estimated retention times and sensi-
tivities that should be achieved by this method for clean water samples.
Detection limits for a typical waste sample would be significantly higher,
7.5.2 Inject 2 to 5 u.1 of the sample extract using the solvent
flush technique. Smaller (1.0 u.1) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 u.1, and the resulting peak size, in area units.
7.5.3 If the peak areas exceed the linear range of the system,
dilute the extract and reanalyze.
7.5.4 If peak detection is prevented by the presence of interfer-
ences, further cleanup is required. Before using any cleanup procedure,
the analyst must process a series of calibration standards through the
procedure to validate elution patterns and the absence of interferences
from the reagents.
7.5.5 An example of a GC/FID chromatogram for nitrobenzene and
isophorone is shown in Figure 1. Figure 2 shows a GC/ECD chromatogram
of the dinitrotoluene.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank, that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed
to validate the sensitivity and accuracy of the,analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 u.g/g of sample, then the sensitivity of the instrument should be
increased or the extract subjected to additional cleanup. Detection limits
to be used for groundwater samples are indicated in Table 1. Where doubt
exists over the identification of a peak on the chromatograph, confirmatory
techniques such as mass spectroscopy should be used.
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
-------
10 / ORGANIC ANALYTICAL METHODS - GC
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 2
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 2.
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION
Parameter
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isophorone
Nitrobenzene
Average
percent
recovery
63
66
73
71
Standard
deviation
(%)
3.1
3.2
4.6
5.9
Spike
range
(H9/1 )
5-100
5-50
50-60
90-100
Number
of
analyses
21
24
21
24
Matrix
types
4
4
4
4
9.0 References
1. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 4 - nitroaromatics and
isophorone. Report for EPA Contract 68-03-2624 (in preparation).
-------
8090 / 11
COLUMN: 1.5% OV-17 +1.95% QF-1
ON GAS CHROM Q
TEMPERATURE: 85°C.
DETECTOR: FLAME IONIZATION
at
5
N
CO
i
Ul
i
O
CL
24 6 8 10 12
RETENTION TIME-MINUTES
Figure 1. Gas chromatogram of nitrobenzene and isophorone.
-------
12 / ORGANIC ANALYTICAL METHODS - GC
COLUMN: 1.5% OV-17-f-1.95% QF-1
ON GAS CHROM Q
TEMPERATURE: 145°C.
DETECTOR: ELECTRON CAPTURE
LU
LU
13
-J
O
O
ec
O
i
co
01
in
3
O
O
cc
•
T
fj
2468
RETENTION TIME-MINUTES
Figure 2. Gas chromatogram of dinitrotoluenes.
-------
METHOD 8100
POLYNUCLEAR AROMATIC HYDROCARBONS
1.0 Scope jndj\j)p_lJ_c_atJ-0Jl
1.1 Method 8100 is used to determine the concentration of certain
polynuclear aromatic hydrocarbons (PAH) in liquid and solid sample matrices.
Specifically, Method 8100 may be used to detect the following substances:
Acenaphthene Dibenz(a,h)anthracene
Acenaphthalene 7H-Dibenzo(c,g)carbazole
Anthracene Dibenzo(a,e)pyrene
Benzo(a)anthracene Dibenzo(a,h)pyrene
Benzo(a)pyrene Dibenzo(a,i jpyrene
Benzo(b)fluoranthene Fluoranthene
Benzo(ghi)perylene Fluorene
Benzo(j)fluoranthene Ideno(l,2,3-cd)pyrene
Benzo(k)fluoranthene 3-Methylcholanthrene
Chrysene Naphthalene
Di benzo(a,h)anthracene Phenanthrene
Dibenz(a,h)acridine Pyrene
Dibenz(a,j)acridine
1.2 The packed-column gas chrornatographic method described here cannot
adequately resolve the following four pairs of compounds: anthracene and
phenanthrene; chrysene and benzo(a)anthracene; benzo(b)fluoranthene and
benzo(k)fluoranthene; and dibenzo(a,h)anthracene and indeno(l,2,3-cd)pyrene.
The use of capillary columns instead of packed columns, as described in this
method, may adequately resolve these PAH. However, unless the purpose
of the analysis can be served by reporting a quantitative sum for an unre-
solved PAH pair, a liquid chromatographic approach (Method 8310) should be
used for these compounds. The liquid chromatographic method will resolve
all PAH compounds listed above.
1.3 Method 8100 is recommended for use only by, or under close
supervision of, experienced residue analysts.
2.0 Summary _jof_ _Met_ho d
2.1 Method 8100 provides cleanup and gas chromatographic conditions
for detecting ppb levels of certain polynuclear aromatic hydrocarbons. Prior
to analysis, samples must be extracted using appropriate techniques. Water
samples are extracted at a neutral pH with methylene chloride as a solvent
using a separatory funnel (Method 3510) or a continuous liquid-liquid extractor
(Method 3520). Both neat and diluted organic liquids may be analyzed by
direct injection. Solid samples are extracted at a neutral pH with methylene
-------
2 / ORGANIC ANALYTICAL METHODS - GC
chloride using either the Soxhlet extraction (Method 3540) or sonication
(Method 3550) procedures. A 2- to 5-u.l aliquot of the extract is injected
into a gas chromatograph (GC) using the solvent flush technique, and compounds
in the GC effluent are detected by a flame ionization detector (FID). An
aliquot of each sample must be spiked with standards to determine the spike
recovery and the limits of detection.
2.2 The sensitivity of Method 8100 usually depends on the level of
interferences rather than on instrumental limitations.
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of the chromatograms. All these materials must be demonstrated to be
free from interferences under the conditions of the analysis by running
method blanks. Specific selection of reagents and purification of solvents
by distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from source to source, depending upon the diversity of the industrial complex
or municipality being sampled. While a general cleanup technique is provided
as part of this method, unique samples may require additional cleanup approaches
to achieve the sensitivities stated in Table 1.
3.3 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.4 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 u.g/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower.
-------
8100 / 3
TABLE 1. GAS CHROMATOGRAPHY OF PAH
Compound3 Retention time (min)
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Dibenzo(a,h)anthracene
Indeno(l,2,3-cd)pyrene
Benzo(ghi )perylene
4.5
10.4
10.8
12.6
15.9
15.9
19.8
20.6
20.6
24.7
28.0
28.0
29.4
36.2
36.2
38.6
aGC conditions: Chromosorb W-AW-DCMs 100/120 mesh coated with
3% OV-17, packed in a 6-ft x 2-mm I.D. glass column, with nitrogen carrier
gas at 40 ml/min flow rate. Column temperature was held at 100° C for 4 min,
then programmed at 8"/min to a final hold at 280° C.
4.0 Apparatus and Materials
4.1 Drying column: 20-mm-I.D. pyrex chromatographic column with coarse
frit.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube: 10ml, graduated (Kontes K-570050-1025
or equivalent). Calibration must be checked. Ground-glass stopper
(Size 22 joint) is used to prevent evaporation of extracts.
4.2.2 Evaporative flask: 500 ml (Kontes K-57001-0500 or equivalent),
Attach to concentrator tube with springs (Kontes K-662750-0012).
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4 / ORGANIC ANALYTICAL METHODS - GC
4.2.3 Snyder column: Three-ball macro (Kontes K-50300-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.2.5 Boiling chips: Solvent extracted, approximately 10/40 mesh.
4.3 Water bath: Heated, with concentric ring cover, capable of temper-
ature control (+2° C). The bath should be used in a hood.
4.4 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection or capillary column injection and
all required accessories including dual flame ionization detectors, column
supplies, recorder, gases, syringes. A data system for measuring peak areas
is recommended.
4.3 Water bath: Heated, with concentric ring cover, capable of temper-
ature control (+2° C). The bath should be used in a hood.
4.4 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection or capillary column injection and all
required accessories including dual flame ionization detectors, column
supplies, recorder, gases, syringes. A data system for measuring peak areas
is recommended.
4.5 Chromatographic column: 250 mm long x 10 mm I.D. with coarse
fritted disc at bottom and Teflon stopcock.
5.0 Reagents
5.1 Preservatives
5.1.1 Sodium hydroxide: (ACS) 10 N in distilled water.
5.1.2 Sulfuric acid: (ACS) Mix equal volumes of cone. H2S04 with
distilled water.
5.1.3 Sodium thiosulfate: (ACS) Granular.
5.2 Methylene chloride, pentane, cyclohexane (pesticide quality or
equivalent).
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400" C for 4 hr in a shallow tray).
5.4 Stock standards: Prepare stock standard solutions at a concen-
tration of 1.00 [ig/u.1 by dissolving 0.100 g of assayed reference material
-------
8100 / 5
in pesticide quality isooctane or other appropriate solvent and diluting
to volume in a 100-ml ground-glass-stoppered volumetric flask. The stock
solution is transferred to ground-glass-stoppered reagent bottles, stored in
a refrigerator, and checked frequently for signs of degradation or evaporation,
especially just prior to preparing working standards.
5.5 Silica gel: 100/120 mesh desiccant (Davison Chemical grade 923
or equivalent). Before use, activate for at least 16 hr at 130° C in a
foil-covered glass container.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not be
prewashed with sample before collection. Composite samples should be col-
lected in refrigerated glass containers in accordance with the requirements
of the program. Automatic sampling equipment must be free of tygon and other
potential sources of contamination.
6.2 The samples must be iced or refrigerated from the time of collection
until extraction. Chemical preservatives should not be used in the field
unless more than 24 hr will elapse before delivery to the laboratory. If
the samples will not be extracted within 48 hr of collection, adjust the
sample to a pH range of 6.0-8.0 with sodium hydroxide or sulfuric acid and
add 35 mg sodium thiosulfate per ppm of free chlorine per liter.
6.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
7.0 Procedures
7.1 Extraction
7.1.1 Extract water samples at a neutral pH with methylene
chloride as a solvent using a separatory funnel (Method 3510), or
a continuous liquid-liquid extractor (Method 3520). Extract solid
samples with methylene chloride using either the Soxhlet extraction
(Method 3540) or sonication (Method 3550) procedures. Spiked samples
are used to verify the applicability of the chosen extraction technique
to each new sample type. An aliquot of each sample should be spiked
with standards to determine the percent recovery and the limit of
detection for the sample.
7.1.2 To achieve maxiumum sensitivity with this method, the
extract must be concentrated to 1.0 ml. Add a clean boiling chip to the
methylene chloride extract in the concentrator tube. Attach a two-ball
-------
6 / ORGANIC ANALYTICAL METHODS - GC
micro-Snyder column. Prewet the micro-Snyder column by adding about
0.5 ml of methylene chloride to the top. Place this micro K-D apparatus
on a hot water bath (60-65° C) so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the apparatus
and water temperature as required to complete the concentration in
5-10 min. At the proper rate of distillation, the balls will actively
chatter but the chambers will not flood. When the apparent volume of
liquid reaches 0.5 ml, remove the K-D apparatus and allow it to drain
for at least 10 min while cooling. Remove the micro-Snyder column and
rinse its lower joint into the concentrator tube with a small volume of
methylene chloride. Adjust the final volume to 1.0 ml and stopper the
concentrator tube.
7.2 Cleanup and separation. If interferences prevent measurement of
these compounds by GC, the following column cleanup procedure can be used to
remove the interferences.
7.2.1 Before the silica gel cleanup technique can be utilized, the
extract solvent must be exchanged to cyclohexane. Add a 1- to 10-ml aliquot
of sample extract (in methylene chloride) and a boiling chip to a clean
K-D concentrator tube. Add 4 ml cyclohexane and attach a micro-Snyder
column. Prewet the micro-Snyder column by adding 0.5 ml methylene
chloride to the top. Place the micro K-D apparatus on a boiling (100° C)
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 concentration in 5-10 min. At the
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
drain for at least 10 min while cooling. Remove the micro-Snyder column
and rinse its lower joint into the concentrator tube with a minimum of
cyclohexane. Adjust the extract volume to about 2 ml.
7.2.2 Prepare a slurry of 10 g activated silica gel in methylene
chloride and place this in a 10-mm-I.D. chromatography column. Gently
tap the column to settle the silica gel and elute the methylene chloride.
Add 1-2 cm of anhydrous sodium sulfate to the top of the silica gel.
7.2.3 Preelute the column with 40 ml pentane. 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 of cyclohexane to complete the transfer.
7.2.4 Just prior to exposure of the sodium sulfate layer to the
air, add 25 ml pentane and continue elution of the column. Discard the
pentane eluate.
7.2.5 Elute the column with 25 ml of 40% methylene chloride/
60% pentane and collect the eluate in a 500-ml K-D flask equipped with
-------
8100 / 7
a 10-ml concentrator tube. Elution of the column should be at a rate
of about 2 ml/rnin.
7.2.6 Concentrate the collected fraction to less than 10 ml
by K-D techniques using pentane to rinse the walls of the glassware.
Proceed with gas chromatographic analysis.
7.3 The recommended gas chromatographic columns and operating condi-
tions for the instrument are:
Column 1: Chromosorb W-AW-DCMs 100/120 mesh coated with 3% OV-17,
packed in a 6-ft x 2-mm I.D. glass column, with nitrogen carrier gas at
40 ml/min flow rate. Column temperature was held at 100° C for 4 min,
then programmed at 8e/min to a final hold at 280° C.
Column 2: 30-m x 0.25-mm I.D. SE-54 fused silica capillary column,
with helium carrier gas at 20 cm/sec flow rate. Column temperature was
held at 35° C for 2 min, then programmed at 10°/min to 265° C and held
for 12 min.
Column 3: 30-m x 0.32-mm I.D. SE-54 fused silica capillary column,
with helium carrier gas at 60 cm/sec flow rate. Column temperature was
held at 35° C for 2 min, then programmed at 10e/min to 265° C and held
for 3 min.
7.4 Calibration
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.3. By injecting secondary standards,
adjust the sensitivity of the analytical system for each compound
being analyzed so as to detect quantities of less than or equal to 1 u.g
for waste samples. Calibrate the chromatographic system using either
the external standard technique (Section 7.4.2) or the internal standard
technique (Section 7.4.3).
7.4.2 External standard calibration procedure
7.4.2.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with isooctane. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
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8 / ORGANIC ANALYTICAL METHODS - GC
7.4.2.2 Using injections of 2 to 5 [il of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
the mass injected, defined as the calibration factor (CF), can be
calculated for each parameter at each standard concentration. If
the relative standard deviation of the calibration factor is less
than 10% over the working range, linearity through the origin can
be assumed and the average calibration factor can be used in place
of a calibration curve.
7.4.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than +10%, the test must
be repeated using a fresh calibration standard. Alternatively, a
new calibration curve or calibration factor must be prepared for
that parameter.
7.4.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards similar
in analytical behavior to the compounds of interest. The analyst must
further demonstrate that the measurement of the internal standard is
not affected by method or matrix interferences. Due to these limita-
tions, no internal standard applicable to all samples can be suggested.
7.4.3.1 Prepare calibration standards at a minimum of three
concentration levels for each parameter of interest by adding
volumes of one or more stock standards to a volumetric flask. To
each calibration standard, add a known constant amount of one or
more internal standards, and dilute to volume with isooctane. One
of the standards should be at a concentration near, but above, the
method detection limit. The other concentrations should correspond
to the expected range of concentrations found in real samples, or
should define the working range of the detector.
7.4.3.2 Using injections of 2 to 5 ul of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
AiS = Response for the internal standard.
-------
8100 / 9
C-js = Concentration of the internal standard in u.g/1.
Cs = Concentration of the parameter to be measured in u.g/1.
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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 against RF.
7.4.3.3 The working calibration curve or RF must be verified
on each working day by the measurement of one or more calibration
standards. If the response for any parameter varies from the
predicted response by more than _+10%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibra-
tion curve must be prepared for that compound.
7.5 Gas chromatographic analysis
7.5.1 Chlorinated hydrocarbons are to be analyzed on a gas chromat-
ograph equipped with a flame ionization detector according to column
conditions described in Section 7.2. Table 1 summarizes retention times
for packed column analyses.
7.5.2 Inject 2-5 u.1 of the sample extract using the solvent flush
technique. Smaller (1.0-u.l) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 \i\, and the resulting peak size, in area units.
7.5.3 If the peak areas exceed the linear range of the system,
dilute the extract and reanalyze.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination. The blank samples should
be carried through all stages of the sample preparation and measurement steps.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be analyzed to
validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 u.g/g of sample, then the sensitivity of the instrument should be
-------
10 / ORGANIC ANALYTICAL METHODS - GC
increased or the extract subjected to additional cleanup. The fortified
samples should be carried through all stages of the sample preparation and
measurement steps. Where doubt exists over the identification of a peak on
the chromatograph, confirmatory techniques such as mass spectroscopy should
be used.
9.0 References
1. Development and application of test procedures for specific organic
toxic substances in wastewaters. Category 9 - PAHs. Report for EPA
Contract 68-03-2624. (In preparation.)
2. Sauter, A.D., Betowski, L.D., Smith, T.R., Strickler, V.A., Beimer,
R.G., Colby, B.N., and Wilkinson, J.E. 1981. Fused silica capillary
column GC/MS for the analysis of priority pollutants. Journal of
HRCSCC 4:366-384.
-------
METHOD 8120
CHLORINATED HYDROCARBONS
1.0 Scope and Application
1.1 Method 8120 is used to determine the concentration of certain
chlorinated hydrocarbons in groundwater, liquid and solid sample matrices.
Specifically, Method 8120 may be used to detect the following substances:
Dichlorobenzenes Benzotrichloride
Di chloromethy1 benzene Pentachlorohexane
Trichlorobenzenes Hexachloroethane
Tetrachlorobenzenes Hexachlorocyclohexane
Hexachlorobenzene Hexachlorocyclopentadiene
Hexachlorobutadiene Hexabutadi ene
Benzyl chloride 2-Chloronaphthalene
1.2 Method 8120 is recommended for use only by, or under the close
supervision of, experienced residue analysts.
2.0 Summary of Method
2.1 Method 8120 provides cleanup and gas chromatographic conditions
for detecting ppb levels of certain chlorinated hydrocarbons. Samples must
be subjected to extraction techniques prior to analysis. Groundwater and
other aqueous samples are extracted at a neutral pH with methylene chloride
as a solvent using a separatory funnel (Method 3510) or a continuous liquid-
liquid extractor (Method 3520). Both neat and diluted organic liquids may be
analyzed by direct injection. Solid samples are extracted at a neutral pH
with methylene chloride using either the Soxhlet extraction (Method 3540) or
sonication (Method 3550) procedures. A 2- to 5-u.l aliquot of the extract
is injected into a gas chromatograph (GC) using the solvent flush technique,
and compounds in the GC effluent are detected by an electron capture detector
(ECD). An aliquot of each sample must be spiked with standards to determine
the spike recovery and the limits of detection.
2.2 The sensitivity of Method 8120 usually depends on the level of
interferences rather than on instrumental limitations. Table 1 lists the
limits of detection that can be obtained in wastewaters in the absence of
interferences. Detection limits for a typical waste sample would be sig-
nificantly higher.
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of gas chromatograms. All these materials must therefore be demonstrated
-------
2 / ORGANIC ANALYTICAL METHODS - GC
to be free from interferences under the conditions of the analysis by running
method blanks. Specific selection of reagents and purification of solvents
by distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are provided as part
of this method, unique samples may require additional cleanup approaches to
achieve desired sensitivities.
3.3 Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used. This should be
followed by detergent washing in hot water. Rinse with tap water, distilled
water, acetone, and finally pesticide-quality hexane. Heavily contaminated
glassware may require treatment in a muffle furnace at 400" C for 15 to 30 min.
Some high boiling materials, such as PCB's, may not be eliminated by this
treatment. Volumetric ware should not be heated in a muffle furnace.
Glassware should be sealed/stored in a clean environment immediately after
drying or cooling to prevent any accumulation of dust or other contaminants.
Store inverted or capped with aluminum foil.
3.4 Phthalate esters contaminate many types of products commonly
found in the laboratory. The analyst must demonstrate that no phthalate
residues contaminate the samples or solvent extract under the conditions of
the analysis. 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 consis-
tent quality control is not practiced.
3.5 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.6 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 ug/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 (below) when
analyzing groundwater samples.
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8120 / 3
TABLE 1. GAS CHROMATOGRAPHY OF CHLORINATED HYDROCARBONS
Retention Method
time (min) Detection limit
Compound Column la (u.g/1)
1,3-dichlorobenzene 4.0 1.19
1,4-dichlorobenzene 4.3 1.34
Hexachloroethane 4.8 0.03
1,2-dichlorobenzene 5.3 1.14
Hexachlorobutadiene 11.6 0.34
1,2,4-trichlorobenzene 12.4 0.05
Hexachlorocyclopentadiene *1.5
2-chloronaphthalene *2.5 0.94
Hexachlorobenzene *7.0 0.05
aGas Chrom Q 80/100 mesh coated with 1.5% OV-1/1.5% OV-225 packed in
a 1.8-m-long x 2-mm-I.D. glass column with 5% methane/95% argon carrier gas at
30 ml/min flow rate. Column temperature is 75* C except where * indicates
160" C. Under these conditions R.T. of Aldrin is 18.8 minutes at 160° C.
4.0 Apparatus and Materials
4.1 Drying column: 20-mm I.D. pyrex chromatographic column with coarse
frit.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube: 10 ml, graduated (Kontes K-570050-1025
or equivalent). Calibration must be checked. Ground glass stopper
(size 19/22 joint) is used to prevent evaporation of extracts.
4.2.2 Evaporative flask: 500 ml (Kontes -57001-0500 or equivalent).
Attach to concentrator tube with springs (Kontes K-662750-0012).
4.2.3 Snyder column: Three-ball macro (Kontes K503000-0121 or
equivalent).
4.2.4 Snyder column: Two-ball micro (Kontes K569001-0219 or
equivalent).
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4 / ORGANIC ANALYTICAL METHODS - GC
4.2.5 Boiling chips: Solvent-extracted, approximately 10/40 mesh.
4.3: Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (+2° C). The bath should be used in a hood.
4.4 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection and all required accessories including
electron-capture or halogen-specific detector, column supplies, recorder,
gases, syringes. A data system for measuring peak areas is recommended.
4.5 Chromatography column: 300 mm long x 10 mm I.D. with coarse
fritted disc at bottom and Teflon stopcock.
5.0 Reagents
5.1 Preservatives
5.1.1 Sodium hydroxide: (ACS) 10 N in distilled water.
5.1.2 Sulfuric acid: (ACS) Mix equal volumes of cone. H2S04
with distil led water.
5.2 Methylene chloride, hexane and petroleum ether (boiling range
30-60° C): Pesticide quality or equivalent.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating at
400° C for 4 hr in a shallow tray).
5.4 Stock standards: Prepare stock standard solutions at a concen-
tration of 1.00 u.g/u.1 by dissolving 0.100 g of assayed reference material
in pesticide quality isooctane or other appropriate solvent and diluting
to volume in a 100-ml ground-glass-stoppered volumetric flask. The stock
solution is transferred to ground-glass-stoppered reagent bottles, stored in
a refrigerator, and checked frequently for signs of degradation or evapora-
tion, especially just prior to preparing working standards.
5.5 Florisil: PR grade (60/100 mesh); purchase activated at 1250° F
and store in the dark in glass containers with glass stoppers or foil-lined
screw caps. Before use, activate each batch at 130° C in foil-covered glass
containers.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers, leaving a
minimum headspace. Conventional sampling practices should be followed,
-------
8120 / 5
except that the bottle must not be prewashed with sample before collection.
Composite samples 'should be collected in refrigerated glass containers in
accordance with the requirements of the program. Automatic sampling equip-
ment must be free of tygon and other potential sources of contamination.
6.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. Chemical preservatives should not be used in the
field unless more than 24 hr will elapse before delivery to the laboratory.
If the samples will not be extracted within 48 hr of collection, the sample
should be adjusted to a pH range of 6.0-8.0 with sodium hydroxide or sulfuric
acid.
6.3 All samples should be extracted immediately and must be extracted
within 7 days and completely analyzed within 30 days of collection.
7.0 Procedures
7.1 Extraction
7.1.1 Extract water samples at a neutral pH with methylene chloride
as a solvent using a separatory funnel (Method 3510) or a continuous
liquid-liquid extractor (Method 3510). Extract solid samples with
methylene chloride using either the Soxhlet extraction (Method 3540) or
sonication (Method 3550) procedures. Spiked samples are used to verify
the applicability of the chosen extraction technique for each new sample
type. An aliquot of each sample should be spiked with standards to
determine the percent recovery and the limits of detection for that
sample.
7.1.2 To avoid significant losses of volatile dichlorobenzenes
during concentration, a constant gentle evaporation rate must be main-
tained, and the liquid volume must not be allowed to fall below 1-2 ml
before removing the K-D from the hot water bath.
7.2 Cleanup and separation. If interferences prevent measurement of
the compounds listed in Section 1.1 by GC, the following column cleanup
procedure can be used to remove the interferences.
7.2.1 Adjust the sample extract to 10 ml.
7.2.2 Place a 12-g charge of activated Florisil (see 6.3) in a
10-mm I.D. chromatography column. After settling the Florisil by
tapping the column, add a 1- to 2-cm layer of anhydrous granular sodium
sulfate to the top.
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6 / ORGANIC ANALYTICAL METHODS - GC
7.2.3 Preelute the column, after cooling, with 100 ml of petro-
leum ether. Discard the eluate and, just prior to exposure of the
sulfate layer to air, quantitatively transfer the sample extract into
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 petroleum ether and
collect the eluate in a 500-ml K-D flask equipped with a 10-ml concen-
trator tube. This fraction should contain all the chlorinated hydro-
carbons.
7.2.4 Concentrate the fraction by K-D, prewetting the column with
hexane. When the apparatus is cool, remove the Snyder column and rinse
the flask and its lower joint into the concentrator tube with 1-2 ml
hexane. Analyze by gas chromatography.
7.3 Gas chromatography conditions. The recommended gas chromatographic
column and operating conditions for the instrument are:
Gas Chrorn Q, 80/100 mesh, coated with 1.5% OV-1/1.5% OV-225 packed in a
1.8-m-long x 2-mm-I.D. glass column with 5% methane/95% argon carrier gas
at 30 ml/min flow rate. Column temperature is 75° C for low molecular
weight compounds and 160° C for high molecular compounds.
7.4 Calibration
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.3. By injecting secondary standards,
adjust the sensitivity of the analytical system for each compound
being analyzed so as to detect quantities of less than or equal to 1 u,g
for waste samples. Detection limits to be used for groundwater analysis
are given in Table 1. Calibrate the chromatographic system using either
the external standard technique (Section 7.4.2) or the internal standard
technique (Section 7.4.3).
7.4.2 External standard calibration procedure
7.4.2.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with isooctane. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
7.4.2.2 Using injections of 2 to 5 u.1 of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
-------
8140 / 7
If the samples will not be extracted within 48 hr of collection, the sample
should be adjusted to a pH range of 6.0 to 8.0 with sodium hydroxide or
sulfuric acid. Prior to addition of acid or base, mark the water meniscus
on the side of the sample bottle for later determination of sample volume.
6.3 All samples must be extracted within 7 days and completely analyzed
within 14 days of collection.
7.0 Procedures
7.1 Sample preparation
7.1.1 Water samples should be extracted at a neutral pH with
methylene chloride as a solvent, using a separatory funnel (Method 3510)
or a continuous liquid-liquid extractor (Method 3520). Soxhlet extrac-
tion (Method 3540) or sonication procedures (Method 3550) are used for
solid samples. Spiked samples are used to verify the applicability of
the chosen extraction technique to each new sample type.
7.2 The recommended gas chromatographic column and operating conditions
for the instrument are:
Column la Conditions: Supelcoport (100/120 mesh) coated with 5% SP-2401
packed in a 180-cm long x 2-mm I.D. glass column with helium carrier gas
at a flow rate of 30 ml/min. Column temperature, programmed: initial
150° C, hold for 1 min, then program at 25° C/min to 220° C and hold.
Column Ib Conditions: Same as Column la, except nitrogen carrier gas at
a flow rate of 30 ml/min. Temperature, programmed: initial 170° C,
hold 2 min, then program at 20° C/min to 220° C and hold.
Column 2 Conditions: Supelcoport (100/120 mesh) coated with 3% SP-2401
packed in a 180-cm long x 2-mm I.D. glass column with helium carrier gas
at a flow rate of 25 ml/min. Column temperature, programmed, initial
170° C, hold for 7 min, then program at 10° C/min to 250° C and hold.
Column 3 Conditions: Gas Chrom Q (100/120 mesh) coated with 15% SE-54
packed in a 50-cm long x 1/8 in. O.D. Teflon column with nitrogen
carrier gas at a flow rate of 30 ml/min. Temperature, programmed:
initial 100° C, then program immediately at 25° C/min to 200° C and
hold.
7.3 Calibration
Establish gas chromatographic operating parameters equivalent to those
indicated in Section 7.2. By injecting secondary standards, adjust the
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8 / ORGANIC ANALYTICAL METHODS - GC
sensitivity of the analytical system for each compound being analyzed so as
to detect quantities of less than or equal to 1 ug for waste samples.
Detection limits to be used for groundwater analysis are given in Table 1.
Calibrate the chromatographic system using either the external standard
technique (Section 7.4.2) or the internal standard technique (Section 7.4.3).
7.3.1 External standard calibration procedure
7.3.1.1 For each parameter of interest, prepare calibration
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with hexane or other suitable solvent. One of
the external standards would be at a concentration near, but
above, the method detection limit. The other concentrations
should correspond to the expected range of concentrations found in
real samples or should define the working range of the detector.
7.3.1.2 Using injections of 2 to 5 ul of each calibration
standard, tabulate peak height or area responses against the mass
injected. The results can be used to prepare a calibration curve
for each parameter. Alternatively, the ratio of the response to
the mass injected, defined as the calibration factor (CF), can be
calculated for each parameter at each standard concentration. If
the relative standard deviation of the calibration factor is less
than 10% over the working range, linearity through the origin can
be assumed and the average calibration factor can be used in place
of a calibration curve.
7.3.1.3 The working calibration curve or calibration
factor must be verified on each working day by the measurement of
one or more calibration standards. If the response for any parameter
varies from the predicted response by more than +10%, the test
must be repeated using a fresh calibration standard. Alternatively,
a new calibration curve or calibration factor may be prepared for
that parameter.
7.3.2 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards
similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the internal
standard is not affected by method or matrix interferences. Due to
these limitations, no internal standard applicable to all samples can
be suggested.
7.3.2.1 Prepare calibration standards at a minimum of
three concentration levels for each parameter of interest by
adding volumes of one or more stock standards to a volumetric
flask. To each calibration standard, add a known constant amount
-------
8140 / 9
of one or more internal standards, and dilute to volume with
hexane or other suitable solvent. One of the standards should be
at a concentration near, but above, the method detection limit.
The other concentrations should correspond to the expected range
of concentrations found in real samples, or should define the
working range of the detector.
7.3.2.2 Using injections of 2 to 5 u.1 of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
Ais = Response for the internal standard.
Cis = Concentration of the internal standard in u.g/1.
Cs = Concentration of the parameter to be measured in u.g/1,
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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 against RF.
7.3.2.3 The working calibration curve or RF must be
verified on each working day by the measurement of one or more
calibration standards. If the response for any parameter varies
from the predicted response by more than _+10%, the test must be
repeated using a fresh calibration standard. Alternatively, a new
calibration curve must be prepared for that compound.
7.4 Analysis
7.4.1 Inject 2 to 5 u.1 of the sample extract using the solvent-
flush technique. Smaller (1.0-u.l) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 u.1, and the resulting peak size, in area units.
7.4.2 If the peak area exceeds the linear range of the system,
dilute the extract and reanalyze.
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10 / ORGANIC ANALYTICAL METHODS - GC
7.4.3 If peak detection is prevented by the presence of inter-
ferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of calibration standards
through the procedure to validate elution patterns and the absence of
interferences from the reagents.
7.4.4 It should be noted that Naled can be completely converted to
Dichlorvos on the GC column.
7.4.5 Examples of chromatograms for organophosphorus pesticides
are shown in Figures 1 through 4.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware and
reagents are interference-free. Each time a set of samples is extracted or
there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified waste samples of waste should be
analyzed to validate the accuracy of the analysis. Detection limits to be
used for groundwater samples are indicated in Table 1. Where doubt exists
over the identification of a peak on the chromatogram, confirmatory techniques
such as mass spectrometry should be used (Section 8.3).
8.3 GC/MS confirmation
8.3.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. The mass spectrometer
should be capable of scanning the mass range from 35 amu to a mass 50
amu above the molecular weight of the compound. The instrument must be
capable of scanning the mass range at a rate to produce at least 5 scans
per peak but not to exceed 3 sec per scan utilizing 70-V (nominal) electron
energy in the electron impact ionization mode. A GC-to-MS interface con-
structed of all-glass or glass-lined materials is recommended. 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 should be interfaced to the mass spectrometer.
8.3.2 Gas chromatographic columns and conditions should be
selected for optimum separation and performance. The conditions
selected must be compatible with standard GC/MS operating practices,
such as those described for Method 8250.
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8120 / 11
Column: 1.5% OV-1+1.5% OV-225 on Gas Chrom Q
Temperature: 160°C
Detector: Electron Capture
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12 / ORGANIC ANALYTICAL METHODS - GC
2. Mills, P.A. 1968. Variation of Florisil activity: Simple method
for measuring absorbent capacity and its use in standardizing Florisil
columns. J. Assoc. Official Analyt. Chem. 51(29).
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION
Parameter
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
1,2,4-Trichlorobenzene
Average
percent
recovery
76
82
86
89
95
96
99
ene 96
Standard Spike Number
deviation range of
(%) (ng/1 ) analyses
25
10
18
20
12
10
12
16
19.1-268
29.8-356
20.4-238
23.0-324
1.29-14.9
3.12-36.8
1.02-14.8
15.1-216
18
18
18
18
18
18
18
18
Matrix
types
3
3
3
3
3
3
3
3
-------
METHOD 8140
ORGANOPHOSPHORUS PESTICIDES
1.0 Scope and Application
1.1 Method 8140 is a gas chromatographic (GC) method for determining
pesticides in groundwater and waste samples. Specifically, Method 8140 may
be used to determine the following parameters:
Azinphos methyl Merphos
Bolster (Sulprofos) Mevinphos
Chlorpyrifos Monochrotophos
Coumaphos Naled
Demeton Parathion methyl
Diazinon Parathion
Dichlorvos Phorate
Dimethoate Ronnel
Disulfoton Stirophos (Tetrachlorvinphos)
EPN Sulfotepp
Ethoprop TEPP
Fensulfothion Tokuthion (Prothiofos)
Fenthion Trichloronate
Malathion
1.2 When Method 8140 is used to analyze unfamiliar samples, compound
identifications should be supported by at least two additional qualitative
technique if mass spectroscopy is not employed. Section 8.3 provides gas
chromatograph/mass spectrometer (GC/MS) criteria appropriate for the quali-
tative confirmation of compound identifications.
1.3 The estimated detection limits for each of the parameters in
wastewater are listed in Table 1. The detection limit for a specific waste
sample may differ from those listed, depending upon the nature of inter-
ferences and the sample matrix.
1.4 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatography and in the interpre-
tation of gas chromatograms.
2.0 Summary of Method
2.1 Method 8140 provides gas chromatographic conditions for the detec-
tion of ppb levels of organophosphorus pesticides. Prior to the use of this
method, appropriate sample extraction techniques must be used. Water samples
are extracted at a neutral pH with methylene chloride as a solvent using a
separatory funnel (Method 3510) or a continuous liquid-liquid extractor
(Method 3520). Both neat and diluted organic liquids may be analyzed by
-------
2 / ORGANIC ANALYTICAL METHODS - GC
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND ESTIMATED
DETECTION LIMITS FOR METHOD 8140 IN WASTEWATER3
Parameter
Demeton-S
Phorate
Disulfoton
Demeton-0
Trichloronate
Fenthion
Tokuthion
Bolstar
Fensulfothion
Azinphos methyl
Coumaphos
Dichlorvos
Mevinphos
Stirophos
Ethoprop
Pa rat hi on methyl
Ronnel
Chlorpyrifos
Merphos
Oiazinon
Naled
GC
column^
la
la
la
la
la
la
la
la
la
la
la
lb,3
Ib
lb,3
2
2
2
2
2
2
3
Retention
time
(min)
1.16
1.43
2.10
2.53
2.94
3.12
3.40
4.23
6.41
6.80
11.6
0.8, 1.50
2.41, 5.51
8.52
3.02
3.37
5.57
6.16
7.45
7.73
3.28
Estimated
detection
limit
(H9/1)
0.25
0.15
0.20
0.25
0.15
0.10
0.5
0.15
1.5
1.5
1.5
0.1
0.3
5.0
0.25
0.3
0.3
0.3
0.25
0.6
0.1
Information taken from Reference 1.
bColumn conditions are as follows:
Column la Conditions: Supelcoport (100/120 mesh) coated with 5% SP-2401
packed in a 180-crn long x 2-mm I.D. glass column with helium carrier gas at a
flow rate of 30 ml/min. Column temperature, programmed: initial 150° C,
hold for 1 min, then program at 25° C/min to 220° C and hold.
Column Ib Conditions: Same as Column la, except nitrogen carrier gas at a
flow rate of 30 ml/min. Temperature, programmed: initial 170° C, hold 2 min,
then program at 20° C/min to 220° C and hold.
Column 2 Conditions: Supelcoport (100/120 mesh) coated with 3% SP-2401
packed in a 180-crn long x 2-mm I.D. glass column with helium carrier gas at
flow rate
for 7 min
of 25 ml/min.
then program
*s - _,
Column temperature, programmed, initial 170° C,
at 10° C/min to 250° C and hold.
a
hold
Column 3 Conditions: Gas Chrom Q (100/120 mesh) coated with 15% SE-54 packed
in a 50-crn long x 1/8 in. O.D. Teflon column with nitrogen carrier gas at a
flow rate of 30 ml/min. Temperature, programmed: initial 100° C, then
program immediately at 25° C/min to 200° C and hold.
-------
8140 / 3
direct injection. Soxhlet extraction (Method 3540) or sonication (Method
3550} procedures are used for solid samples. Spiked samples are used to
verify the applicability of the chosen extraction technique to each new
sample type. A gas chromatograph with a flame photometric or thermionic
detector is used for analysis.
2.2 Each sample must be spiked with an appropriate standard to determine
the percent recovery and the detection limit for that sample.
3.0 Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms. All these materials
must be routinely demonstrated to be free from interferences under the
conditions of the analysis by running laboratory reagent blanks as described
in Section 8.1.
3.1.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. This should be followed by detergent washing with hot water and
rinses with tap and distilled water. The glassware should then be
drained dry and heated in a muffle furnace at 400" C for 15 to 30 min.
Some thermally stable materials such as PCB's may not be eliminated by
this treatment. Solvent rinses with acetone and pesticide quality
hexane may be substituted for the muffle furnace heating. Volumetric
ware should not be heated in a muffle furnace. After drying and
cooling, glassware should be sealed and stored in a clean environment
to prevent any accumulation of dust or other contaminants. Store
inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of solvents by distillation
in all-glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from waste to waste, depending upon the nature and diversity of
the waste being sampled. Unique samples may require special cleanup
approaches to achieve the estimated detection of limits listed in Table 1.
The use of florisil and silica gel as cleanup materials for the compounds in
this method has been demonstrated to yield recoveries less than 85% and is
not recommended for use in this method (1). Use of phosphorus- or halogen-
specific detectors, however, often obviates the necessity for cleanup for
relatively clean sample matrices. If particular circumstances demand the use
of an alternative cleanup procedure, the analyst must determine the elution
-------
4 / ORGANIC ANALYTICAL METHODS - GC
profile and demonstrate that the recovery of each compound of interest is no
less than 85%.
3.3 Use of a flame photometric detector in the phosphorus mode will
minimize interferences from materials that do not contain phosphorus.
Elemental sulfur, however, may interfere with the determination of certain
organophosphorus pesticides by flame photometric gas chromatography.
3.4 A halogen-specific detector (electrolytic conductivity or micro-
coulometric) is very selective for the halogen-containing pesticides and is
recommended for use with dichlorvos, naled and stirophos.
3.5 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used.
3.6 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 u.g/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 when analyzing
groundwater samples.
4.0 Apparatus and Materials
4.1 Glassware.
4.1.1 Drying column: Chromatographic column 400-mm long x
19-mm I.D. with coarse frit.
4.1.2 Chromatographic column: 300-mm long x 10-mm I.D. with
coarse fritted disc at bottom and Teflon stopcock.
4.1.3 Concentrator tube, Kuderna-Danish: 10-ml, graduated.
Calibration must be checked at the volumes employed in the test.
Ground glass stopper is used to prevent evaporation of extracts.
-------
8140 / 5
4.1.4 Evaporative flask, Kuderna-Danish: 500-ml. Attach to
concentrator,tube with springs.
4.1.5 Snyder column, Kuderna-Danish: three-ball macro.
4.1.6 Vials: Amber glass, 10- to 15-ml capacity with Teflon-
lined screw-cap.
4.2 Boiling chips: Approximately 10/40 mesh. Heat to 400" C for
30 min or Soxhlet extract with methylene chloride.
4.3 Water bath: Heated, with concentric ring cover, capable of
temperature control (+_2° C). The bath should be used in a hood.
4.4 Balance: Analytical, capable of accurately weighing to the
nearest 0.0001 g.
4.5 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection and all required accessories including
syringes, analytical columns, gases, detector and stripchart recorder. A
data system is recommended for measuring peak areas.
4.5.1 Columns:
Column 1: 180-cm long x 2-mm I.D. glass, packed with 5%
SP-2401 on Supelcoport, 100/120 mesh (or equivalent).
Column 2: 180-cm long x 2-mm I.D. glass, packed with 3%
SP-2401 on Supelcoport, 100/120 mesh (or equivalent).
Column 3: 50-cm long x 1/8 inch O.D. Teflon, packed with 15%
SE-54 on Gas Chrom Q (80/100 mesh).
4.5.2 Detector: These detectors have proven effective in analysis
for the parameters listed in Section 1.1 and were used to develop the
accuracy and precision statements in Section 8.4.
Phosphorus-specific: Nitrogen/Phosphorus (N/P), operated in
phosphorus-sensitive mode, or Flame Photometric (FPD). The
FPD is more selective for phosphorus than the N/P.
Halogen-specific: Electrolytic Conductivity or Microcoulometric.
These are very selective for those pesticides containing
halogen substituents.
-------
6 / ORGANIC ANALYTICAL METHODS - GC
5.0 Reagents
5.1 Reagent water: Reagent water is defined as a water in which
an interferent is not observed at the method detection limit of each parameter
of interest.
5.2 Hexane, methylene chloride: Pesticide quality or equivalent.
5.3 Sodium sulfate: (ACS) Granular, anhydrous. Purify by heating at
400° C for 4 hr in a shallow tray.
5.4 Stock standard solutions (1.00 u.g/u.1): Stock standard solutions
can be prepared from pure standard materials or purchased as certified
solutions.
5.4.1 Prepare stock standard solutions by accurately weighing
about 0.0500 g of pure material. Dissolve the material in pesticide-
quality iso-octane or other suitable solvent and dilute to volume in a
10-ml volumetric flask. Larger volumes can be used at the convenience
of the analyst. If compound purity is certified at 96% or greater, the
weight can be used without correction to calculate the concentration of
the stock standard. Commercially prepared stock standards can be used
at any concentration if they are certified by the manufacturer or by
an independent source. (Disulfoton standards should be prepared on a
monthly basis.)
5.4.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4° C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
5.4.3 Stock standard solutions must be replaced after 6 months,
or sooner if comparison with check standards indicates a problem.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not be
prewashed with sample before collection. Composite groundwater samples
should be collected in refrigerated glass containers in accordance with the
requirements of the program. Automatic sampling equipment must be free of
Tygon and other potential sources of contamination.
6.2 The samples must be iced or refrigerated from the time of collec-
tion until extraction. Chemical preservatives should not be used in the
field unless more than 24 hr will elapse before delivery to the laboratory.
-------
8140 / 11
Column: 5% SP-2401 on Supelcoport
Temperature: 170°C 7 Minutes, then
10°C/Minuteto250°C
Detector: Phosphorus-Specific Flame Photometric
45678
RETENTION TIME (MINUTES)
10
11
12
Figure 1. Gas chromatogram of organophosphorus pesticides (Example 1).
-------
12 / ORGANIC ANALYTICAL METHODS - GC
Column: 3% SP-2401
Program: 170°C7 Minutes, 10°C/Minute
to 250°C
Detector: Phosphorus/Nitrogen
65432
RETENTION TIME (MINUTES)
Figure 2. Gas chromatogram of organophosphorus pesticides (Example 2).
-------
8140 / 13
Column: 15% SE-54 on Gas Chrom Q
Temperature: 100°C Initial, then
250C/Minute to 200°C
Detector: Hall Electrolytic Conductivity-Oxidative Mode
7654321
RETENTION TIME (MINUTES)
Figure 3. Gas chromatogram of organophosphorus pesticides (Example 3).
-------
14 / ORGANIC ANALYTICAL METHODS - GC
Column: 5% SP-2401 on Supelcoport
Temperature: 170°C 2 Minutes, then 20°C/Minute to 220°C
Detector: Phosphorus-Specific Flame Photometric
345
RETENTION TIME (MINUTES)
Figure 4. Gas chromatogram of organophosphorus pesticides (Example 4).
-------
8140 / 15
8.3.3 At the beginning of each day that confirmatory analyses are
to be performed, the GC/MS system must be checked to see that all DFTPP
(decafluorotriphenyl phosphine) performance criteria are achieved, as
described in Method 8250.
8.3.4 To confirm an identification of a compound, the background-
corrected mass spectrum of the compound must be obtained from the
sample extract and compared with a mass spectrum from a stock or
calibration standard analyzed under the same chromatographic conditions.
At least 25 nanograms of material should be injected into the GC/MS.
The following criteria must be met for qualitative confirmation:
1. The molecular ion and all other ions present above 10%
relative abundance in the mass spectrum of the standard must be
present in the mass spectrum of the sample with agreement to ^10%.
For example, if the relative abundance of an ion is 30% in the mass
spectrum of the standard, the allowable limits for the relative
abundance of that ion in the mass spectrum for the sample would
be 20-40%.
2. The retention time of the compound in the sample must be
within 6 sec of the retention time for the same compound in the
standard solution.
3. Compounds that have very similar mass spectra can be
explicitly identified by GC/MS only on the basis of retention time
data.
8.3.5 Where available, chemical ionization mass spectra may be
employed to aid in the qualitative identification process.
8.3.6 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps
may include the use of alternate packed or capillary GC columns or
additional cleanup.
8.4 Method performance
8.4.1 Estimated detection limits (EDL) and associated chromato-
graphic conditions for wastewater are listed above in Table 1. The
detection limit is calculated from the minimum detectable GC response
being equal to five times the GC background noise.
8.4.2 Single operator accuracy and precision studies have been
conducted using spiked wastewater samples. The results of these
studies are presented in Table 2.
-------
16 / ORGANIC ANALYTICAL METHODS - GC
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION FOR METHOD 8140a
Parameter
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Disulfoton
Ethoprop
Fensulfothion
Fenthion
Merphos
Mevinphos
Naled
Parathion methyl
Phorate
Ronnel
Stirophos
Tokuthion
Trichloronate
Average Standard
percent deviation
recovery (%)
72.7
64.6
98.3
109.0
67.4
67.0
72.1
81.9
100.5
94.1
68.7
120.7
56.5
78.0
96.0
62.7
99.2
66.1
64.6
105.0
18.8
6.3
5.5
12.7
10.5
6.0
7.7
9.0
4.1
17.1
19.9
7.9
7.8
8.1
5.3
8.9
5.6
5.9
6.8
18.6
Spike Number
range of
(ng/1 ) analyses
21-250
4.9-46
1.0-50.5
25-225
11.9-314
5.6
15.6-517
5.2-92
1.0-51.5
23.9-110
5.3-64
1.0-50
15.5-520
25.8-294
0.5-500
4.9-47
1.0-50
30.3-505
5.3-64
20
17
17
18
17
17
7
16
17
18
17
17
18
16
16
21
17
18
16
17
3
Information taken from Reference 3.
-------
8140 / 17
9.0 References
1. Development of analytical test procedures for organic pollutants
in wastewater; Report for EPA Contract No. 68-03-2711. (In
preparation)
2. Burke, J.A. 1965. Gas chromatography for pesticide residue
analysis; some practical aspects. Journal of the Association of
Official Analytical Chemists 48:1037.
3. Pesticide methods evaluation. Letter Reports #6, 12A, and 14 in
EPA Contract No. 68-03-2697.
-------
METHOD 8150
CHLORINATED HERBICIDES
1.0 Scope and Application
1.1 Method 8150 is a gas chromatographic (GC) method for determining
certain chlorinated acid herbicides in groundwater and waste samples.
Specifically, Method 8150 may be used to determine the following compounds:
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP
Dalapon
Dicamba
Dichloroprop
Dinoseb
MCPA
MCPP
Since these compounds are produced and used in various forms (i.e., acid,
salt, ester, etc.), the method includes a hydrolysis step to convert the
herbicide to the acid form prior to analysis.
1.2 When Method 8150 is used to analyze unfamiliar samples, compound
identifications should be supported by at least one additional qualitative
technique. This method describes analytical conditions for a second gas
chromatographic column that can be used to confirm measurements made with the
primary column. Section 8.3 provides gas chromatograph/mass spectrometer
(GC/MS) criteria appropriate for the qualitative confirmation of compound
identifications.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatography and in the interpre-
tation of gas chromatograms. Only experienced analysts should be allowed to
work with diazomethane due to the potential hazards associated with its use
(explosive, carcinogenic).
2.0 Summary of Method
Method 8150 provides extraction, esterification and gas chromatographic
conditions for the analysis of chlorinated acid herbicides in water and waste
samples. Spiked samples are used to verify the applicability of the chosen
extraction technique to each new sample type. The esters are hydrolyzed with
potassium hydroxide and extraneous organic material is removed by a solvent
wash. After acidification, the acids are extracted with solvent and converted
to their methyl esters using diazomethane as the derivatizing agent. After
excess reagent is removed, the esters are determined by gas chromatography
-------
2 / ORGANIC ANALYTICAL METHODS - GC
employing an electron capture detector, microcoulometric detector, or
electrolytic conductivity detector (2). The results are reported as the
acid equivalents.
2.2 The sensitivity of Method 8150 usually depends on the level of
interferences rather than on instrumental limitations. Table 1 lists the
limits of detection that can be obtained in wastewaters in the absence of
interferences. Detection limits for a typical waste sample would be
significantly higher.
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND DETECTION
LIMITS FOR METHOD 8150 IN WASTEWATER
Retention time (min)a
Parameter
Col. la Col. Ib Column 2 Column 3
Estimated
detection
limit (ug/1)
Dicamba
2,4-D
2,4,5-TP
2,4,5-T
2,4-DB
Dalapon
MCPP
MCPA
Dichloroprop
Dinoseb
1.2
2.0
2.7
3.4
4.1
3.4
4.1
4.8
11.2
1.0
1.6
2.0
2.4
--
--
_-
__
--
--
1.0
1.0
0.1
0.1
1.0
5.0 1.0
200
200
1.0
0.1
aColumn conditions are as follows:
Column la conditions: 95% Argon/5% Methane carrier gas as a flow rate of
70 ml/min. Column temperature isothermal at 185° C.
Column Ib temperature: 140° C for 6 min and then programmed to 200' C at
lO'/min.
Column 2 conditions: 95% Argon/5% Methane carrier gas at a flow rate of
70 ml/min. Column temperature isothermal at 185" C.
Column 3 conditions: UHP Nitrogen carrier gas at a flow rate of 25 ml/min.
Column temperature programmed from 100° C to 150° C at 10e/min.
-------
8150 / 3
3.0 Interferences
3.1 Method interferences may be caused by contaminants in solvents,
reagents, glassware and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms. All these materials
must be routinely demonstrated to be free from interferences under the
conditions of the analysis by running laboratory reagent blanks as described
in Section 8.1.
3.1.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. This should be followed by detergent washing with hot water and
rinses with tap and distilled water. The glassware should then be
drained dry and heated in a muffle furnace at 400° C for 15 to 30 min.
Some thermally stable materials such as PCB's may not be eliminated by
this treatment. Solvent rinses with acetone and pesticide quality
hexane may be substituted for the muffle furnace heating. Volumetric
ware should not be heated in a muffle furnace. After drying and
cooling, glassware should be sealed and stored in a clean environment
to prevent any accumulation of dust or other contaminants. Store
inverted or capped with aluminum foil.
3.1.2 The use of high purity reagents and solvents helps to
minimize interference problems. Purification of solvents by distillation
in all-glass systems may be required.
3.2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from waste to waste, depending upon the nature and diversity of
the waste being sampled.
3.3 Organic acids, especially chlorinated acids, cause the most
direct interference with the determination. Phenols, including chlorophenols,
may also interfere with this procedure.
3.4 Alkaline hydrolysis and subsequent extraction of the basic solution
removes many chlorinated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis.
3.5 The herbicides, being strong organic acids, react readily with
alkaline substances and may be lost during analysis. Therefore, glassware
and glass wool must be acid-rinsed and sodium sulfate must be acidified with
sulfuric acid prior to use to avoid this possibility.
3.6 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
-------
4 / ORGANIC ANALYTICAL METHODS - GC
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak on the gas
chromatogram, confirmatory techniques such as mass spectroscopy should be
used. Detection limits for groundwater and EP extracts are given in Table 1,
Detection limits for these compounds in wastes should be set at 1 u.g/g.
4.0 Apparatus and Materials
4.1 Glassware (all specifications are suggested. Catalog numbers are
included for illustration only).
4.1.1 Separatory funnel: 2000-ml, with Teflon stopcock.
4.1.2 Drying column: Chromatographic column 400 mm long x
19 mm I.D. with coarse frit.
4.1.3 Chromatographic column: 300 mm long x 10 mm I.D. with
coarse fritted disc at bottom and Teflon stopcock.
4.1.4 Concentrator tube, Kuderna-Danish: 10-ml, graduated.
Calibration must be checked at the volumes employed in the test.
Ground-glass stopper is used to prevent evaporation of extracts.
4.1.5 Evaporative flask, Kuderna-Danish: 500-ml. Attach to
concentrator tube with springs.
4.1.6 Snyder column, Kuderna-Danish: three-ball macro.
4.1.7 Snyder column, Kuderna-Danish: two-ball micro.
4.1.8 Vials: Amber glass, 10- to 15-ml capacity with Teflon-
lined screw-cap.
4.1.9 Erlenmeyer flask: Pyrex, 250-ml with 24/40 ground-
glass joint.
4.2 Boiling chips: approximately 10/40 mesh. Heat to 400" C for
30 min or Soxhlet extract with methylene chloride.
4.3 Diazald Kit: recommended for the generation of diazomethane
(available from Aldrich Chemical Co., Cat. No. 210,025-2).
4.4 Water bath: Heated, with concentric ring cover, capable of
temperature control (+2° C). The bath should be used in a hood.
4.5 Glass wool: Acid washed.
-------
8150 / 5
4.6 Balance: Analytical, capable of accurately weighing to the
nearest 0.0001 g.
4.7 Pipet: Pasteur, glass, disposable (140-mm x 5-mm I.D.).
4.8 Gas chromatograph: Analytical system complete with gas chromato-
graph suitable for on-column injection and all required accessories including
syringes, analytical columns, gases, detector and stripchart recorder. A
data system is recommended for measuring peak areas.
4.8.1 Column 1: 180 cm long x 4 mm I.D. glass, packed with 1.5%
SP-2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or equivalent.
4.8.2 Column 2: 180 cm long x 4 mm I.D. glass, packed with 5%
OV-210 on Gas Chrom Q (100/120 mesh) or equivalent.-
4.8.3 Column 3: 180 cm long x 2 mm I.D. glass, packed with 0.1%
SP-1000 on 80/100 mesh Carbopak C or equivalent.
4.8.4 Detector: Electron capture. This detector has proven
effective in the analysis of wastewaters for the parameters listed in
Section 1.1. Guidelines for the use of alternate detectors are provided
in Section 7.4.
4.9 Wrist Shaker: Burrel Model 75 or equivalent.
5.0 Reagents
5.1 Reagent water: Reagent water is defined as a water in which an
interferent is not observed at the method detection limit of each parameter
of interest.
5.2 Sodium hydroxide solution (10 N): Dissolve 40 g NaOH in reagent
water and dilute to 100 ml.
5.3 Sulfuric acid solution (1:1): Slowly add 50 ml ^$04
(sp. gr. 1.84) to 50 ml of reagent water.
5.4 Sulfuric acid solution (1:3): Slowly add 1 part ^$04
(sp. gr. 1.84) to 3 parts reagent water.
5.5 Hydrochloric acid: (ACS) Mix 1 part of concentrated acid with
9 parts distilled water (v/v).
5.6 Potassium hydroxide solution: 37% aqueous solution (w/v).
Prepare with reagent grade potassium hydroxide pellets and distilled water.
-------
6 / ORGANIC ANALYTICAL METHODS - GC
5.7 Acetone, hexane, toluene, methanol: Pesticide quality or
equivalent.
5.8 Diethyl ether: Nanograde, redistilled in glass if necessary.
Must be free of peroxides as indicated by EM Quant test strips (available
from Scientific Products Co., Cat. No. P1126-8, and other suppliers).
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.
5.9 Sodium sulfate: (ACS) Granular, acidified as follows: Slurry
100 g sodium sulfate with enough diethyl ether to just cover the solid, then
add 0.1 ml of concentrated sulfuric acid. Remove the ether under a vacuum.
Mix 1 g of the resulting solid with 5 ml of reagent water and measure the pH
of the mixture. It must be below pH 4. Store at 130° C. Several levels of
purification may be required in order to reduce background phthalate levels to
an acceptable level: (1) Heat 4 hr at 400° C in a shallow tray, (2) Heat 16 hr
at 450-400° C in a shallow tray, (3) Soxhlet extract with methylene chloride
for 48 hr.
5.10 Carbitol (diethylene glycol monoethyl ether).
5.11 N-methyl (-N-nitroso-p-toluenesulfonamide (Diazald): High
purity available from Aldrich Chemical Co.
5.12 5% acidified Na2S04: Use 50 g of acidified anhydrous
N32S04 to every 1000 ml distilled H20.
5.13 Stock standard solutions (1.00 ug/u/l): Stock standard solutions
can be prepared from pure standard materials or purchased as certified
solutions.
5.13.1 Prepare stock standard solutions by accurately weighing
about 0.0100 g of pure acids. Dissolve the material in pesticide-quality
diethyl ether and dilute to volume in a 10-ml volumetric flask. Larger
volumes can be used at the convenience of the analyst. If compound
purity is certified at 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration
if they are certified by the manufacturer or by an independent source.
5.13.2 Transfer the stock standard solutions into Teflon-sealed
screw-cap bottles. Store at 4° C and protect from light. Stock
standard solutions should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards
from them.
-------
8150 / 7
5.13.3 Stock standard solutions must be replaced after 1 week,
or sooner if comparison with check standards indicates a problem.
5.14 Diazomethane solution: Follow generator kit instructions. Store
in freezer in glass bottle stoppered with cork. Check for deterioration.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed; however, the bottle must not be
prerinsed with sample before collection. Composite samples should be collected
in refrigerated glass containers in accordance with the requirements of the
program. Automatic sampling equipment must be as free as possible of Tygon
and other potential sources of contamination.
6.2 The samples must be iced or refrigerated at 4° C from the time of
collection until extraction.
6.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of extraction.
7.0 Procedures
7.1 Sample preparation
7.1.1 Solid extraction
7.1.1.1 Thoroughly mix moist solids and weigh an amount of
wet sample equivalent to 50 g of dry weight into 500-ml wide-mouth
Erlenmeyer flasks.
7.1.1.2 Acidify solids with reagent grade concentrated
hydrochloric acid using 2-3 ml to pH 2. Allow to stand for 15
min with occasional stirring until the pH remains below 2. Add
more acid if necessary.
7.1.1.3 Add 20 ml of acetone to each flask containing the
acidified sample and clamp the stopper in place. Mix the contents
of the flasks for 20 min using the wrist-action shaker. Add
80 ml of redistilled ethyl ether to the same flasks and shake
again for 20 min.
7.1.1.4 Decant the extracts into 2-liter separatory
funnels containing 250 ml of 5% acidified sodium sulfate. If an
emulsion forms, slowly add 5 g of acidified sodium sulfate (anhydrous)
until the solvent-water mixture separates. A quantity of acidified
-------
8 / ORGANIC ANALYTICAL METHODS - GC
sodium sulfate equal to the weight of the sample may be added if
necessary.
7.1.1.5 To ensure adequate recovery, measure the volume of
extract into a graduated cylinder at each decanting step before
adding the extract to the separatory funnel. If the recovered
volume is not better than 75%, an additional extraction must be
conducted.
7.1.1.6 Check the pH to ensure that it remains below 2.
If the pH is not below 2, add more hydrochloric acid until stabilized.
Add 20 ml of acetone to each Erlenmeyer flask containing the
sediment and shake on the wrist-action shaker for 10 min. Again,
add 80 ml of ethyl ether, shake for 10 min and decant extract into
their respective separatory funnels. Repeat this step once more,
collecting the acetone-ether extracts in the funnels containing the
5% acidified sodium sulfate solution.
7.1.1.7 Gently mix the content of each separatory funnel
for about 1 min and allow the layers to separate. Collect the
aqueous phase in a clean beaker and the extract (top layer) in a
500-ml ground-glass Erlenmeyer flask. Reextract the water layer
with 25 ml of ethyl ether. Allow the layers to separate and
discard the aqueous layer. Combine the ether extracts in the
respective Erlenmeyer flasks.
7.1.1.8 Add 30 ml of distilled water to the extract in the
Erlenmeyer flasks and refrigerate. Note: This is a good stopping
point or, if time permits, continue to step 7.1.1.12.
7.1.1.9 Add 5 ml of 37% (w/w) aqueous potassium hydroxide
and boiling chips to the extract in the flask and fit them with a
one-ball Snyder column. Evaporate the ethyl ether on the steam
bath and continue to heat for 90 min.
7.1.1.10 Remove the flasks from the steam bath, allow them
to cool, and transfer the water solutions to 125-ml separatory
funnels. Extract the basic solutions once with 40 ml and then
twice with 20 ml of redistilled ethyl ether. Allow sufficient
time for the layers to separate, and discard the ether layer each
time. Note: This is a solvent cleanup step. The phenoxy acid
herbicides remain soluble in the aqueous phase as potassium
salts.
7.1.1.11 Add 5 ml cold 25% (v/v) sulfuric acid to the
contents of each funnel to adjust the pH to 2. Be sure to check
the pH at this point. Extract the herbicides once with 40 ml and
two more times with 20 ml of ethyl ether.
-------
8150 / 9
7.1.1.12 Collect the ether extracts in 125-ml Erlenmeyer
flasks containing 1.0 g of acidified anhydrous ^$04. Stopper
and allow the extracts to remain in contact with the acidified
Na2S04. Store the samples overnight in the refrigerator.
Note: This is a good stopping point.
7.1.1.13 Concentrate extract and perform esterification,
starting with step 7.2.2.7.
7.1.2 Liquid extraction
7.1.2.1 Mark the water meniscus on the side of the sample
bottle for later determination of sample volume. Pour the entire
sample into a 2-liter separatory funnel. Check the pH with wide-
range pH paper and adjust to pH less than 2 with sulfuric acid
(1:1).
7.1.2.2 Add 150 ml diethyl ether to the sample bottle,
seal, and shake 30 sec to rinse the walls. Transfer the solvent
into the separatory funnel. Extract the sample by shaking the
funnel for 2 min with periodic venting to release excess vapor
pressure. Allow the organic layer to separate from the water
phase for a minimum of 10 min. If the emulsion interface between
the 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, but may
include stirring, filtration of the emulsion through glass wool, or
centrifugation. Drain the water phase into a 1-liter Erlenmeyer
flask. Then collect the extract in a 250-ml ground-glass Erlenmeyer
flask containing 2 ml of 37% aqueous potassium hydroxide. Approxi-
mately 80 ml of the diethyl ether will remain dissolved in the
aqueous phase.
7.1.2.3 Extract the sample two more times using 50 ml of
diethyl ether each time. Combine the extracts in the Erlenmeyer
flask. (Rinse the 1-liter flask with each additional aliquot of
extracting solvent.)
7.1.2.4 Add 1 or 2 clean boiling chips to the 250-ml
flask, add 15 ml distilled water, and attach a three-ball Snyder
column. Prewet the Snyder column by adding 1 ml diethyl ether to
the top. Place the apparatus on a hot water bath (60° to 65° C),
such that the bottom of the flask is bathed in the water vapor.
Although the diethyl ether will evaporate in about 15 min, continue
heating for a total of 60 min, beginning from the time the flask is
placed in the water bath. Remove the apparatus and let stand at
room temperature for at least 10 min.
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10 / ORGANIC ANALYTICAL METHODS - GC
7.1.2.5 Transfer the solution to a 60-ml separatory funnel
using 5 to 10 ml of distilled water. Wash the basic solution twice
by shaking for 1 min with 20-ml portions of diethyl ether. Discard
the organic phase. The herbicides remain in the aqueous phase.
7.1.2.6 Acidify the contents of the separatory funnel to
pH 2 by adding 2 ml of cold (4° C) sulfuric acid (1:3). Test with
pH indicator paper. Add 20 ml diethyl ether and shake vigorously
for 2 min. Drain the aqueous layer into the 250-ml Erlenrneyer,
then pour the organic layer into a 125-ml Erlenmeyer containing
about 0.5 g of acidified anhydrous sodium sulfate. Repeat the
extraction twice more with 10-ml aliquots of diethyl ether, com-
bining all solvent in the 125-ml flask. Allow the extract to
remain in contact with the sodium sulfate for approximately 2 hr.
7.1.2.7 Transfer the ether extract, through a funnel
plugged with acid-washed glass wool, into a 500-ml Kuderna-Danish
flask equipped with a 10-ml concentrator tube. Use liberal washings
of ether. Use a glass rod to crush any caked sodium sulfate during
the transfer.
7.1.2.8 Add 1 to 2 clean boiling chips to the flask and
attach a three-ball Snyder column. Prewet the Snyder column by
adding about 1 ml diethyl ether to the top. Place the K-D apparatus
on a hot water bath (60° to 65° C) so that the concentrator tube is
partially immersed in the hot water, and the entire lower rounded
surface of the flask is bathed in vapor. Adjust the vertical
position of the apparatus and the water temperature as required
to complete the concentration in 15 to 20 min. At the proper rate
of distillation, the balls of the column will actively chatter but
the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow it to drain for
at least 10 min while cooling.
7.1.2.9 Remove the Snyder column and rinse the flask and
its lower joint into the concentrator tube with 1 to 2 ml of
diethyl ether. Final volume should be 4.0 ml. The sample is now
ready for derivatization with diazomethane to form methyl esters.
7.1.3 Esterification
7.1.3.1 The diazomethane derivatization (1) procedure
described below will react efficiently with all of the chlorinated
herbicides described in this method and should be used only by
experienced analysts, due to the potential hazards associated with
its use. Diazomethane is a carcinogen and can explode under
certain conditions. The following precautions should be taken:
-------
8150 / 11
• Use a safety screen.
• Use mechanical pipetting aides.
• Do not heat above 90* C - EXPLOSION may result.
• Avoid grinding surfaces, ground-glass joints, sleeve
bearings, glass stirrers - EXPLOSION may result.
• Store away from alkali metals - EXPLOSION may result.
• Solutions of diazomethane decompose rapidly in the
presence of solid materials such as copper powder,
calcium chloride, and boiling chips.
7.1.3.2 Instructions for preparing diazomethane are provided
with the generator kit.
7.1.3.3 Add 2 ml of diazomethane solution and let sample
stand for 10 min with occasional swirling.
7.1.3.4 Rinse inside wall of ampule with several hundred
u.1 of ethyl ether. Take sample to approximately 2 ml to remove
excess diazomethane by allowing solvent to evaporate spontaneously
(room temperature).
7.1.3.5 Dissolve residue in 5 ml of hexane. Analyze by
gas chromatography.
7.2 Gas chromatography conditions
7.2.1 The recommended gas chromatographic column materials and
operating conditions for the instrument are:
Parameter Column
Dicamba la,2
2,4-D la,2
2,4,5-TP la,2
2,4,5-T la,2
2,4-DB la
Dalapon 3
MCPP Ib
MCPA Ib
Dichloroprop Ib
Dinoseb Ib
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12 / ORGANIC ANALYTICAL METHODS - GC
Column la conditions: 95% Argon/5% Methane carrier gas at a flow rate
of 70 ml/min. Column temperature isothermal at 185° C.
Column Ib^temperature: 140° C for 6 min and then programmed to 200° C
at 10°/min.
Column 2 conditions: 95% Argon/5% Methane carrier gas at a flow rate
of 70 ml/min. Column temperature, isothermal at 185° C.
Column 3 conditions: UHP Nitrogen carrier gas at a flow rate of
25 ml/min. Column temperature programmed from 100° to 150° C at 10°/min.
7.2.2 The use of capillary (open-tubular) columns is acceptable
if appropriate response and separation can be demonstrated.
7.3 Calibration
7.3.1 Establish gas chromatographic operating parameters equiva-
lent to those indicated above in Table 1. The gas chromatographic
system can be calibrated using the external standard technique (Sec-
tion 7.3.2) or the internal standard technique (Section 7.3.3).
7.3.2 External standard calibration procedure
7.3.2.1 For each parameter of interest, prepare working
standards at a minimum of three concentration levels by adding
volumes of one or more stock standards to a volumetric flask and
diluting to volume with diethyl ether. One of the external standards
should be at a concentration near, but above, the method detection
limit. The other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the detector.
7.3.2.2 Prepare calibration standards from the free acids by
esterification of the working standards as described under Liquid
Extraction, Section 7.1.2. Using injections of 2 to 5 u.1 of each
esterified working standard, tabulate peak height or area responses
against the mass injected. The results can be used to prepare a
calibration curve for each parameter. Alternatively, the ratio of
the response to the mass injected, defined as the calibration .
factor (CF), can be calculated for each parameter at each standard
concentration. If the relative standard deviation of the calibration
factor is less than 10% over the working range, linearity through
the origin can be assumed and the average calibration factor can be
used in place of a calibration curve.
-------
8150 / 13
7.3.2.3 The working calibration curve or calibration factor
must be verified on each working day by the measurement of one or
more calibration standards. If the response for any parameter
varies from the predicted response by more than _+10%, the test must
be repeated using a fresh calibration standard. Alternatively,
a new calibration curve or calibration factor may be prepared for
that parameter.
7.3.3 Internal standard calibration procedure. To use this
approach, the analyst must select one or more internal standards
similar in analytical behavior to the compounds of interest. The
analyst must further demonstrate that the measurement of the
internal standard is not affected by method or matrix interferences.
Due to these limitations, no internal standard applicable to all
samples can be suggested.
7.3.3.1 Prepare working standards at a minimum of three concen-
tration levels for each parameter of interest in the acid form by
adding volumes of one or more stock standards to a volumetric
flask, and dilute to volume with diethyl ether. One of the
standards should be at a concentration near, but above, the method
detection limit. The other concentrations should correspond to
the expected range of concentrations found in real samples, or
should define the working range of the detector.
7.3.3.2 Prepare calibration standards from the free acids by
esterification of the working standards as described under Liquid
Extraction, Section 7.1.2.
7.3.3.3 Prior to injection, add a known constant amount of
one or more internal standards to each calibration standard.
7.3.3.4 Using injections of 2 to 5 u.1 of each calibration
standard, tabulate the peak height or area responses against the
concentration for each compound and internal standard. Calculate
response factors (RF) for each compound as follows:
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
Ajs = Response for the internal standard.
C-js = Concentration of the internal standard in uxj/1 •
Cs = Concentration of the parameter to be measured in u.g/1.
-------
14 / ORGANIC ANALYTICAL METHODS - GC
If the RF value over the working range is constant, less than 10%
relative standard deviation, 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 against RF.
7.3.3.5 The working calibration curve or RF must be veri-
• fied on each working day by the measurement of one or more calibra-
tion standards. If the response for any parameter varies from the
predicted response by more than +10%, the test must be repeated
using a fresh calibration standard. Alternatively, a new calibra-
tion curve must be prepared for that compound.
7.3.4 Before using any cleanup procedure, the analyst must
process a series of standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
7.4 Analysis
7.4.1 Inject 2 to 5 u.1 of the sample extract using the solvent-
flush technique. Smaller (1.0-u.l) volumes can be injected if automatic
devices are employed. Record the volume injected to the nearest
0.05 u.1, and the resulting peak size, in area units.
7.4.2 If the peak area exceeds the linear range of the system,
dilute the extract and reanalyze.
7.4.3 If peak detection is prevented by the presence of inter-
ferences, further cleanup is required. Before using any cleanup
procedure, the analyst must process a series of calibration standards
through the procedure to validate elution patterns and the absence of
interferences from the reagents.
7.4.4 Examples of chrornatograms for chlorophenoxy herbicides are
shown in Figures 1 to 3.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a distilled water method blank that all glassware and
reagents are interference-free. Each time a set of samples is extracted or
there is a change in reagents, a method blank should be processed as a
safeguard against chronic laboratory contamination.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
-------
8150 / 15
Column: 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 Mesh)
Temperature: Isothermal at 185°C
Detector: Electron Capture
0 12345
RETENTION TIME (MINUTES)
Figure 1. Gas chomatogram of chlorinated herbicides.
-------
16 / ORGANIC ANALYTICAL METHODS - GC
Column: 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 Mesh)
Program: 140°Cfor 6 Min, 10°C/Minute to 200°C
Detector: Electron Capture
CL
o
I
I
468
RETENTION TIME (MINUTES)
10
12
Figure 2. Gas chromatogram of chlorinated herbicides.
-------
8150 / 17
Column: 0.1% SP-1000 on 80/100 Mesh Carbopak C
Program: 100°C, 10°C/Min to 150°C
Detector: Electron Capture
I
JO
ra
Q
I
0246
RETENTION TIME (MINUTES)
Figure 3. Gas chromatogram of dalapon, column 3.
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18 / ORGANIC ANALYTICAL METHODS - GC
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified waste samples should be analyzed
to validate the accuracy of the analysis. Detection limits to be used for
groundwater samples are indicated in Table 1. Where doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques such as
mass spectrometry should be used (Section 8.3).
8.3 GC/MS confirmation
8.3.1 GC/MS techniques should be judiciously employed to support
qualitative identifications made with this method. The mass spectrometer
should be capable of scanning the mass range from 35 amu to a mass 50 amu
above the molecular weight of the compound. The instrument must be
capable of scanning the mass range at a rate to produce at least 5 scans
per peak but not to exceed 3 sec per scan utilizing 70 V (nominal)
electron energy in the electron impact ionization mode. A GC-to-MS
interface constructed of all-glass or glass-lined materials is recom-
mended. 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 should be
interfaced to the mass spectrometer.
8.3.2 Gas chromatographic columns and conditions should be
selected for optimum separation and performance. The conditions
selected must be compatible with standard GC/MS operating practices,
such as those described for Method 8250.
8.3.3 At the beginning of each day that confirmatory analyses are
to be performed, the GC/MS system must be checked to see that all DFTPP
(decafluorotriphenyl phosphine) performance criteria are achieved, as
described in Method 8250.
8.3.4 To confirm an identification of a compound, the background-
corrected mass spectrum of the compound must be obtained from the
sample extract and compared with a mass spectrum from a stock or
calibration standard analyzed under the same chromatographic conditions.
At least 25 ng of material should be injected into the GC/MS. The
following criteria must be met for qualitative confirmation:
1. The molecular ion and all other ions present above 10% relative
abundance in the mass spectrum of the standard must be present
in the mass spectrum of the sample with agreement to _ilO%. For
example, if the relative abundance of an ion is 30% in the mass
spectrum of the standard, the allowable limits for the relative
abundance of that ion in the mass spectrum for the sample would
be 20-40%.
-------
8150 / 19
2. The retention time of the compound in the sample must be within
6 sec of the retention time for the same compound in the
standard solution.
3. Compounds that have very similar mass spectra can be explicitly
identified by GC/MS only on the basis of retention time data.
8.3.5 Where available, chemical ionization mass spectra may be
employed to aid the qualitative identification process.
8.3.6 Should these MS procedures fail to provide satisfactory
results, additional steps may be taken before reanalysis. These steps
may include the use of alternate packed or capillary GC columns or
additional cleanup.
9.0 References
1. U.S. EPA. 1971. National Pollutant Discharge Elimination System,
Appendix A, Fed. Reg., 38, No. 75, Pt. II, Method for Chlorinated
Phenoxy Acid Herbicides in Industrial Effluents, Cincinnati, Ohio.
2. Goerlitz, D.G., and W.L. Lamar. 1967. Determination of phenoxy
acid herbicides in water by electron capture and microcoulometric
gas chromatography. U.S. Geol. Survey Water Supply Paper, 1817-C.
3. Burke, J.A., 1965. Gas chromatography for pesticide residue analysis;
some practical aspects. Journal of the Association of Official
Analytical Chemists 48:1037.
4. U.S. EPA. 1972. Extraction and cleanup procedure for the deter-
mination of phenoxy acid herbicides in sediment. EPA Toxicant and
Analysis Center, Bay St. Louis, Mississippi.
-------
8.2 Gas Chromatographic/Mass Spectroscopy Methods (8200 series)
Methods appropriate for organic analysis by GC/MS methods are included
on the following pages.
-------
METHOD 8240
GC/MS METHOD FOR VOLATILE ORGANICS
1.0 Scope and Application
1.1 Method 8240 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all
types of samples, regardless of water content, including groundwater, aqueous
sludges, caustic liquors, acid liquors, waste solvents, oily wastes, mousses,
tars, fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments.
1.2 The detection limit of Method 8240 for an individual compound is
approximately 1 u.g/g (wet weight) in waste samples. For samples containing
more than 1 mg/g of total volatile material, the detection limit is propor-
tionately higher.
1.3 Method 8240 is based upon a purge-and-trap, gas chromatographic/
mass spectrometric (GC/MS) procedure. This method is restricted to use by or
under the supervision of analysts experienced in the use of purge-and-trap
systems and gas chromatograph/mass spectrometers and skilled in the interpre-
tation of mass spectra and their use as a quantitative tool.
2.0 Summary of Method
2.1 The volatile compounds are introduced to the gas chromatograph by
direct injection, the Headspace Method (Method 5020), or the Purge-and-Trap
Method (Method 5030). Method 5030 should be used for groundwater analysis.
The components are separated via the gas chromatograph and detected using a
mass spectrometer which is used to provide both qualitative and quantitative
information. The chromatographic conditions as well as typical mass spec-
trometer operating parameters are given.
2.2 If the above sample introduction techniques are not applicable,
a portion of the sample can be dispersed in methanol or polyethylene glycol
(PEG) to dissolve the volatile organic constituents. A portion of the
methanolic or PEG solution is combined with water in a specially designed
purging chamber. An inert gas is then bubbled through the solution at
ambient temperature and the volatile comnponents are efficiently transferred
from the aqueous phase to the vapor phase. The vapor is swept through a
sorbent column where the volatile components are trapped. After purging is
completed, the sorbent column is heated and backflushed with inert gas to
desorb the components onto a gas chromatographic column. The gas chroma-
tographic column is heated to elute the components, which are detected with a
mass spectrometer.
2.3 An aliquot of each sample must be spiked with an appropriate
standard to determine percent recovery and detection limits for that sample.
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2 / ORGANIC ANALYTICAL METHODS - GC/MS
2.4 Table 1 lists detection limits that can be obtained in wastewaters
in the absence of interferences. Detection limits for a typical waste sample
would be significantly higher.
TABLE 1. CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Parameter
Retention time
(min)
Column la
Method
detection limit
(ug/1)
Chloromethane 2.3 ND
Bromomethane 3.1 ND
Vinyl chloride 3.8 ND
Chloroethane 4.6 ND
Methylene chloride 6.4 2.8
Trichlorofluoromethane 8.3 ND
1,1-Dichloroethene 9.0 2.8
1,1-Dichloroethane 10.1 4.7
trans-l,2-Dichloroethene 10.8 1.6
Chloroform 11.4 1.6
1,2-Dichloroethane 12.1 2.8
1,1,1-Trichloroethane 13.4 3.8
Carbon tetrachloride 13.7 2.8
Bromodichloromethane 14.3 2.2
1,2-Dichloropropane 15.7 6.0
trans-l,3-Dichloropropene 15.9 5.0
Trichloroethene 16.5 1.9
Benzene 17.0 4.4
Dibromochloromethane 17.1 3.1
1,1,2-Trichloroethane 17.2 5.0
cis-l,3-Dichloropropene 17.2 ND
2-Chloroethylvinyl ether 18.6 ND
Bromoform 19.8 4.7
1,1,2,2-Tetrachloroethane 22.1 6.9
Tetrachloroethene 22.2 4.1
Toluene 23.5 6.0
Chlorobenzene 24.6 6.0
Ethyl benzene 26.4 7.2
1,3-Dichlorobenzene 33.9 ND
1,2-Dichlorobenzene 35.0 ND
1,4-Dichlorobenzene 35.4 ND
ND = not determined.
aColumn conditions: Carbopack B (60/80 mesh) coated with
1% SP-1000 packed in a 6-ft by 2-mm I.D. glass column with helium
carrier gas at a flow rate of 30 ml/min. Column temperature is
isothermal at 45° C for 3 min, then programmed at 8° C per minute
to 220" and held for 15 min.
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8240 / 3
3.0 Interferences
3.1 Interferences coextracted from the samples will vary considerably
from source to source, depending upon the particular waste or extract being
tested. The analytical system, however, should be checked to ensure
freedom from interferences under the conditions of the analysis by running
method blanks. Method blanks are run by analyzing organic-free water in the
normal manner. The use of non-TFE plastic tubing, 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) through the septum seal into the sample
during shipment and storage. A field blank prepared from organic-free water
and carried through the sampling and handling protocol can serve as a check
on such contamination.
3.3 Cross contamination can occur whenever high-level and low-level
samples are sequentially analyzed. To reduce cross contamination, the
purging device and sample syringe should be rinsed out twice, between samples,
with organic-free water. Whenever an unusually concentrated sample is
encountered, it should be followed by an analysis of organic-free water to
check for cross contamination. For samples containing large amounts of
water-soluble materials, suspended solids, high boiling compounds, or high
organohalide levels, it may be necessary to wash out the purging device with
a soap solution, rinse with distilled water, and then dry in a 105° C oven
between analyses.
3.4 Low molecular weight impurities in PEG can be volatilized during
the purging procedure. Thus, the PEG employed in this method must be puri-
fied before use as described in Section 5.2.
4.0 Apparatus and Materials
4.1 Sampling equipment
4.1.1 Vial: 25-ml capacity or larger, equipped with a screw cap
(Pierce #13075 or equivalent). Detergent wash, rinse with tap and
distilled water, and dry for 1 hr at 105° C before use.
4.1.2 Septum: Teflon-faced silicone (Pierce #12722 or equivalent).
Detergent wash, rinse with tap and distilled water and dry at 105* C for
1 hr before use.
4.2 Purge-and-trap device: The purge-and-trap device consists of
three separate pieces of equipment: the purging chamber, trap, and the
desorber. Several complete devices are now commercially available.
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4 / ORGANIC ANALYTICAL METHODS - GC/MS
4.2.1 The purging chamber must be designed to accept 5-ml or
25-ml samples with a water column at least 3 cm deep. The gaseous head
space 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 purging chamber, illustrated in Figure 1, meets
these design criteria.
4.2.2 The trap must be at least 25 cm long and have an inside
diameter of at least 2.5 mm. The trap must be packed to contain the
following minimum lengths-of-adsorbents: 1.0 cm of methyl-silicone-
coated packing (Section 5.3.2), 15 cm of 2,6-diphenylene oxide polymer
(Section 5.3.1), and 8 cm of silica gel (Section 5.3.3). The minimum
specifications for the trap are illustrated in Figure 2.
4.2.3 The desorber must be capable of rapidly heating the trap
to 180* C within 30 sec. The polymer section of the trap should
not be heated higher than 180* C and the remaining sections should not
exceed 220° C. The desorber design, illustrated in Figure 2, meets
these criteria.
4.2.4 The purge-and-trap device may be assembled as a separate
unit or be coupled to a gas chromatograph as illustrated in Figures 3
and 4.
4.3 Gas chromatograph/mass spectrometer system
4.3.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases.
4.3.2 Column: 2-m x 2-mm I.D. stainless steel or glass, packed
with 1% SP-1000 on 60/80 mesh Carbopack B or equivalent.
4.3.3 Mass spectrometer: Capable of scanning from 40 to 250 amu
every 3 sec or less, utilizing 70 volts (nominal) electron energy
in the electron impact ionization mode and producing a mass spectrum
which meets all the criteria in Table 1 when 50 ng of 4-bromofluoro-
benzene (BFB) is injected through the GC inlet or introduced in the
purge-and-trap mode.
4.3.4 GC/MS interface: Any GC-to-MS interface that gives
acceptable calibration points at 50 ng per injection for each compound
of interest and achieves acceptable tuning performance criteria (see
Section 9) may be used. GC-to-MS interfaces constructed of all glass
or glass-lined materials are recommended. Glass can be deactivated by
silanizing with dichlorodimethylsilane. The interface must be capable
of transporting at least 10 ng of the components of interest from the
GC to the MS.
-------
8240 / 5
OPTIONAL
FOAM TRAP
Exit 1/4 Inch O. D.
14 mm 0. D.
Inlet % Inch 0. D.
11
I I
I I
I I
/ I
I 1
11
I I
I I
% Inch 0. D. Exit
10 mm Glass Frit
Medium Porosity
«£
Sample Inlet
2-Way Syringe Valve
17 cm, 20 Gauge Syringe Needle
6 mm 0. D. Rubber Septum
10 mm O. D.
Inlet
'/». Inch 0. D.
1/16 InchO. D.
Stainless Steel
13x Molecular
Sieve Purge
Gas Filter
Purge Gas
Flow Control
Figure 1. Purging chamber.
-------
6 / ORGANIC ANALYTICAL METHODS - GC/MS
Packing Procedure
Construction
Glass Wool 5 mm
Grade 15 j
Silica Gel 8cm
Tenax 15cm
3% OV-1
Glass Wool
1 cnV
5 mm
I
Compression
Fitting Nut
and Ferrules
14 Ft. 7^/Foot
Resistance Wire
Wrapped Solid
Thermocouple/
Controller
Sensor
Electronic
Temperature-
Control and
Pyrometer
Tubing 25 cm
0.105 In. I.D.
0.125 In.O.D.
Stainless Steel
Trap Inlet
Figure 2. Trap packings and construction to include desorb capability.
-------
8240 / 7
CARRIER GAS FLOW CONTROL
PRESSURE REGULATOR
UOUIO INJECTION PORTS
\
PURGE GAS v _ ,
R.OW CONTROL \"~tj
COLUMN OVEN
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
1M MOLECULAR —
SiEVE FILTER
OPTIONAL 4—POUT COLUMN
SELECTION VALVE
TRAP INLET
/ RESISTANCE WIRE
HEATER CONTROL
r v
TRAP
PURGING
OEVICS-
No(«:AU. UNE5 BETWEEN
TRAP AND GC
SHOULD S£ HEATED
TO aox
FIGURE 3. Schematic of purge and trap device - purge mode
CAS81EH GAS
FLOW CONTTOL
PURG2 GAS
FLOW CONTROL , ,
MOLECULAR ^
SIEVE RLTE3
'//
UQUIO INJECTION PORTS
/ ,-COLUMN OVEN
\OPT10NAL
sascnoN VALVE
TRAP INLET
RESISTANCE WIRE
CONFIRMATORY COLUMN
DETECTOR
ANALYTICAL COLUMN
COLUMN
HEATHS
CONTROL
Note:
ALL UNE5 BETWEEN
PURGING TRAP AND GC
DEVICE SHOULD BE HEATED
TO 35CC.
Figure 4. Schematic of purge and trap device - desoro mode
-------
8 / ORGANIC ANALYTICAL METHODS - GC/MS
4.3.5 Data system: A computer system must be interfaced to the
mass spectrometer that allows the continuous acquisition and storage on
machine-readable media of all mass spectra obtained throughout the
duration of the chromatographic program. The computer must have
software that allows searching any GC/MS data file for ions of a
specific 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 integrat-
ing the abundance in any EICP between specified time or scan number
limits. Hardware and software must be available to transform the data
into a compatible format. These generally consist of a 9-inch, 800-bpi
tape drive and the associated software.
4.4 Sample transfer implements: Implements are required to transfer
portions of solid, semisolid, and liquid wastes from sample containers to
laboratory glassware. The transfer must be accomplished rapidly to avoid
loss of volatile components during the transfer step. Liquids may be trans-
ferred using a hypodermic syringe with a wide-bore needle or no needle
attached. Samples should be introduced into the syringe by (1) removing
the plunger from the syringe, (2) pouring the sample into the barrel, and
(3) replacing the barrel and inverting the syringe to remove any air trapped
in the syringe. Do not draw the sample up into the syringe. Solids may be
transferred using a conventional laboratory spatula, spoon, or coring device.
A coring device that is suitable for handling some samples can be made by
using a glass tubing saw to cut away the closed end of the barrel of a glass
hypodermic syringe.
TABLE 2. BFB KEY ION ABUNDANCE CRITERIA
Mass Ion abundance criteria
50
75
95
96
173
174
175
176
177
15 to 40% of mass 95
30 to 60% of mass 95
Base Peak, 100% Relative
5 to 9% of mass 95
less than 2% of mass 174
greater than 50% of mass
5 to 9% of mass 174
greater than 95% but less
of mass 174
5 to 9% of mass 176
Abundance
95
than 100%
-------
8240 / 9
4.5 Syringes: 5-ml and 25-ml glass hypodermic, equipped with 20-gauge
needle, at least 15 cm in length.
4.6 Micro syringes: 10-ul, 25-ul, 100-ul, 250-ul, and 1000-ul. These
syringes should be equipped with 20-gauge needles having a length sufficient
to extend from the sample inlet to within 1 cm of the glass frit in the
purging device (see Figure 1). The needle length required will depend upon
the dimensions of the purging device employed.
4.7 Centrifuge tubes: 50-ml round-bottom glass centrifuge tubes with
Teflon-lined screw caps. The tubes must be marked before use to show an
approximate 20-ml graduation.
4.8 Centrifuge: Capable of accommodating 50-ml glass tubes.
4.9 Syringe valve: 2-way, with Luer ends (2 each) (Hamilton #86725
valve equipped with one Hamilton #35033 Luer fitting, or equivalent).
4.10 Syringe: 5-ml, gas-tight with shut-off valve.
4.11 Bottle: 15-ml, screw-cap, Teflon cap liner.
4.12 Balance: Analytical, capable of accurately weighing 0.0001 g.
4.13 Rotary evaporator: equipped with Teflon-coated seals (Buchi
Rotavapor R-110, or equivalent).
4.14 Vacuum pump: mechanical, two-stage.
5.0 Reagents
5.1 Reagent water: Reagent water is defined as a water in which an
interferent is not observed at the method detection limit of the compounds of
interest.
5.1.1 Reagent water may be generated by passing tap water through
a carbon filter bed containing about 500 g of activated carbon (Calgon
Corp., Filtrasorb-300, or equivalent).
5.1.2 A water purification system (Millipore Super-Q or equiva-
lent) may be used to generate reagent water.
5.1.3 Reagent water may also be prepared by boiling water for
15 min. Subsequently, while maintaining the temperature at 90° C,
bubble a contaminant-free inert gas through the water for 1 hr.
While still hot, transfer the water to a narrow-mouth screw-cap bottle
and seal with a Teflon-lined septum and cap.
-------
10 / ORGANIC ANALYTICAL METHODS - GC/MS
5.1.4 Reagent water may also be purchased under the name "HPLC
water" from several manufacturers (Burdick and Jackson, Baker and
Waters, Inc.).
5.2 Reagent PEG: Reagent PEG is defined as PEG having a nominal
average molecular weight of 400, and in which interferents are not observed
at the method detection limit for compounds of interest.
5.2.1 Reagent PEG is prepared by purification of commercial PEG
having a nominal average molecular weight of 400. The PEG 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 in a
water bath at 90-100° C and vacuum is maintained at less than 10 mm Hg
for at least 1 hr 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.
5.2.2 In order to demonstrate that all interfering volatiles
have been removed from the PEG, a reagent water/PEG blank must be
analyzed.
5.3 Trap materials
5.3.1 2,6-Diphenylene oxide polymer: 60/80-mesh Tenax, chromato-
graphic grade or equivalent.
5.3.2 Methyl silicone packing: 3 percent OV-1 on 60/80 mesh
Chromosorb-W or equivalent.
5.3.3 Silica gel, Davison Chemical (35/60 mesh), grade-15 or
equivalent.
5.3.4 Prepared trapping columns may be purchased from several
chromatography suppliers.
5.4 Methanol: Distilled-in-glass quality or equivalent.
5.5 Calibration standards; stock solutions (2 mg/ml): Stock solu-
tions of calibration standards may be prepared from pure standard materials
or purchased as certified solutions. Prepare stock standard solutions of
individual compounds in methanol using assayed liquids or gases as appro-
priate. 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 gas respirator should be worn by analysts when handling high
concentrations of these materials.
5.5.1 Place about 9.8 ml of methanol in a 10-ml ground-glass-
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 min or until all alcohol-wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
-------
8240 / 11
5.5.2 Add the assayed reference material as described below.
5.5.2.1 Liquids: Using a 100-uT syringe, immediately add
2 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.
5.5.2.2 Gases: To prepare standards for any compounds
that boil below 30" C (e.g., bromomethane, chloroethane, chloro-
methane, or vinyl chloride), fill a 5-ml valved gas-tight syringe
with a reference standard to the 5.0-ml mark. Lower the needle to
5 mm above the methanol meniscus. Slowly introduce the reference
standard above the surface of the liquid. The heavy gas rapidly
dissolves in the methanol.
5.5.3 Reweigh, dilute to volume, stopper, then mix by gently
inverting the flask several times. Calculate the concentration in
ug/ul per microliter from the net gain in weight. When compound
purity is assayed to be 96% or greater, the weight may be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards may be used at any concentration
if they are certified by the manufacturer or by an independent source.
5.5.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at -10 to -20° C and
protect from light.
5.5.5 Prepare fresh standards weekly for gases or for reactive
compounds such as 2-chloroethylvinyl ether. All other standards must
be replaced after one month, or sooner if comparison with check
standards indicates a problem.
5.6 Calibration standards; secondary dilution solutions: Using stock
solutions described in Section 5.5, prepare secondary dilution standards in
methanol that contain the compounds of interest, either singly or mixed
together. The secondary dilution standards should be prepared at concentra-
tions such that the methanol or aqueous PEG calibration solutions prepared as
described in Section 6.3.2 will bracket the working range of the analytical
system. Secondary dilution standards should be stored with minimal headspace
and should be checked frequently for signs of evaporation, especially just
prior to preparing calibration standards from them.
5.7 Surrogate standards: Surrogate standards may be added to samples
and calibration solutions to assess the effect of the sample matrix on
recovery efficiency. The compounds employed for this purpose are 1,2-
dibromotetrafluoroethane, bis(perfluoroisopropyl) ketone, fluorobenzene,
and m-bromobenzotrifluoride. Prepare methanolic solutions of the surrogate
standards using the procedures described in Sections 5.5 and 5.6. The
-------
12 / ORGANIC ANALYTICAL METHODS - GC/MS
concentrations prepared and the amount of solution added to each sample
should be those required to give an amount of each surrogate in the purging
device that is equal to the amount of each internal standard added, assuming
a 100% recovery of the surrogate standards.
5.8 Internal standards: In this method, internal standards are
employed during analysis of all samples and during all calibration procedures
The analyst must select one or more internal standards that are similar in
analytical behavior to the compounds of interest. The analyst must further
demonstrate that the measurement of the internal standard is not affected by
method or matrix interferences. Because of these limitations, no internal
standard can be suggested that is applicable to all samples. However, for
general use, D4-l,2-dichloroethane, Ds-benzene, and Ds-ethyl benzene are
recommended as internal standards covering a wide boiling point range.
5.9 4-Bromofluorobenzene (BFB): BFB is added to the internal standard
solution or analyzed alone to permit the mass spectrometer tuning for each
GC/MS run to be checked.
5.10 Internal standard solution: Using the procedures described in
Sections 5.5 and 5.6, prepare a methanolic solution containing each internal
standard at a concentration of 12.5
5.11 Sodium monohydrogen phosphate: 2.0 \i in distilled water.
5.12 n-Nonane and n-dodecane, 98+% purity.
5.13 N-Hexadecane, distil led-in-glass (Burdick and Jackson, or
equivalent).
6.0 Sample Collection, Handling, and Preservation
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Section One of this manual.
6.2 All samples must be stored in Teflon-lined screw cap vials. Sample
containers should be filled as completely as possible so as to minimize
headspace or void space. Vials containing liquid sample should be stored in
an inverted position.
6.3 All samples must be iced or refrigerated from the time of collection
to the time of analysis, and should be protected from light.
-------
8240 / 13
7.0 Procedure
7.1 Calibration
7.1.1 Assemble a purge-and-trap device that meets the specifications
in Section 4.2 and connect the device to a GC/MS system. Condition the
trap overnight at 180° C by backflushing 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.
7.1.2 Operate the gas chromatograph using the conditions described
in Section 7.3.5 and operate the mass spectrometer using the conditions
described in Section 7.3.2.
7.1.3 Calibration procedure
7.1.3.1 Conduct calibration procedures using a minimum of
three concentration levels for each calibration standard. One of
the concentration levels should be at a concentration near but
above the method detection limit. The remaining two concentration
levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the
GC/MS system.
7.1.3.2 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate
standards, directly in the purging device. To the purging device,
add 5.0 ml of reagent water or reagent water/PEG solution. This
solution is prepared by taking 4.0 ml of reagent water or reagent
PEG and diluting to 100 ml with reagent water. The reagent water/
PEG solution 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 in-
sertion of a 20-gauge needle. Next, using a 10-ul or 25-ul micro-
syringe equipped with a long needle (see Section 4.6), take a
volume of the secondary dilution solution containing appropriate
concentrations of the calibration standards (see Section 5.6). Add
the aliquot of calibration solution directly to the reagent water
or reagent water/PEG solution 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 reagent water or water/PEG solu-
tion. Similarly, add 20 u.1 of the internal standard solution (see
Section 5.10). Close the 2-way syringe valve at the sample inlet.
7.1.3.3 Carry out the purge and analysis procedure as
described in Section 7.3.4. Tabulate the area response of the
primary characteristic ion against concentration for each compound
-------
14 / ORGANIC ANALYTICAL METHODS - GC/MS
including the internal standards.
for each compound as follows:
Calculate response factors (RF)
= (AsCis)/AisCs)
where:
As = Area of the primary characteristic ion for the compound
to be measured
AJS = Area of the primary characteristic ion of the internal
standard
'IS
= Concentration of the internal standard
Cs = Concentration of the compound to be measured.
The internal standard selected for the calculation of the RF of a
compound and subsequent quantification of the compound is generally
the internal standard that has a retention time closest to that of
the compound. It is assumed that a linear calibration plot will be
obtained over the range of concentrations used. If the RF value
over the working range is a constant (less than 10% relative
standard deviation), 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.
7.1.3.4 The RF must be verified on each working day. The
concentrations selected should be near the midpoint of the working
range. The response factors obtained for the calibration standards
analyzed immediately before and after a set of samples must be
within +20% of the response factor used for quantification of the
sample concentrations.
7.2 Daily GC/MS performance tests
7.2.1 At the beginning of each day that analyses are to be performed,
the GC/MS system must be checked to see that acceptable performance
criteria are achieved for BFB (see Table 2).
7.2.2 The BFB performance test requires the following instrumental
parameters:
Electron Energy:
Mass Range:
Scan Time:
70 volts (nominal)
40 to 250 amu
to give approximately 6 scans per peak but not
to exceed 3 sec per scan.
-------
8240 / 15
7.2.3 Bleed BFB vapor into the mass spectrometer and tune the
instrument to achieve all the key ion criteria for the mass spectrum of
BFB given in Table 1. A solution containing 20 ng of BFB may be injected
onto the gas chromatographic column in order to check the key ion
criteria.
7.2.4 The peak intensity of D6-benzene is used to monitor the mass
spectrometer sensitivity. The peak intensity for Ds-benzene observed
during each sample analysis must be between 0.7 and 1.4 times the D5-benzene
peak intensity observed during the applicable calibration runs. For example,
if the peak intensity of Ds-benzene observed during calibration was 355,000
area counts, then each subsequent sample or blank must give a Ds-benzene
peak intensity of between 250,000 and 500,000 area counts. If the Ds-benzene
peak intensity is outside the specified range, the sample must be reanalyzed.
If the peak intensity is again outside the specified range, the analyst must
investigate the cause of the variability in sensitivity and correct the
problem.
7.3 Sample extraction and analysis
7.3.1 The analytical procedure involves extracting the non-aqueous
sample with methanol or polyethylene glycol (PEG) and analyzing a
portion of the extract by a purge-and-trap GC/MS procedure. The amount
of the extract to be taken for the GC/MS analysis is based on the
estimated total volatile content (TVC) of the sample. The TVC is
estimated by extracting the sample with n-hexadecane and analyzing the
n-hexadecane extract by gas chromatography.
7.3.2 The estimated TVC is based on the total area response
relative to that of n-nonane for all components eluting prior to the
retention time of n-dodecane. The response factor for n-nonane and the
retention time of n-dodecane are determined by analyzing a 2-u.l aliquot
of an n-hexadecane solution containing 0.20 mg/ml of n-nonane and
n-dodecane.
7.3.2.1 The GC analyses are conducted using a flame ioniza-
tion detector and a 3-m x 2-mm I.D. glass column packed with 10%
OV-101 on 100-200 mesh Chromosorb W-HP. The column temperature is
programmed from 80° C to 280* C at 8°/min and held at 280° for
10 min.
7.3.2.2 Determine the area response for n-nonane and divide
by 0.2 to obtain the area response factor. Record the retention
time of n-dodecane.
7.3.2.3 Add 1.0 g of sample to 20 ml of n-hexadecane and
2 ml of 2.0 M Na2HP04 contained in a 50-ml glass centrifuge
tube and cap securely with a Teflon-lined screw cap. Shake the
mixture vigorously for one minute. If the sample does not disperse
-------
16 / ORGANIC ANALYTICAL METHODS - GC/MS
during the shaking process, sonify the mixture in an ultrasonic
bath for 30 min. Allow the mixture to stand until a clear
supernatant is obtained. Centrifuge if necessary to facilitate
phase separation.
7.3.2.4 Analyze a 2-u.l aliquot of the n-hexadecane super-
natant using the conditions described in Section 7.3.2.1. Determine
the total area response of all components eluting prior to the
retention time of n-dodecane and subtract the corresponding area of
an n-hexadecane blank. Using the area response factor determined
for n-nonane in Section 7.3.2.2, calculate the TVC as follows:
TVC = TARsample " TARblank x 2Q
n-Nonane Area Response Factor
where:
TVC = total volatile content of the sample in mg/g
TARsamp]e = total area response obtained for the sample
TARblank = total area response obtained for a blank.
7.3.3 The transfer of an aliquot of the sample for extraction
with methanol or PEG should be made as quickly as possible to minimize
loss of volatiles from the sample.
7.3.3.1 To a 50-ml glass centrifuge tube with Teflon-lined
cap, add 40 ml of reagent methanol or PEG. Weigh the capped
centrifuge tube and methanol or PEG on an analytical balance.
7.3.3.2 Using an appropriate implement (see Section 4.4),
transfer approximately 2 g of sample to the methanol or PEG in the
centrifuge tube in such a fashion that the sample is dissolved in
or submerged in the methanol or PEG as quickly as possible. Take
care not to touch the sample-transfer implement to the methanol or
PEG. Recap the centrifuge tube immediately and weigh on an analytical
balance to determine an accurate sample weight.
7.3.3.3 Disperse the sample by vigorous agitation for 1 min.
The mixture may be agitated manually or with the aid of a vortex-mixer.
If the sample does not disperse during this process, sonify the
mixture in an ultrasonic bath for 30 min. Allow the mixture to
stand until a clear supernatant is obtained as the sample extract.
Centrifuge if necessary to facilitate phase separation.
-------
8240 / 17
7.3.3.4 The sample extract may be stored for future analytical
needs. If this is desired, transfer the solution to a 10-ml screw
cap vial with Teflon cap liner. Store at -10 to -20° C, and protect
from light.
7.3.4 Reagent water, internal standard solution, and the sample
extract are added to a purging chamber that is connected to the purge-and-
trap device and that has been flushed with helium during a 7-min trap
reconditioning step (see Section 7.3.4.4). The additions are made using
an appropriately sized syringe equipped with a 15-cm 20-gauge needle.
Open the syringe valve of the sample inlet (shown in Figure 1) and
insert the needle through the valve.
7.3.4.1 Add 5.0 ml of reagent water or aqueous sample to
which 20.0 ul of the internal standard solution has been added (see
Section 5.10) to the purging chamber. Insert the needle of the
syringe well below the surface of the water for the addition of
the internal standard solution. If the sample is aqueous go to
Section 7.3.5.
7.3.4.2 Add an aliquot of the sample extract from Section
7.3.3.4. The total quantity of volatile components injected should
not exceed approximately 10 ug. If the total volatile content
(TVC) of the sample as determined in Section 7.3.1.4 is 1.0 mg/g or
less, use a 200-ul aliquot of the sample extract. If the TVC is
greater than 1.0 mg/g, use an aliquot of the sample extract that
contains approximately 10 ug of total volatile components; the
volume (in ul) of the aliquot to be taken can be calculated by
dividing 200 by the TVC. If the TVC is greater than 20 mg/g, take
a 500-ul aliquot of the sample extract and dilute to 10 ml with
PEG. In this case calculate the aliquot volume (in ul) of the
undiluted extract to be taken by dividing 4,000 by the TVC. If the
TVC is less than 1.0 mg/g and greater sensitivity is desired, use a
large purging chamber containing 25 ml of reagent water and use a
1.0-ml aliquot of the sample extract.
7.3.4.3 Close the 2-way syringe valve at the sample inlet.
7.3.5 The sample in the purging chamber is purged with helium to
transfer the volatile components to the trap. The trap is then heated
to desorb the volatile components which are swept by the helium carrier
gas onto the GC column for analysis.
7.3.5.1 Adjust the gas (helium) flow rate to 40 +_ 3 ml/min.
Set the purging device to purge, and purge the sample for
11.0 +_ 0.1 min at ambient temperature.
-------
18 / ORGANIC ANALYTICAL METHODS - GC/MS
7.3.5.2 At the conclusion of the purge time, adjust the
device to the desorb mode, and begin the GC/MS analysis and data
acquisition using the following GC operating conditions:
Column: 6-ft x 2-mm I.D. glass column of 1% SP-1000 on
Carbo-pack B (60-80 mesh).
Temperature: Isothermal at 45" C for 3 min, then increased at
8* C/min to 220* C, and maintained at 220* C for 15 min.
Concurrently, introduce the trapped materials to the GC column by
rapidly heating the trap to 180* C while backflushing the trap with
helium at a flow rate of 30 ml/min for 4 min. If this rapid
heating requirement cannot be met, the GC column must be used as a
secondary trap by cooling it to 30* C or lower during the 4-min
desorb step and starting the GC program after the desorb step.
7.3.5.3 Return the purge-and-trap device to the purge mode
and continue acquiring GC/MS data.
7.3.5.4 Allow the trap to cool for 8 min. Replace the
purging chamber with a clean purging chamber. The purging chamber
is cleaned after each use by sequential washing with acetone,
methanol, detergent solution and distilled water, and then dried
at 105* C.
7.3.5.5 Close the syringe valve on the purging chamber
after 15 sec to begin gas flow through the trap. Purge the trap at
ambient temperature for 4 min. Recondition the trap by heating it
to 180* C. Do not allow the trap temperature to exceed 180" C,
since the sorption/desorption is adversely affected when the trap
is heated to higher temperatures. After heating the trap for
approximately 7 min, turn off the trap heater. When cool, the trap
is ready for the next sample.
7.3.6 If the response for any ion exceeds the working range of the
system, repeat the analysis using a correspondingly smaller aliquot of
the sample extract described in Section 7.3.2.3.
7.4 Qualitative identification
7.4.1 Obtain an EICP for the primary characteristic ion and at
least two other characteristic ions for each compound when practical.
The following criteria must be met to make a qualitative identification.
7.4.1.1 The characteristic ions of each compound of interest
must maximize in the same or within one scan of each other.
-------
8240 / 19
7.4.1.2 The retention time must fall within +30 sec of the
retention time of the authentic compound.
7.4.1.3 The relative peak heights of the characteristic
ions in the EICP's must fall within +20% of the relative intensities
of these ions in a reference mass spectrum. Reference spectra may
be generated from the standards analyzed by the analyst or from a
reference library. All reference spectra generated from standards
must be obtained from an appropriately tuned mass spectrometer.
7.5 Quantitative determination
7.5.1 When a compound has been identified, the quantification of
that compound will be based on the integrated abundance from the EICP of
the primary characteristic ion. In general, the primary characteristic
ion selected should be a relatively intense ion, as interference-free as
possible, and as close as possible in mass to the characteristic ion of
the internal standard used. Generally, the base peak of the mass
spectrum is used.
8.0 Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and the analysis
of spiked samples as a continuing check on performance. The laboratory is
required to maintain performance records to define the quality of the data
that are generated. Ongoing performance checks must be compared with
established performance criteria to determine if the results of analyses are
within the accuracy and precision limits expected of the method.
8.1.1 Before performing any analyses, the analyst must demon-
strate the ability to generate acceptable accuracy and precision with
this method. This ability is established as described in Section 8.2.
8.1.2 The laboratory must spike all samples including check
samples with surrogate standards to monitor continuing laboratory
performance. This procedure is described in Section 8.4.
8.1.3 Before processing any samples, the analyst should daily
demonstrate, through the analysis of an organic-free water method blank,
that the entire analytical system is interference-free. The blank
samples should be carried through all stages of the sample preparation
and measurement steps.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations using a
representative sample as a check sample.
-------
20 / ORGANIC ANALYTICAL METHODS - GC/MS
8.2.1 Analyze four aliquots of the unspiked check sample
according to the method in Section 7.3.
8.2.2 For each compound to be measured, select a spike
concentration representative of twice the level found in the unspiked
check sample or a level equal to 10 times the expected detection limit,
whichever is greater. Prepare a spiking solution by dissolving the
compounds in methanol at the appropriate levels.
8.2.3 Spike a minimum of four aliquots of the check sample with
the spiking solution to achieve the selected spike concentrations.
Spike the samples by adding the spiking solution to the PEG used for
the extraction. Analyze the spiked aliquots according to the method in
Section 7.3.
8.2.4 Calculate the average percent recovery, R, and the
standard deviation of the percent recovery, s, for all compounds and
surrogate standards. Background corrections must be made before R and
s calculations are performed. The average percent recovery must be
greater than 20 for all compounds to be measured and greater than 60
for all surrogate compounds. The percent relative standard deviation
of the percent recovery, s/R x 100, must be less than 20 for all
compounds to be measured and all surrogate compounds.
8.3 The analyst must calculate method performance criteria for each
of the surrogate standards.
8.3.1 Calculate upper and lower control limits for method
performance for each surrogate standard, using the values for R and s
calculated in Section 8.2.4:
Upper Control Limit (UCL) = R + 3s
Lower Control Limit (LCL) = R - 3s
The UCL and LCL can be used to construct control charts that are useful
in observing trends in performance.
8.3.2 For each surrogate standard, the laboratory must maintain
a record of the R and s values obtained for each surrogate standard in
each waste sample analyzed. An accuracy statement should be prepared
from these data and updated regularly.
8.4 The laboratory is required to spike all samples with the surrogate
standards to monitor spike recoveries. The spiking level used should be that
which will give an amount in the purge apparatus that is equal to the amount
of the internal standard assuming a 100% recovery of the surrogate standards.
If the recovery for any surrogate standard does not fall within the control
limits for method performance, the results reported for that sample must be
-------
8240 / 21
qualified as being outside of control limits. The laboratory must monitor
the frequency of data so qualified to ensure that it remains at or below 5%.
Four surrogate standards, namely 1,2-dibromodifluoroethane, bis(perfluoro-
isopropyl) ether, fluorobenzene, and m-bromobenzotrifluoride, are recommended
for general use to monitor recovery of volatile compounds varying in volatility
and polarity.
8.5 Each day, the analyst must demonstrate through the analysis of a
process blank that all glassware and reagent interferences are under control.
8.6 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. Field replicates may be analyzed to monitor the precision of
the sampling technique. Whenever possible, the laboratory should perform
analysis of standard reference materials and participate in relevant per-
formance evaluation studies.
8.7 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed
to validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 ug/g of sample, then the sensitivity of the instrument should be
increased or the extract subjected to additional cleanup. Detection limits
to be used for groundwater samples are indicated in Table 1. Where doubt
exists over the identification of a peak on the chromatograph, confirmatory
techniques such as mass spectroscopy should be used.
8.8 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.9 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 3
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 3.
-------
22 / ORGANIC ANALYTICAL METHODS - GC/MS
TABLE 3. ACCURACY AND PRECISION FOR PURGEABLE ORGANICS
Reagent Water
Parameter
Benzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Dibromochloromethane
1,1-Di chloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Average
percent
recovery
99
102
104
100
102
100
97
101
101
99
103
101
100
102
99
102
105
104
100
96
102
101
101
101
101
101
103
100
Standard
deviation
(%)
9
12
14
20
16
7
22
13
10
19
11
10
8
17
12
8
15
11
8
16
9
9
9
11
10
9
11
13
Wastewater
Average
percent
recovery
98
103
105
88
104
102
103
95
101
99
104
104
102
99
101
103
102
100
103
89
104
100
98
102
104
100
107
98
Standard
deviation
(%)
10
10
16
23
15
9
31
17
12
24
14
15
10
15
10
12
19
18
10
28
14
11
14
16
15
12
19
25
Samples were spiked between 10 and 1000
-------
METHOD 8250
GC/MS METHOD FOR SEMIVOLATILE ORGANICS:
PACKED COLUMN TECHNIQUE
1.0 Scope and Application
1.1 Method 8250 is used to determine the concentration of semi volatile
organic compounds (see Tables 1 and 2) in a variety of solid waste matrices.
1.2 This method is applicable to nearly all types of samples, regard-
less of water content, including groundwater, aqueous sludges, caustic
liquors, acid liquors, waste solvents, oily wastes, mousses, tars, fibrous
wastes, polymeric emulsions, filter cakes, spent carbons, spent catalysts,
soils, and sediments.
1.3 Method 8250 can be used to quantify most neutral, acidic, and basic
organic compunds that are soluble in methylene chloride and capable of being
eluted without derivatization as sharp peaks from a gas chromatographic
column. Such compounds include polynuclear aromatic hydrocarbons, chlori-
nated hydrocarbons and pesticides, phthalate esters, organophosphate esters,
nitrosamines, haloethers, aldehydes, ethers, ketones, anilines, pyridines,
quinolines, aromatic nitro compounds, and phenols, including nitrophenols.
1.4 The detection limit of Method 8250 for determining an individual
compound is approximately 1 ug/g (wet weight) in waste samples. For samples
that contain more than 1 mg/g of total solvent extractable material, the
detection limit is proportionately higher.
1.5 Method 8250 is based upon a solvent extraction, gas chromatographic/
mass spectrometric (GC/MS) procedure.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatograph/mass spectrometers and
skilled in the interpretation of mass spectra. Each analyst must demonstrate
the ability to generate acceptable results with this method.
2.0 Summary of Method
2.1 Prior to using this method, the waste samples should be prepared
for chromatography (if necessary) using the appropriate sample preparation
method - i.e., separatory funnel liquid-liquid extraction (Method 3510), acid
base extraction (Method 3530), sonication (Method 3550), or soxhlet extraction
(Method 3540). For groundwater samples Method 3530 should be used. If
emulsions are a problem, continuous extraction techniques should be used.
This method describes chromatographic conditions which allow for the separa-
tion of the compounds in the extract.
-------
2 / ORGANIC ANALYTICAL METHODS - GC/MS
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-------
6 / ORGANIC ANALYTICAL METHODS - GC/MS
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of chromatograms. All these materials must be demonstrated to be free
from interferences under the conditions of the analysis by running method
blanks. Specific selection of reagents and purification of solvents by
distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from source to source, depending upon the diversity of the industrial complex
or waste being sampled.
3.2.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Heating in a muffle furnace at 450" C for 5 to 15 hr is recom-
mended whenever feasible. Alternatively, detergent washes, water
rinses, acetone rinses, and oven drying may be used. Cleaned glassware
should be sealed and stored in a clean environment to prevent any
accumulation of dust or other contaminants.
3.2.2 The use of high purity reagents and solvents helps to
minimize interference problems.
4.0 Apparatus
4.1 Sampling equipment: Glass screw-cap vials or jars of at least
100-ml capacity. Screw caps must be Teflon lined.
4.2 Glassware
4.2.1 Beaker: 400-ml.
4.2.2 Centrifuge tubes: approximately 200-ml capacity, glass
with screw cap (Corning #1261 or equivalent). Screw caps must be fitted
with Teflon liners.
4.2.3 Concentrator tube, Kuderna-Danish: 25-ml, graduated
(Kontes K 570050-2526 or equivalent). Calibration must be checked at
the volumes employed in the test. Ground-glass stopper is used to
prevent evaporation of extracts.
4.2.4 Evaporative flask: Kuderna-Danish 250-ml (Kontes K-570001-0250
or equivalent). Attach to concentrator tube with springs.
4.2.5 Snyder column, Kuderna-Danish: Three-ball macro (Kontes
K-503000-0121 or equivalent).
-------
8250 / 7
4.2.6 Snyder column, Kuderna-Danish: Two-ball micro (Kontes
K-569001-0219 or equivalent).
4.3 Filter assembly
4.3.1 Syringe: 10-ml gas-tight with Teflon Luerlock (Hamilton
1010TLL or equivalent).
4.3.2 Filter holder: 13-mm Swinny (Millipore XX30-012 or equiva-
lent)
4.3.3 Prefilters: glass fiber (Millipore AP-20-010 or equivalent).
4.3.4 Membrane filter: 0.2-um Teflon (Millipore FGLP-013 or
equivalent)
4.4 Micro syringe: lOO-u/l (Hamilton #84858 or equivalent).
4.5 Weighing pans, micro: approximately 1-cm diameter aluminum foil.
Purchase or fabricate from aluminum foil.
4.6 Boiling chips: Approximately 10-40 mesh carborundum (A.H. Thomas
#1590-030 or equivalent). Heat to 450° C for 5-10 hr or extract with methy-
lene chloride.
4.7 Water bath: Heated, capable of temperature control (+2° C). The
bath should be used in a hood.
4.8 Balance: Analytical, capable of accurately weighing 0.0001 g.
4.9 Microbalance: Capable of accurately weighing to 0.001 mg (Mettler
model ME-30 or equivalent).
4.10 Homogenizer, high speed: Brinkmann Polytron model PT 10ST with
Teflon bearings, or equivalent.
4.11 Centrifuge: Capable of accommodating 200-ml glass centrifuge
tubes.
4.12 pH Meter and electrodes: Capable of accurately measuring pH to
jK).l pH unit.
4.13 Spatula: Having a metal blade 1-2 cm in width.
4.14 Heat lamp: 250-watt reflector-type bulb (GE #250R-40/4 or equiva-
lent) in a heat-resistant fixture whose height above the sample may be
conveniently adjusted.
-------
8 / ORGANIC ANALYTICAL METHODS - GC/MS
4.15 Gas chromatograph/mass spectrometer data system
4.15.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph and all required accessories
including syringes, analytical columns, and gases.
4.15.2 Column for base-neutral compounds: 2-m x 2-mm I.D. stain-
less steel or glass, packed with 3% SP-2250-DB on 100/120 mesh Supelcoport
or equivalent.
4.15.3 Column for acidic compounds: 2-m x 2-mm I.D. glass
packed with 1% SP 1240-DA on 100/120 mesh Supelcoport.
4.15.4 Mass spectrometer: Capable of scanning from 35 to 450 amu
every 3 sec or less, utilizing 70 volts (nominal) electron energy in the
electron impact ionization mode and producing a mass spectrum which
meets all the criteria in Table 3 when 50 ng of decafluorotriphenyl-
phosphine (DFTPP) is injected through the GC inlet.
TABLE 3. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA^
Mass Ion abundance criteria
51 30-60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40-60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17-23% of mass 442
aJ.W. Eichelberger, L.E. Harris, and W.L. Budde. 1975. Reference
compound to calibrate ion abundance measurement in gas chromatography-mass
spectrometry. Analytical Chemistry 47:995.
-------
8250 / 9
4.15.4 GC/MS interface: Any GC-to-MS interface that gives accept-
able calibration points at 50 ng per injection for each compound of
interest and achieves acceptable tuning performance criteria (see
Sections 7.2.1-7.2.4) may be used. GC-to-MS interfaces constructed of
all glass or glass-lined materials are recommended. Glass can be
deactivated by silanizing with dichlorodimethylsilane. The interface
must be capable of transporting at least 10 ng of the components of
interest from the GC to the MS.
4.15.5 Data system: A computer system must be interfaced to the
mass spectrometer. The system must allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained through-
out the duration of the chromatographic program. The computer must have
software that can search any GC/MS data file for ions of a specific mass
and that can plot 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 integrating the abundance in
any EICP between specified time or scan number limits.
4.16 Gel permeation chromatography system
4.16.1 Chromatographic column: 600-mm x 25-mm I.D. glass column
fitted for upward flow operation.
4.16.2 Bio-beads S-X8: 80 g per column.
4.16.3 Pump: Capable of constant flow of 0.1 to 5 ml/min at up
to 100 psi.
4.16.4 Injector: With 5-ml loop.
4.16.5 Ultraviolet detector: 254 mm.
4.16.6 Strip chart recorder.
5.0 Reagents
5.1 Reagent water: Reagent water is defined as a water in which an
interferent is not observed at the method detection limit of each compound of
interest.
5.2 Potassium phosphate, tribasic (K3P04): Granular (ACS).
5.3 Phosphoric acid (H3P04): 85% aqueous solution (ACS).
5.4 Sodium sulfate, anhydrous (Na2S04): Powder (ACS).
5.5 Methylene chloride: Distilled-in-glass quality (Burdick and
Jackson, or equivalent).
-------
10 / ORGANIC ANALYTICAL METHODS - GC/MS
5.6 DjQ-Phenanthrene.
5.7 Decafluorotriphenylphosphine (DFTPP).
5.8 Retention time standards: D3~Phenol, Ds-naphthalene,
Phenanthrene, Di2-chrysene, and Di2-benzo(a)pyrene. Dig-perylene may
be used in place of Di2-benzo(a)pyrene.
5.9 Column performance standards: D3~phenol, D5~aniline, 05-
nitrobenzene, and D3-2,4-dinitrophenol.
5.10 Surrogate standards: Decafluorobiphenyl, 2-fluoroaniline, and
pentafluorophenol.
5.11 GPC calibration solution: Methylene chloride containing 100 mg
corn oil, 20 mg di-n-octyl phthalate, 3 mg coronene, and 2 mg sulfur per
100 ml.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers having Teflon-
lined screw caps. Sampling equipment must be free of oil and other potential
sources of contamination.
6.2 The samples must be iced or refrigerated at 4° C from the time
of collection until extraction.
6.3 All samples must be extracted within 14 days of collection and
completely analyzed within 40 days of extraction.
7.0 Procedure
7.1 Calibration
7.1.1 An internal standard calibration procedure is used. To use
this approach, the analyst must select one or more internal standards
that are similar in analytical behavior to the compounds of interest.
The analyst must further demonstrate that measurement of the internal
standard is not affected by method or matrix interferences. DIQ-
phenanthrene is recommended for this purpose for general use. Use the
base peak ion as the primary ion for quantification of the standards.
If interferences are noted, use the next most intense ion as the second-
ary ion. The internal standard is added to all calibration standards
and all sample extracts analyzed by GC/MS. Retention time standards,
column performance standards, and a mass spectrometer tuning standard
are included in the internal standard solution used.
-------
8250 / 11
7.1.1.1 A set of five or more retention time standards is
selected that will permit all components of interest in a chroma-
togram to have retention times of 0.85 to 1.20 relative to at
least one of the retention time standards. The retention time
standards should be similar in analytical behavior to the compounds
of interest and their measurement should not be affected by method
or matrix interferences. The following retention time standards are
recommended for general use: D3-phenol, Ds-naphthalene, $\2~
chrysene, and Di2-benzo(a)pyrene. Di5-perylene may be substi-
tuted for Di2-benzo(a)pyrene. DiQ-phenanthrene serves as a
retention time standard as well as an internal standard.
7.1.1.2 Representative acidic, basic, and polar netural
compounds are added with the internal standard to assess the
column performance of the GC/MS system. The measurement of the
column performance standards should not be affected by method or
matrix interferences. The following column performance standards
are recommended for general use: Ds-phenol, D5-aniline,
Ds-nitrobenzene, and D3-2,4-dinitrophenol. These compounds
can also serve as retention time standards if appropriate and the
retention time standards recommended in Section 7.1.1.1 can serve
as column performance standards if appropriate.
7.1.1.3 Decafluorotriphenylphosphine (DFTPP) is added to
the internal standard solution to permit the mass spectrometer
tuning for each GC/MS run to be checked.
7.1.1.4 Prepare the internal standard solution by dissolving,
in 50.0 ml of methylene chloride, 10.0 mg of each standard compound
specified in Sections 7.1.1.1, 7.1.1.2, and 7.1.1.3. The resulting
solution will contain each standard at a concentration of 200 u.g/ml.
7.1.2 Prepare calibration standards at a minimum of three concen-
tration levels for each compound of interest. Each ml of each calibra-
tion standard or standard mixture should be mixed with 250 u.1 of the
internal standard solution. One of the calibration standards should be
at a concentration near, but above, the method detection limit, 1 to
10 pig/ml, and the other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the GC/MS system.
7.1.3 Analyze 1 u.1 of each calibration standard and tabulate the
area of the primary characteristic ion against concentration for each
compound including standard compound. Calculate response factors (RF)
for each compound as follows:
RF = (AsCis)/(AisCs)
-------
12 / ORGANIC ANALYTICAL METHODS - GC/MS
where:
As = Response for the parameter to be measured.
AJS = Response for the internal standards.
CTS = Concentration of the internal standard in u.g/1 .
Cs = Concentration of the compound to be measured in ug/1 .
If the RF value over the working range is constant (less than 20%
relative standard deviation), 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/A-js,
against RF.
7.1.4 The RF must be verified on each working day by the measure-
ment of two or more calibration standards, including one at the beginning
of the day and one at the end of the day. The response factors obtained
for the calibration standards analyzed immediately before and after a
set of samples must be within +;20% of the response factor used for
quantification of the sample concentrations.
7.2 Daily GC/MS performance tests
7.2.1 At the beginning of each day that analyses are to be
performed, the GC/MS system must be checked to see that acceptable
performance criteria are achieved for DFTPP.
7.2.2 The DFTPP performance test requires the following instru-
mental parameters:
Electron energy: 70 volts (nominal)
Mass Range: 40 to 450 amu
Scan Time: 1 sec per scan
7.2.3 Inject a solution containing 50 u.g/ml of DFTPP into the
GC/MS system or bleed DFTPP vapor directly into the mass spectrometer
and tune the instrument to achieve all the key ion criteria for the mass
spectrum of DFTPP given in Table 1.
7.2.4 DFTPP is included in the internal standard solution added
to all samples and calibration solutions. If any key ion abundance
observed for DFTPP during the analysis of a sample differs by more than
10% from that observed during the analysis of the calibration solution,
then the analysis in question is considered invalid. The instrument
-------
8250 / 13
must be retuned or the sample and/or calibration solution reanalyzed
until the above condition is met.
7.3 Sample extraction
7.3.1 The extraction procedure involves homogenization of the
sample with methylene chloride, neutralization to pH 7, and the addition
of anhydrous sodium sulfate to remove the water. The amount of acid or
base required for the neutralization is determined by titration of the
sample. Aqueous samples are extracted using Method 3510 while organic
liquids may be analyzed neat or diluted with CH2 and analyzed. Solids
and semi sol ids are extracted by Method 3540 and 3550 or by the extraction
described in Steps 7.3.1 through 7.4.3.
7.3.1.1 Thoroughly mix the sample to enable a representative
sample to be obtained. Weight 3.0 g (wet weight) of sample into a
400-ml beaker. Add 75 ml methylene chloride and 150 ml water.
7.3.1.2 Homogenize the mixture for a total of 1 min using a
high-speed homogenizer. Use a metal spatula to dislodge any
material that adheres to the beaker or to the homogenizer before or
during the homogenization to ensure thorough dispersion of the sample.
7.3.1.3 Adjust the pH of the mixture to 7.0 _+ 0.2 by titration
with 0.4 M H3P04 or 0.4 M K3P04 using a pH meter to measure
the pH. Record the volume of acid or base required.
7.3.2 The extraction with methylene chloride is performed using a
fresh portion of the sample. Weigh 3.0 g (wet weight) of sample into a
200-ml centrifuge tube. Spike the sample with surrogate standards as
described in Section 8.4. Add 150 ml of methylene chloride followed by
1.0 ml of 4 M phosphate buffer pH 7.0, and an amount of 4 M H3P04 or
4 M K3P04 equal to one tenth of the pH 7 acid or base volume requirement
determined in Section 7.3.1.3. For example, if the acid requirement in
Section 7.3.1.3 was 2.0 ml of 0.4 M ^04, the amount of 4 M ^04
needed would be 0.2 ml.
7.3.3 Homogenize the mixture for a total of 30 sec using a high-
speed homogenizer at full speed. Cool the mixture in an ice bath
or cold water bath, if necessary, to maintain a temperature of 20-30° C.
Use a metal spatula to help dislodge any material that adheres to the
centrifuge tube or homogenizer during the homogenization to obtain as
thorough a dispersion of the sample as possible. Some samples, espe-
cially those that contain much water, may not disperse well in this step
but will disperse after sodium sulfate is added. Add an amount of
anhydrous sodium sulfate powder equal to 15.0 g plus 3.0 g per ml of
the 4 M H3P04 or 4 M KsP04 added in Section 7.3.2. Homogenize
the mixture again for a total of 30 sec using a high-speed homoge-
nizer at full speed. Use a metal spatula to dislodge any material that
adheres to the centrifuge tube or homogenizer during the homogenization
to ensure thorough dispersion. (NOTE: This step may cause rapid
deterioration of the Teflon bearing in the homogenizer. The bearing
-------
14 / ORGANIC ANALYTICAL METHODS - GC/MS
must be replaced whenever the rotor shaft becomes loose to prevent
damage to stainless steel parts.) Allow the mixture to stand until a
clear supernatant is obtained. Centrifuge if necessary to facilitate
the phase separation. Filter the supernatant required for Sections
7.3.4, 7.3.5, and 7.3.7 (at least 2 ml) through a 0.2-um Teflon filter.
7.3.4 Estimate the total solvent extractable content (TSEC) of the
sample by determining the residue weight of an aliquot of the supernatant
from Section 7.3.3. Transfer 0.1 ml of the supernatant to a tared
aluminum weighing dish, place the weighing dish under a heat lamp at a
distance of 8 cm from the lamp for 1 min to allow the solvent to
evaporate, and weigh on a microbalance. If the residue weight of the
0.1-ml aliquot is less than 0.05 mg, concentrate 25 ml of the supernatant
to 1.0 ml and obtain a residue weight on 0.1 ml of the concentrate. For
the concentration step, use a 25-ml evaporator tube fitted with a micro
Snyder column; add two boiling chips and heat in a water bath at 60-65° C.
Calculate the TSEC as milligrams of residue per gram of sample using
Equation 1 if concentration was not required or Equation 2 if concentra-
tion was required.
mg of residue res i^uje_w^i^ht__(nvg_)__o_f _0_. l__ml of supernatant^
g of fample ~ 0.002"
mg of residue _ £e_sj.du.e_we_i_g_ht_Jnig_) of__0.ljnl_ o_f_ cone. _suj)e_rnatant
g of s~ample~ ~" 0.05
7.3.5 If the TSEC of the sample (as determined in Section 7.3) is
less than 50 mg/g, concentrate an aliquot of the supernatant that
contains a total of only 10 to 20 mg of residual material. For example,
if the TSEC is 44 mg/g, use a 20-ml aliquot of the supernatant, which
will contain 17.6 mg of residual material, or if the TSEC is 16 mg/g,
use a 50-ml aliquot of the supernatant, which will contain 16.0 mg of
residual material. If the TSEC is less than 10 mg/g, use 100 ml of the
supernatant. Perform the concentration by transferring the aliquot of
the supernatant to a K-D flask fitted into a 25-ml concentrator tube.
Add two boiling chips, attach a three-ball macro Snyder 'column to the
K-D flask, and concentrate the extract using a water bath at 60 to 65° C.
Place the K-D apparatus in the water bath so that the concentrator
tube is about half immersed in the water and the entire rounded surface
of the flask is bathed with water vapor. Adjust the vertical position
of the apparatus and the water temperature as required to complete the
concentration in 15 to 20 min. At the proper rate of distillation, the
balls of the column actively chatter but the chambers do not flood.
When the liquid has reached an apparent volume of 5 to 6 ml, remove the
K-D apparatus from the water bath and allow the solvent to drain for at
least 5 min while cooling. Remove the Snyder column and rinse the
flask and its lower joint into the concentrator tube with the rnethylene
chloride to bring the volume to 10.0 ml. Mix the contents of the
concentrator tube by inserting a stopper and inverting several times.
-------
8250 / 15
7.3.6 Analyze the concentrate from Section 7.3.5 or, if the TSEC
of the sample is 50 mg/g or more, analyze the supernatant from Section
7.3 using gas chrornatography. Use a 30-m x 0.25-mm bonded-phase silicone
coated fused-silica capillary column under the chromatographic conditions
described in Section 7.5. Estimate the concentration factor or dilution
factor required to give the optimum concentration for the subsequent
GC/MS analysis. In general, the optimum concentration will be one in
which the average peak height of the five largest peaks or the height of
an unresolved envelope of peaks is the same as that of an internal
standard at a concentration of 50-100 u,g/ml.
7.3.7 If the optimum concentration determined in Section 7.3.6 is
20 mg of residual material per ml or less, proceed to Section 7.3.8. If
the optimum concentration is greater than 20 mg of residual material per
ml and if the TSEC is greater than 50 mg/g, apply the GPC cleanup
procedure described in Section 7.4. For the GPC cleanup, concentrate
90 ml of the supernatant from Section 7.3.3 or a portion of the super-
natant that contains a total of 600 mg of residual material (whichever
is the smaller volume). Use the concentration procedure described in
Section 7.3.5 and concentrate to a final volume of 15.0 ml. Stop the
concentration prior to reaching 15.0 ml if any oily or semisolid mate-
rial separates out and dilute as necessary (up to a maximum final volume
equal to the volume of supernatant used) to redissolve the material.
(Disregard the presence of small amounts of inorganic salts that may
settle out.)
7.3.8 Concentrate further or dilute as necessary an aliquot of the
concentrate from Section 7.3.5 or an aliquot of the supernatant from
Section 7.3.3, or if GPC cleanup was necessary, an aliquot of the
concentrate from Section 7.4.3 to obtain 1.0 ml of a solution having
the optimum concentration, as described in Section 7.3.6, for the GC/MS
analysis. If the aliquot needs to be diluted, dilute it to a volume of
1.0 ml with methylene chloride. If the aliquot needs to be concentrated,
concentrate it to 1.0 ml as decribed in Section 7.3.4. Do not let the
volume in the concentrator tube go below 0.6 ml at any time. Stop the
concentration prior to reaching 1.0 ml if any oily or semisolid material
separates out and dilute as necessary (up to a maximum final volume
of 10 ml) to redissolve the material. (Disregard the presence of small
amounts of inorganic salts that may settle out). Add 250 u.1 of the
internal standard solution, containing 50 pig each of the internal
standard, retention time standards, column performance standards, and
DFTPP, to 1.0 ml of the final concentrate and save for GC/MS analysis as
described in Section 7.5. Calculate the concentration in the original
sample that is represented by the internal standard using Equation 3 if
an aliquot of the concentrate from Section 7.3.5 was used in Section
7.3.8, Equation 4 if an aliquot of the supernatant from Section 7.3.3
was used in Section 7.3.8 or Equation 5 if an aliquot of the GPC concen-
trate from Section 7.4.3 was used in Section 7.3.8.
-------
16 / ORGANIC ANALYTICAL METHODS - GC/MS
ug of IjvU_ StCL. J50 150 10__ Final Vol_._(m]J_ ,F ~*
g-ofsaTn-pTe ' 3 V$-,7.5.5)\ (7.X3.8) "I"- lEq. 3)
of Int. Std. 50 150 w Final Vol. (ml
--- = ~ - --- "
ug of Int. Std. _ 50 150 _F___ Final Vol. (ml)
g of Tarapir- - 3 x T;(7 J>7) V^ (*<3>7) "I ~
where:
Vs = Volume of supernatant from Section 7.3.3 used in
Sections 7.3.5, 7.3.8, 7.3.7
^c(7.3.8) = Volume of concentrate from Section 7.3.5 used in
Section 7.3.8
Vp (7.3.7) = Final volume of concentrate in Section 7.3.7
= Volume of GPC concentrate from Section 7.4.3 used in
Section 7.3.8
Use this calculated value for the quantification of individual compounds
as described in Section 7.7.2.
7.4 Cleanup using gel permeation chromatography
7.4.1 Prepare a 600-mm x 25-mm I.D. gel permeation chromatography
(GPC) column by slurry packing using 80 g of Bio-Beads S-X8 that have
been swelled in methylene chloride for at least 4 hr. Prior to
initial use, rinse the column with methylene chloride at 1 rnl/min for
16 hr to remove any traces of contaminants. Calibrate the system by
injecting 5 ml of the GPC calibration solution, eluting with methylene
chloride at 5 ml/min for 50 min and observing the resultant UV
detector trace. The column may be used indefinitely as long as no
darkening or pressure increases occur and a column efficiency of at least
500 theoretical plates is achieved. The pressure should not be permitted
to exceed 50 psi. Recalibrate the system daily.
7.4.2 Inject a 5-ml aliquot of the concentrate from Section 7.3.7
onto the GPC column and elute with methylene chloride at 5 ml/min for
50 min. Discard the first fraction that elutes up to a retention time
represented by the minimum between the corn oil peak and the di-n-octyl
phthalate peak in the calibration run. Collect the next fraction
eluting up to a retention time represented by the minimum between the
coronene peak and the sulfur peak in the calibration run. Apply the
-------
8250 / 17
above GPC separation to a second 5-ml aliquot of the concentrate from
Section 7.3.7 and combine the fractions collected.
7.4.3 Concentrate the combined GPC fractions to 10.0 ml as
described in Section 7.3.5. Estimate the TSEC of the concentrate as
described in Section 7.3.4. Estimate the TSVC of the concentrate as
described in Section 7.3.6.
7.5 Gas chromatography/mass spectrometry
7.5.1 Analyze the 1-ml concentrate from Method 3510, 3540, or
3550, or Section 7.3.8 by GC/MS using the appropriate column (see Sec-
tion 4,15). The recommended GC operating conditions to be used are as
follows:
Conditions for base neutral analysis (3% SP-2250-DB)
Initial column temperature hold: 50° C for 4 min
Column temperature program: 50-300° C at 8 degrees/min
Final column temperature hold: 300^ C for 20 min.
Conditions for acid analysis (1% SP-1240-DA)
Initial column temperature: 70° C for 2 min
Column temperature program: 70-200° C at 8 degrees/min
Final column temperature hold: 200° C for 20 min
Injector temperature: 300° C
Transfer line temperature: 300° C
Sample volume: 1-2 u.1
Carrier gas: Helium at 30 ml/min
7.5.2 If the response for any ion exceeds the working range of the
GC/MS system, dilute the extract and reanalyze.
7.5.3 Perform all qualitative and quantitative measurements as
described in Sections 7.6 and 7.7. When the extracts are not being used
for analyses, store them at 4° C protected from light in screw-cap vials
equipped with unpierced Teflon-lined septa.
-------
18 / ORGANIC ANALYTICAL METHODS - GC/MS
7.6 Qualitative identification. Obtain an EICP for the primary charac-
teristic ion and at least two other characteristic ions for each compound
when practical. The following criteria must be met to make a qualitative
identification.
7.6.1 The characteristic ions for each compound of interest
must maximize in the same or within one scan of each other.
7.6.2 The retention time must fall within _+ 15 sec (based on the
relative retention time) of the retention time of the authentic compound.
7.6.3 The relative peak heights of the characteristic ions in
the EICP's must fall within +_2Q% of the relative intensities of these
ions in a reference mass spectrum.
7.7 Quantitative determination
7.7.1 When a compound has been identified, the quantification of
that compound will be based on the integrated abundance from the EICP of
the primary characteristic ion. In general, the primary characteristic
ion selected should be a relatively intense ion as interference-free as
possible, and as close as possible in mass to the characteristic ion of
the internal standard used.
7.7.2 Use the internal standard technique for performing the
quantification. Calculate the concentration of each individual compound
of interest in the sample using Equation 6.
Concentration, M/g - ^of 'stpf/' « ^ x fc (Eq' "
where:
of n . St .
_ interna] standard concentration factor calculated
g of sample 1f) $ection
As = Area of the primary characteristic ion of the
compound being quantified
A-js = Area of the primary characteristic ion of the
internal standard
RF = Response factor of the compound being quantified
(determined in Section 7.1.3).
7.7.3 Report results in ng/g without correction for recovery data.
When duplicate and spiked samples are analyzed, report all data obtained
with the sample results.
-------
8250 / 19
7.7.4 If the surrogate standard recovery falls outside the control
limits in Section 8.3, the data for all compounds in that sample must
be labeled as suspect.
8.0 Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and the analysis
of spiked samples as a continuing check on performance. The laboratory is
required to maintain performance records to define the quality of data that
is generated. Ongoing performance checks must be compared with established
performance criteria to determine if the results of analyses are within the
accuracy and precision limits expected of the method.
8.1.1 Before performing any analyses, the analyst must demon-
strate the ability to generate acceptable accuracy and precision with
this method. This ability is established as described in Section 8.2.
8.1.2 The laboratory must spike all samples including check
samples with surrogate standards to monitor continuing laboratory
performance. This procedure is described in Section 8.4.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations using a repre-
sentative sample as a check sample.
8.2.1 Analyze four aliquots of the unspiked check sample according
to the method beginning in Section 7.3.
8.2.2 For each compound to be measured, select a spike concen-
tration representative of twice the level found in the unspiked check
sample or a level equal to 10 times the expected detection limit,
whichever is greater. Prepare a spiking solution by dissolving the
compounds in methylene chloride at the appropriate levels.
8.2.3 Spike a minimum of four aliquots of the check sample with
the spiking solution to achieve the selected spike concentrations.
Spike the samples after they have been transferred to centrifuge tubes
for extraction. Analyze the spiked aliquots according to the method
described beginning in Section 7.3.
8.2.4 Calculate the average percent recovery (R) and the standard
deviation of the percent recovery (s) for all compounds and surrogate
standards. Background corrections must be made'before R and s calcula-
tions are performed. The average percent recovery must be greater than
20 for all compounds to be measured and greater than 60 for all surro-
gate compounds. The percent relative standard deviation of the percent
recovery (s/R x 100) must be less than 20 for all compounds to be
measured and all surrogate compounds.
-------
20 / ORGANIC ANALYTICAL METHODS - GC/MS
8.3 The analyst must calculate method performance criteria for each of
the surrogate standards.
8.3.1 Calculate upper and lower control limits for method perform-
ance for each surrogate standard, using the values for R and s calculated
in Section 8.2.4:
Upper Control Limit (UCL) = R + 3s
Lower Control Limit (LCL) = R - 3s
The UCL and LCL can be used to construct control charts that are useful
in observing trends in performance.
8.3.2 For each surrogate standard, the laboratory must maintain a
record of the R and s values obtained for each surrogate standard in
each waste sample analyzed. An accuracy statement should be prepared
from these data and updated regularly.
8.4 The laboratory is required to spike all samples with the surrogate
standard to monitor spike recoveries. The spiking level used should be that
which will give a concentration in the final extract used for GC/MS analysis
that is equal to the concentration of the internal standard assuming a 100%
recovery of the surrogate standards. For unknown samples, the spiking level
is determined by performing the extraction steps in Section 7.3 on a separate
aliquot of the sample and calculating the amount of internal standard per
gram of sample as described in Section 7.3.8. If the recovery for any surro-
gate standard does not fall within the control limits for method performance,
the results reported for that sample must be qualified as being outside of
control limits. The laboratory must monitor the frequency of data so qualified
to ensure that it remains at or below 5%. Three surrogate standards, namely
decafluorobiphenyl, 2-fluoroaniline, and pentafluorophenol, are recommended
for general use to monitor recovery of neutral, basic, and acidic compounds,
respectively.
8.5 Before processing any samples, the analyst must demonstrate through
the analysis of a process blank that all glassware and reagent interferences
are under control. Each time a set of samples is extracted or there is a
change in reagents, a process blank should be analyzed to determine the level
of laboratory contamination.
8.6 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. Field replicates may be analyzed to monitor the precision
of the sample technique. Whenever possible, the laboratory should perform
analysis of standard reference materials and participate in relevant perform-
ance evaluation studies.
-------
8250 / 21
8.7 The features that must be monitored for each GC/MS analysis run for
quality control purposes and for which performance criteria must be met are
as follows:
0 Relative ion abundances of the mass spectrometer tuning compound
DFTPP.
• Response factors of column performance standards and retention time
standards.
• Relative retention time of column performance standards and retention
time standards.
• Peak area intensity of the internal standard, e.g., Dig-phenanthrene.
8.8 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples should be carried through
all stages of sample preparation and measurement; they should be analyzed
to validate the sensitivity and accuracy of the analysis. If the fortified
waste samples do not indicate sufficient sensitivity to detect less than or
equal to 1 u,g/g of sample, then the sensitivity of the instrument should be
increased or the extract subjected to additional cleanup. Detection limits
to be used for groundwater samples are indicated in Tables 1 and 2. Where
doubt exists over the identification of a peak on the chromatograph, con-
firmatory techniques such as mass spectroscopy should be used.
8.9 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Tables 1 and 2
were obtained using reagent water. Similar results were achieved using
representative wastewaters. The MDL actually achieved in a given analysis
will vary depending on instrument sensitivity and matrix effects.
8.10 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Tables 4
and 5 were obtained. The standard deviation of the measurement in percent
recovery is also included in Tables 4 and 5.
-------
22 / ORGANIC ANALYTICAL METHODS - GC/MS
TABLE 4. ACCURACY AND PRECISION FOR BASE/NEUTRAL EXTRACTABLES
Reagent water
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo(a)anthracene
6enzo(b)fluoranthene
8enzo(k)fluoranthene
Benzo(ghi )perylene
Benzo(a)pyrene
Benzidine
Butyl benzyl phthalate
3-BHC
6-BHC
Bis (2-chloroethoxy) methane
Bis (2-chloroethyl ) ether
Bis (2-chloroisopropyl ) ether
Bis (2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo(a,h)anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 ,4-Di chl orobenzene
3,3-Dichlorobenzidine
Diethylphthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octylphthalate
Endosulfan sulfate
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Average
percent
recovery
77
78
72
84
83
96
96
80
90
87
47
69
56
84
56
71
129
80
73
45
83
80
69
63
82
70
59
55
61
184
42
25
83
79
97
79
89
77
69
82
Standard
deviation
(*)
23
22
6
14
19
68
68
45
22
61
32
25
18
33
36
33
50
17
24
11
19
9
20
15
39
25
27
28
31
174
28
33
32
18
37
29
19
16
6
7
Wastewater
Average
percent
recovery
83
82
--
76
75
41
47
68
43
63
74
—
--
82
72
71
82
75
79
—
75
—
—
—
70
93
62
54
63
143
48
35
79
79
89
--
80
80
—
--
Standard
deviation
(%)
29
23
--
22
28
21
27
40
21
55
43
--
--
74
37
39
63
20
27
__
28
—
--
--
40
51
28
24
35
145
28
36
34
25
62
__
26
20
_.
-------
4 / ORGANIC ANALYTICAL METHODS - GC/MS
4.15 Gas chromatograph/mass spectrometer data system
4.15.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
injection and all required accessories including syringes, analytical
columns, and gases.
4.15.2 Column: 30-m x 0.25-mm bonded-phase silicone-coated fused
silica capillary column (J&W Scientific DB-5 or equivalent), with a film
thickness of 0.25 u or equivalent.
4.15.3 Mass spectrometer: Capable of scanning from 35 to 450 arnu
every 1 sec or less, utilizing 70 volts (nominal) electron energy in the
electron impact ionization mode and producing a mass spectrum which
meets all the criteria in Table 1 when 50 ng of decafluorotriphenyl-
phosphine (DFTPP) is injected through the GC inlet.
TABLE 1. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA3
Mass Ion abundance criteria
51 30-60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40-60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17-23% of mass 442
aJ.W. Eichelberger, L.E. Harris, and W.L. Budde. 1975. Reference
compound to calibrate ion abundance measurement in gas chromatography-mass
spectrometry. Analytical Chemistry 47:995.
-------
8250 / 23
TABLE 4. (CONT.)
Reagent water
Parameter
Hexachlorobenzene
Hexachl orobutadi ene
Hexachl orocycl opentadi ene
Hexachl oroethane
Indeno (1,2,3-cd) pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi-n-propylamine
N-Nitrosodiphenylamine
PCB-1221
PCB-1254
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
Average
percent
recovery
79
46
27
46
65
75
67
72
68
84
77
80
84
86
64
Standard
deviation
(X)
20
25
25
21
37
33
32
31
39
24
11
13
14
15
16
Wastewater
Average
percent
recovery
71
48
12
52
81
77
75
82
76
86
__
--
76
80
69
Standard
deviation
(X)
22
28
12
26
43
42
35
54
45
31
--
—
22
23
26
Spiked between 5 and 2400
TABLE 5. ACCURACY AND PRECISION FOR ACID EXTRACTABLES
Reagent water
Wastewater
Average Standard
percent deviation
Parameter
4-Chloro-3-rnethyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-di nitrophenol
4-Nitrophenol
2-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
recovery
79
70
74
64
78
83
41
75
86
36
77
(X)
18
23
24
25
21
18
20
25
20
14
20
Average
percent
recovery
75
71
80
58
108
90
43
75
66
36
81
Standard
deviation
(X)
21
25
21
26
56
35
16
27
36
21
20
Spikes ranged from 10 to 1500 |ig/l
-------
METHOD 8270
GC/MS METHOD FOR SEMIVOLATILE ORGANICS:
CAPILLARY COLUMN TECHNIQUE
1.0 Scope and Application
1.1 Method 8270 is used to determine the concentration of semivolatile
organic compounds in a variety of solid waste matrices.
1.2 This method is applicable to nearly all types of samples, regard-
less of water content, including aqueous sludges, caustic liquors, acid
liquors, waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
meric emulsions, filter cakes, spent carbons, spent catalysts, soils, and
sediments.
1.3 Method 8270 can be used to quantify most neutral, acidic, and basic
organic compunds that are soluble in methylene chloride and capable of being
eluted without derivatization as sharp peaks from a gas chromatographic fused
silica capillary column coated with a slightly polar silicone. Such compounds
include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons and
pesticides, phthalate esters, organophosphate esters, nitrosamines, haloethers,
aldehydes, ethers, ketones, anilines, pyridines, quinolines, aromatic nitro
compounds, and phenols, including nitrophenols.
1.4 The detection limit of Method 8270 for determining an individual
compound is approximately 1 u.g/g (wet weight). For samples that contain more
than 1 mg/g of total solvent extractable material, the detection limit is
proportionately higher.
1.5 Method 8270 is based upon a solvent extraction, gas chromatographic/
mass spectrometric (GC/MS) procedure.
1.6 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatograph/mass spectrometers and
skilled in the interpretation of mass spectra. Each analyst must demonstrate
the ability to generate acceptable results with this method.
2.0 Summary of Method
2.1 Prior to using this method, the waste samples should be prepared
for chromatography (if necessary) using the appropriate sample preparation
method - i.e., separatory funnel liquid-liquid extraction (Method 3510),
sonication (Method 3550), or soxhlet extraction (Method 3540). If emulsions
are a problem, continuous extraction techniques should be used. This method
describes chromatographic conditions which allow for the separation of the
compounds in the extract.
-------
2 / ORGANIC ANALYTICAL METHODS - GC/MS
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of chromatograms. All these materials must be demonstrated to be free
from interferences under the conditions of the analysis by running method
blanks. Specific selection of reagents and purification of solvents by
distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from source to source, depending upon the diversity of the industrial complex
or waste being sampled.
3.2.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by rinsing with the last solvent used in
it. Heating in a muffle furnace at 450' C for 5 to 15 hr is recom-
mended whenever feasible. Alternatively, detergent washes, water
rinses, acetone rinses, and oven drying may be used. Cleaned glassware
should be sealed and stored in a clean environment to prevent any
accumulation of dust or other contaminants.
3.2.2 The use of high purity reagents and solvents helps to
minimize interference problems.
4.0 Apparatus
4.1 Sampling equipment: Glass screw-cap vials or jars of at least
100-ml capacity. Screw caps must be Teflon lined.
4.2 Glassware
4.2.1 Beaker: 400-ml.
4.2.2 Centrifuge tubes: approximately 200-ml capacity, glass
with screw cap (Corning #1261 or equivalent). Screw caps must be fitted
with Teflon liners.
4.2.3 Concentrator tube, Kuderna-Danish: 25-ml, graduated
(Kontes K 570050-2526 or equivalent). Calibration must be checked at
the volumes employed in the test. Ground-glass stopper is used to
prevent evaporation of extracts.
4.2.4 Evaporative flask: Kuderna-Danish 250-ml (Kontes K-570001-0250
or equivalent). Attach to concentrator tube with springs.
4.2.5 Snyder column, Kuderna-Danish: Three-ball macro (Kontes
K-503000-0121 or equivalent).
-------
8270 / 3
4.2.6 Snyder column, Kuderna-Danish: Two-ball micro (Kontes
K-569001-0219 or equivalent).
4.3 Filter assembly
4.3.1 Syringe: 10-ml gas-tight with Teflon luer lock (Hamilton
1010TLL or equivalent).
4.3.2 Filter holder: 13-mm Swinny (Millipore XX30-012 or equiva-
lent)
4.3.3 Prefilters: glass fiber (Millipore AP-20-010 or equivalent).
4.3.4 Membrane filter: 0.2-u.m Teflon (Millipore FGLP-013 or
equivalent)
4.4 Micro syringe: 100-uJ (Hamilton #84858 or equivalent).
4.5 Weighing pans, micro: approximately 1-cm diameter aluminum foil.
Purchase or fabricate from aluminum foil.
4.6 Boiling chips: Approximately 10-40 mesh carborundum (A.M. Thomas
#1590-030 or equivalent). Heat to 450° C for 5-10 hr or extract with methy-
lene chloride.
4.7 Water bath: Heated, capable of temperature control (+_2° C). The
bath should be used in a hood.
4.8 Balance: Analytical, capable of accurately weighing 0.0001 g.
4.9 Microbalance: Capable of accurately weighing to 0.001 mg (Mettler
model ME-30 or equivalent).
4.10 Homogenizer, high speed: Brinkmann Polytron model PT 10ST with
Teflon bearings, or equivalent.
4.11 Centrifuge: Capable of accommodating 200-ml glass centrifuge
tubes.
4.12 pH Meter and electrodes: Capable of accurately measuring pH to
jK).l pH unit.
4.13 Spatula: Having a metal blade 1-2 cm in width.
4.14 Heat lamp: 250-watt reflector-type bulb (GE #250R-40/4 or equiva-
lent) in a heat-resistant fixture whose height above the sample may be
conveniently adjusted.
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4 / ORGANIC ANALYTICAL METHODS - GC/MS
4.15 Gas chromatograph/mass spectrometer data system
4.15.1 Gas chromatograph: An analytical system complete with a
temperature-programmable gas chromatograph suitable for splitless
Injection and all required accessories including syringes, analytical
columns, and gases.
4.15.2 Column: 30-m x 0.25-mm bonded-phase si 11 cone-coated fused
silica capillary columm (J&W Scientific DB-5 or equivalent).
4.15.3 Mass spectrometer: Capable of scanning from 35 to 450 amu
every 1 sec or less, utilizing 70 volts (nominal) electron energy in the
electron impact ionization mode and producing a mass spectrum which
meets all the criteria in Table 1 when 50 ng of decafluorotriphenyl-
phosphine (DFTPP) is injected through the GC inlet.
TABLE 1. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA3
Mass Ion abundance criteria
51 30-60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40-60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17-23% of mass 442
aJ.W. Eichelberger, L.E. Harris, and W.L. Budde. 1975. Reference
compound to calibrate ion abundance measurement in gas chromatography-mass
spectrometry. Analytical Chemistry 47:995.
-------
8270 / 5
4.15.4 GC/MS interface: Any GC-to-MS interface that gives accept-
able calibration points at 50 ng per injection for each compound of
interest and achieves acceptable tuning performance criteria (see
Sections 7.2.1-7.2.4) may be used. GC-to-MS interfaces constructed of
all glass or glass-lined materials are recommended. Glass can be
deactivated by silanizing with dichlorodimethylsilane. The interface
must be capable of transporting at least 10 ng of the components of
interest from the GC to the MS. The fused silica column may also be
inserted directly into the MS source housing.
4.15.5 Data system: A computer system must be interfaced to the
mass spectrometer. The system must allow the continuous acquisition and
storage on machine-readable media of all mass spectra obtained through-
out the duration of the chromatographic program. The computer must have
software that can search any GC/MS data file for ions of a specific mass
and that can plot 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 integrating the abundance in
any EICP between specified time or scan number limits.
4.16 Gel permeation chromatography system
4.16.1 Chromatographic column: 600-mm x 25-mm I.D. glass column
fitted for upward flow operation.
4.16.2 Bio-beads S-X8: 80 g per column.
4.16.3 Pump: Capable of constant flow of 0.1 to 5 ml/min at up
to 100 psi.
4.16.4 Injector: With 5-ml loop.
4.16.5 Ultraviolet detector: 254 mm.
4.16.6 Strip chart recorder.
5.0 Reagents
5.1 Reagent water: Reagent water is defined as a water in which an
interferent is not observed at the method detection limit of each compound of
interest.
5.2 Potassium phosphate, tribasic (<3P04): Granular (ACS).
5.3 Phosphoric acid (^04): 85% aqueous solution (ACS).
5.4 Sodium sulfate, anhydrous (Na2S04): Powder (ACS).
-------
6 / ORGANIC ANALYTICAL METHODS - GC/MS
5.5 Methylene chloride: Distilled-in-glass quality (Burdick and
Jackson, or equivalent).
5.6 DiQ-Phenanthrene.
5.7 Decafluorotriphenylphosphine (DFTPP).
5.8 Retention time standards: D3-phenol, Ds-naphthalene,
Dio-phenanthrene, Di2-chrysene, and Di2-benzo(a)pyrene. Dig-perylene
may be used in place of Di2-benzo(a)pyrene.
5.9 Column performance standards: D3~phenol, D5-aniline,
D5»nitrobenzene, and D3-2,4-dinitrophenol.
5.10 Surrogate standards: Decaf1uorobiphenyl, 2-fluoroaniline, and
pentafluorophenol.
5.11 GPC calibration solution: Methylene chloride containing 100 mg
corn oil, 20 mg di-n-octyl phthalate, 3 mg coronene, and 2 mg sulfur per
100 ml.
6.0 Sample Collection, Preservation, and Handling
6.1 Grab samples must be collected in glass containers having Teflon-
lined screw caps. Sampling equipment must be free of oil and other potential
sources of contamination.
6.2 The samples must be iced or refrigerated at 4* C from the time
of collection until extraction.
6.3 All samples must be extracted within 14 days of collection and
completely analyzed within 40 days of extraction.
7.0 Procedure
7.1 Calibration
7.1.1 An internal standard calibration procedure is used. To use
this approach, the analyst must use D3-phenol, Ds-naphthalene,
Dig-phenanthrene, Di2-chrysene and Di2~benzo(a)pyrene. Di2-perylene
may be substituted for Di2benzo(a)pyrene. The analyst must further
demonstrate that measurement of the internal standard is not affected by
method or matrix interferences. Use the base peak ion as the primary
ion for quantification of the standards. If interferences are noted,
use the next most intense ion as the secondary ion. The internal
standard is added to all calibration standards and all sample extracts
analyzed by GC/MS. Retention time standards, column performance standards,
-------
8270 / 7
and a mass spectrometer tuning standard may be included in the internal
standard solution used.
7.1.1.1 A set of five or more retention time standards is
selected that will permit all components of interest in a chroma-
togram to have retention times of 0.85 to 1.20 relative to at
least one of the retention time standards. The retention time
standards should be similar in analytical behavior to the compounds
of interest and their measurement should not be affected by method
or matrix interferences. The following retention time standards are
recommended for general use: D3-phenol, Ds-naphthalene,
Di2-chrysene, and Di2-benzo(a)pyrene. Di2-perylene may be
substituted for Di2-benzo(a)pyrene. DiQ-phenanthrene serves
as a retention time standard as well as an internal standard.
7.1.1.2 Representative acidic, basic, and polar netural
compounds are added with the internal standard to assess the
column performance of the GC/MS system. The measurement of the
column performance standards should not be affected by method or
matrix interferences. The following column performance standards
are recommended for general use: D5~phenol or D3~phenol,
Ds-aniline, Ds-nitrobenzene, and D3-2,4-dinitrophenol.
These compounds can also serve as retention time standards if
appropriate and the retention time standards recommended in
Section 7.1.1.1 can serve as column performance standards if
appropriate.
7.1.1.3 Decafluorotriphenylphosphine (DFTPP) is added to
the internal standard solution to permit the mass spectrometer
tuning for each GC/MS run to be checked.
7.1.1.4 Prepare the internal standard solution by dissolving,
in 50.0 ml of methylene chloride, 10.0 mg of each standard compound
specified in Sections 7.1.1.1, 7.1.1.2, and 7.1.1.3. The resulting
solution will contain each standard at a concentration of 200 pig/ml.
7.1.2 Prepare calibration standards at a minimum of three concen-
tration levels for each compound of interest. Each ml of each calibra-
tion standard or standard mixture should be mixed with 250 u.1 of the
internal standard solution. One of the calibration standards should be
at a concentration near, but above, the method detection limit, 1 to
10 ug/ml» and the other concentrations should correspond to the expected
range of concentrations found in real samples or should define the
working range of the GC/MS system.
7.1.3 Analyze 1 u.1 of each calibration standard and tabulate the
area of the primary characteristic ion against concentration for each
compound including standard compound. Calculate response factors (RF)
for each compound as follows:
-------
8 / ORGANIC ANALYTICAL METHODS - GC/MS
RF = (AsCis)/(AisCs)
where:
As = Response for the parameter to be measured.
A-JS = Response for the internal standards.
C-js = Concentration of the internal standard in u.g/1.
Cs = Concentration of the compound to be measured in u.g/1.
If the RF value over the working range is constant (less than 20%
relative standard deviation), 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/A-js,
against RF.
7.1.4 The RF must be verified on each working day by the measure-
ment of two or more calibration standards, including one at the beginning
of the day and one at the end of the day. The response factors obtained
for the calibration standards analyzed immediately before and after a
set of samples must be within _+20% of the response factor used for
quantification of the sample concentrations.
7.2 Daily GC/MS performance tests
7.2.1 At the beginning of each day that analyses are to be
performed, the GC/MS system must be checked to see that acceptable
performance criteria are achieved for DFTPP.
7.2.2 The DFTPP performance test requires the following instru-
mental parameters:
Electron energy: 70 volts (nominal)
Mass Range: 40 to 450 amu
Maximum Scan Time: 1 sec per scan
7.2.3 Inject a solution containing 50 u.g/ml of DFTPP into the
GC/MS system or bleed DFTPP vapor directly into the mass spectrometer
and tune the instrument to achieve all the key ion criteria for the mass
spectrum of DFTPP given in Table 1.
7.2.4 DFTPP is included in the internal standard solution added
to all samples and calibration solutions. If any key ion abundance
observed for DFTPP during the analysis of a sample differs by more than
10% absolute abundance from that observed during the analysis of the
-------
8270 / 9
calibration solution, then the analysis in questino is considered
invalid. The instrument must be retuned or the sample and/or cali-
bration solution reanalyzed untilthe above condition is met.
7.3 Sample extraction
7.3.1 Samples may be extracted by Methods 3510, 3540, or 3550,
or by the following procedure. The extraction procedure involves
homogenization of the sample with methylene chloride, neutralization to
pH 7, and the addition of anhydrous sodium sulfate to remove the water.
The amount of acid or base required for the neutralization is determined
by titration of the sample. Aqueous samples are extracted using Method 3510
while organic liquids may be analyzed neat or diluted with CH2C12 and
analyzed. Solids and semi sol ids are extracted by Methods 3540 and 3550 or by
the extraction described in Steps 7.3.1 through 7.3.3.
7.3.1.1 Thoroughly mix the sample to enable a representative
sample to be obtained. Weight 3.0 g (wet weight) of sample into a
400-ml beaker. Add 75 ml methylene chloride and 150 ml water.
7.3.1.2 Homogenize the mixture for a total of 1 min using a
high-speed homogenizer. Use a metal spatula to dislodge any
material that adheres to the beaker or to the homogenizer before or
during the homogenization to ensure thorough dispersion of the sample.
7.3.1.3 Adjust the pH of the mixture to 7.0 _+ 0.2 by titration
with 0.4 M H3P04 or 0.4 M 1^04 using a pH meter to measure
the pH. Record the volume of acid or base required.
7.3.2 The extraction with methylene chloride is performed using a
fresh portion of the sample. Weigh 3.0 g (wet weight) of sample into a
200-ml centrifuge tube. Spike the sample with surrogate standards as
described in Section 8.4. Add 150 ml of methylene chloride followed by
1.0 ml of 4 M phosphate buffer pH 7.0, and an amount of 4 M ^04 or
4 M K3P04 equal to one tenth of the pH 7 acid or base volume requirement
determined in Section 7.3.1.3. For example, if the acid requirement in
Section 7.3.1.3 was 2.0 ml of 0.4 M H3P04, the amount of 4 M H3P04
needed would be 0.2 ml.
7.3T3 Homogenize the mixture for a total of 30 sec using a high-
speed homogenizer at full speed. Cool the mixture in an ice bath
or cold water bath, if necessary, to maintain a temperature of 20-30° C.
Use a metal spatula to help dislodge any material that adheres to the
centrifuge tube or homogenizer during the homogenization to obtain as
thorough a dispersion of the sample as possible. Some samples, espe-
cially those that contain much water, may not disperse well in this step
but will disperse after sodium sulfate is added. Add an amount of
anhydrous sodium sulfate powder equal to 15.0 g plus 3.0 g per ml of
the 4 M H3P04 or 4 M ^04 added in Section 7.3.2. Homogenize
the mixture again for a total of 30 sec using a high-speed homoge-
nizer at full speed. Use a metal spatula to dislodge any material that
adheres to the centrifuge tube or homogenizer during the homogenization
-------
10 / ORGANIC ANALYTICAL METHODS - GC/MS
to ensure thorough dispersion. (NOTE: This step may cause rapid
deterioration of the Teflon bearing in the homogenizer. The bearing
must be replaced whenever the rotor shaft becomes loose to prevent
damage to stainless steel parts.) Allow the mixture to stand until a
clear supernatant is obtained. Centrifuge if necessary to facilitate
the phase separation. Filter the supernatant required for Sections
7.3.4, 7.3.5, and 7.3.7 (at least 2 ml) through a 0.2-um Teflon filter.
7.3.4 Estimate the total solvent extractable content (TSEC) of the
sample by determining the residue weight of an aliquot of the supernatant
from Section 7.3.3. Transfer 0.1 ml of the supernatant to a tared
aluminum weighing dish, place the weighing dish under a heat lamp at a
distance of 8 cm from the lamp for 1 min to allow the solvent to
evaporate, and weigh on a microbalance. If the residue weight of the
0.1-ml aliquot is less than 0.05 mg, concentrate 25 ml of the supernatant
to 1.0 ml and obtain a residue weight on 0.1 ml of the concentrate. For
the concentration step, use a 25-ml evaporator tube fitted with a micro
Snyder column; add two boiling chips and heat in a water bath at 60-65* C.
Calculate the TSEC as milligrams of residue per gram of sample using
Equation 1 if concentration was not required or Equation 2 if concentra-
tion was required.
mg of residue residue weight (mg) of 0.1 ml of supernatant
g of sample " 0.002
mg of residue residue weight (mg) of 0.1 ml of cone, supernatant
g of sample " 0.05
7.3.5 If the TSEC of the sample (as determined in Section 7.3) is
less than 50 mg/g, concentrate an aliquot of the supernatant that
contains a total of only 10 to 20 mg of residual material. For example,
if the TSEC is 44 mg/g, use a 20-ml aliquot of the supernatant, which
will contain 17.6 mg of residual material, or if the TSEC is 16 mg/g,
use a 50-ml aliquot of the supernatant, which will contain 16.0 mg of
residual material. If the TSEC is less than 10 mg/g, use 100 ml of the
supernatant. Perform the concentration by transferring the aliquot of
the supernatant to a K-D flask fitted into a 25-ml concentrator tube.
Add two boiling chips, attach a three-ball macro Snyder column to the
K-D flask, and concentrate the extract using a water bath at 60 to 65* C.
Place the K-D apparatus in the water bath so that the concentrator
tube is about half immersed in the water and the entire rounded surface
of the flask is bathed with water vapor. Adjust the vertical position
of the apparatus and the water temperature as required to complete the
concentration in 15 to 20 min. At the proper rate of distillation, the
balls of the column actively chatter but the chambers do not flood.
When the liquid has reached an apparent volume of 5 to 6 ml, remove the
K-D apparatus from the water bath and allow the solvent to drain for at
least 5 min while cooling. Remove the Snyder column and rinse the
flask and its lower joint into the concentrator tube with the methylene
-------
8270 / 11
chloride to bring the volume to 10.0 ml. Mix the contents of the
concentrator tube by inserting a stopper and inverting several times.
7.3.6 Analyze the concentrate from Section 7.3.5 or, if the TSEC
of the sample is 50 mg/g or more, analyze the supernatant from Section
7.3 using gas chromatography. Use a 30-m x 0.25-mm bonded-phase silicone-
coated fused-silica capillary column under the chromatographic conditions
described in Section 7.5. Estimate the concentration factor or dilution
factor required to give the optimum concentration for the subsequent
GC/MS analysis. In general, the optimum concentration will be one in
which the average peak height of the five largest peaks or the height of
an unresolved envelope of peaks is the same as that of an internal
standard at a concentration of 50-100 |ig/ml.
7.3.7 If the optimum concentration determined in Section 7.3.6 is
20 mg of residual material per ml or less, proceed to Section 7.3.8. If
the optimum concentration is greater than 20 mg of residual material per
ml and if the TSEC is greater than 50 mg/g, apply the GPC cleanup
procedure described in Section 7.4. For the GPC cleanup, concentrate
90 ml of the supernatant from Section 7.3.3 or a portion of the super-
natant that contains a total of 600 mg of residual material (whichever
is the smaller volume). Use the concentration procedure described in
Section 7.3.5 and concentrate to a final volume of 15.0 ml. Stop the
concentration prior to reaching 15.0 rnl if any oily or semisolid mate-
rial separates out and dilute as necessary (up to a maximum final volume
equal to the volume of supernatant used) to redissolve the material.
(Disregard the presence of small amounts of inorganic salts that may
settle out.)
7.3.8 Concentrate further or dilute as necessary an aliquot of the
concentrate from Section 7.3.5 or an aliquot of the supernatant from
Section 7.3.3, or if GPC cleanup was necessary, an aliquot of the
concentrate from Section 7.4.3 to obtain 1.0 ml of a solution having
the optimum concentration, as described in Section 7.3.6, for the GC/MS
analysis. If the aliquot needs to be diluted, dilute it to a volume of
1.0 ml with methylene chloride. If the aliquot needs to be concentrated,
concentrate it to 1.0 ml as decribed in Section 7.3.4. Do not let the
volume in the concentrator tube go below 0.6 ml at any time. Stop the
concentration prior to reaching 1.0 ml if any oily or semisolid material
separates out and dilute as necessary (up to a maximum final volume of
10 ml) to redissolve the material. (Disregard the presence of small
amounts of inorganic salts that may settle out). Add 250 j^l of the
internal standard solution, containing 50 \ig each of the internal
standard, retention time standards, column performance standards, and
DFTPP, to 1.0 ml of the final concentrate and save for GC/MS analysis as
described in Section 7.5. Calculate the concentration in the original
sample that is represented by the internal standard using Equation 3 if
an aliquot of the concentrate from Section 7.3.5 was used in Section
7.3.8, Equation 4 if an aliquot of the supernatant from Section 7.3.3
-------
12 / ORGANIC ANALYTICAL METHODS - GC/MS
was used in Section 7.3.8 or Equation 5 if an aliquot of the GPC concen-
trate from Section 7.4.3 was used in Section 7.3.8.
ug of Int. Std. _
g of sample
_50 150
r\ /\ iT
"»
F1na1
's(7.3.5) vc (7.3.8)
(Eq. 3)
ug of Int. Std. _ _50 ^50 Final Vol. (ml)
g of sample
s(7.3.8)
(Eq. 4)
of Int. Std.
g of sample
where:
50 150
-3 x „
Final Vol. (ml)
s(7.3.7) GPC (7.3.7)
(Eq. 5)
Vs = Volume of supernatant from Section 7.3.3 used in
Sections 7.3.5, 7.3.8, 7.3.7
vc(7.3.8) = Volume of concentrate from Section 7.3.5 used in
Section 7.3.8
VF (7.3.7) = Final volume of concentrate in Section 7.3.7
= Volume of GPC concentrate from Section 7.4.3 used in
Section 7.3.8
Use this calculated value for the quantification of individual compounds
as described in Section 7.7.2.
7.4 Cleanup using gel permeation chromatography
7.4.1 Prepare a 600-mm x 25-mm I.D. gel permeation chromatography
(GPC) column by slurry packing using 80 g of Bio-Beads S-X8 that have
been swelled in methylene chloride for at least 4 hr. Prior to
initial use, rinse the column with methylene chloride at 1 ml/min for
16 hr to remove any traces of contaminants. Calibrate the system by
injecting 5 ml of the GPC calibration solution, eluting with methylene
chloride at 5 ml/min for 50 min and observing the resultant UV
detector trace. The column may be used indefinitely as long as no
darkening or pressure increases occur and a column efficiency of at least
500 theoretical plates is achieved. The pressure should not be permitted
to exceed 50 psi. Recalibrate the system daily.
7.4.2 Inject a 5-ml aliquot of the concentrate from Section 7.3.7
onto the GPC column and elute with methylene chloride at 5 ml/min for
50 min. Discard the first fraction that elutes up to a retention time
represented by the minimum between the corn oil peak and the di-n-octyl
-------
8270 / 13
phthalate peak in the calibration run. Collect the next fraction
eluting up to a retention time represented by the minimum between the
coronene peak and the sulfur peak in the calibration run. Apply the
above GPC separation to a second 5-ml aliquot of the concentrate from
Section 7.3.7 and combine the fractions collected.
7.4.3 Concentrate the combined GPC fractions to 10.0 ml as
described in Section 7.3.5. Estimate the TSEC of the concentrate as
described in Section 7.3.4. Estimate the TSVC of the concentrate as
described in Section 7.3.6.
7.5 Gas chromatography/mass spectrometry
7.5.1 Analyze the 1-ml concentrate from Section 7.3.8 by GC/MS
using a 30-m x 0.25-mm bonded-phase silicone-coated fused-silica capillary
column. The recommended GC operating conditions to be used are as follows:
Initial column temperature hold: 40° C for 4 min
Column temperature program: 40-270° C at 10 degrees/min
Final column temperature hold: 270° C (until Benzo(ghi)perylene
has eluted)
Injector temperature: 290° C
Transfer line temperature: 300° C
Injector: Grob-type, splitless
Sample volume: 1-2 u.1
Carrier gas: Hydrogen (preferred) at 50 cm/sec or helium at
30 cm/sec
7.5.2 If the response for any ion exceeds the working range of the
GC/MS system, dilute the extract and reanalyze.
7.5.3 Perform all qualitative and quantitative measurements as
described in Sections 7.6 and 7.7. When the extracts are not being used
for analyses, store them at 4° C protected from light in screw-cap vials
equipped with unpierced Teflon-lined septa.
7.6 Qualitative identification
7.6.1 Obtain an EICP for the primary characteristic ion and at
least two other characteristic ions for each compound when practical.
The following criteria must be met to make a qualitative identification.
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14 / ORGANIC ANALYTICAL METHODS - GC/MS
7.6.1.1 The characteristic ions for each compound of interest
must maximize in the same or within one scan of each other.
7.6.1.2 The retention time must fall within +15 sec (based on
the relative retention time) of the retention time of the authentic
compound.
7.6.1.3 The relative peak heights of the characteristic ions
in the EICP's must fall within ^20% of the relative intensities of
these ions in a reference mass spectrum.
7.7 Quantitative determination
7.7.1 When a compound has been identified, the quantification of
that compound will be based on the integrated abundance from the EICP of
the primary characteristic ion. In general, the primary characteristic
ion selected should be a relatively intense ion as interference-free as
possible, and as close as possible in mass to the characteristic ion of
the internal standard used.
7.7.2 Use the internal standard technique for performing the
quantification. Calculate the concentration of each individual compound
of interest in the sample using Equation 6.
Concentration, ug/g = "9 of Int. Std. x ^s_ x J_ (E 6)
g of sample A-js RF
where:
° n * *
= internal standard concentration factor calculated
- —
9 of samPle in Section 7.3.8.
As = Area of the primary characteristic ion of the
compound being quantified
A-JS = Area of the primary characteristic ion of the
internal standard
RF = Response factor of the compound being quantified
(determined in Section 7.1.3).
7.7.3 Report results in ng/g without correction for recovery data.
When duplicate and spiked samples are analyzed, report all data obtained
with the sample results.
7.7.4 If the surrogate standard recovery falls outside the control
limits in Section 8.3, the data for all compounds in that sample must
be labeled as suspect.
-------
8270 / 15
8.0 Quality Control
8.1 Each laboratory that uses this method is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and the analysis
of spiked samples as a continuing check on performance. The laboratory is
required to maintain performance records to define the quality of data that
is generated. Ongoing performance checks must be compared with established
performance criteria to determine if the results of analyses are within the
accuracy and precision limits expected of the method.
8.1.1 Before performing any analyses, the analyst must demon-
strate the ability to generate acceptable accuracy and precision with
this method. This ability is established as described in Section 8.2.
8.1.2 The laboratory must spike all samples including check
samples with surrogate standards to monitor continuing laboratory
performance. This procedure is described in Section 8.4.
8.2 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations using a repre-
sentative sample as a check sample.
8.2.1 Analyze four aliquots of the unspiked check sample according
to the method beginning in Section 7.3.
8.2.2 For each compound to be measured, select a spike concen-
tration representative of twice the level found in the unspiked check
sample or a level equal to 10 times the expected detection limit,
whichever is greater. Prepare a spiking solution by dissolving the
compounds in methylene chloride at the appropriate levels.
8.2.3 Spike a minimum of four aliquots of the check sample with
the spiking solution to achieve the selected spike concentrations.
Spike the samples after they have been transferred to centrifuge tubes
for extraction. Analyze the spiked aliquots according to the method
described beginning in Section 7.3.
8.2.4 Calculate the average percent recovery (R) and the standard
deviation of the percent recovery (s) for all compounds and surrogate
standards. Background corrections must be made before R and s calcula-
tions are performed. The average percent recovery must be greater than
20 for all compounds to be measured and greater than 60 for all surro-
gate compounds. The percent relative standard deviation of the percent
recovery (s/R x 100) must be less than 20 for all compounds to be
measured and all surrogate compounds.
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16 / ORGANIC ANALYTICAL METHODS - GC/MS
8.3 The analyst must calculate method performance criteria for each of
the surrogate standards.
8.3.1 Calculate upper and lower control limits for method perform-
ance for each surrogate standard, using the values for R and s calculated
in Section 8.2.4:
Upper Control Limit (UCL) = R + 3s
Lower Control Limit (LCL) = R - 3s
The UCL and LCL can be used to construct control charts that are useful
in observing trends in performance.
8.3.2 For each surrogate standard, the laboratory must maintain a
record of the R and s values obtained for each surrogate standard in
each waste sample analyzed. An accuracy statement should be prepared
from these data and updated regularly.
8.4 The laboratory is required to spike all samples with the surrogate
standard to monitor spike recoveries. The spiking level used should be that
which will give a concentration in the final extract used for GC/MS analysis
that is equal to the concentration of the internal standard assuming a 100%
recovery of the surrogate standards. For unknown samples, the spiking level
is determined by performing the extraction steps in Section 7.3 on a separate
aliquot of the sample and calculating the amount of internal standard per
gram of sample as described in Section 7.3.8. If the recovery for any surro-
gate standard does not fall within the control limits for method performance,
the results reported for that sample must be qualified as being outside of
control limits. The laboratory must monitor the frequency of data so qualified
to ensure that it remains at or below 5%. Three surrogate standards, namely
decaf1uorobipheny1, 2-fluoroaniline, and pentafluorophenol, are recommended
for general use to monitor recovery of neutral, basic, and acidic compounds,
respectively.
8.5 Before processing any samples, the analyst must demonstrate through
the analysis of a process blank that all glassware and reagent interferences
are under control. Each time a set of samples is extracted or there is a
change in reagents, a process blank should be analyzed to determine the level
of laboratory contamination.
8.6 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. Field replicates may be analyzed to monitor the precision
of the sample technique. Whenever possible, the laboratory should perform
analysis of standard reference materials and participate in relevant perform-
ance evaluation studies.
-------
8270 / 17
8.7 The features that must be monitored for each GC/MS analysis run for
quality control purposes and for which performance criteria must be met are
as follows:
t Relative ion abundances of the mass spectrometer tuning compound
DFTPP.
• Response factors of column performance standards and retention time
standards.
• Relative retention time of column performance standards and retention
time standards.
• Peak area intensity of the internal standard, e.g., DiQ-phenanthrene.
-------
8.3 High Performance Liquid Chromatographic Methods (8300's)
Methods appropriate for organic analysis by HPLC methods are included
on the following pages.
-------
METHOD 8310
POLYNUCLEAR AROMATIC HYDROCARBONS
1.0 Scope and Application
Method 8310 is used to determine the concentration of certain polynuclear
aromatic hydrocarbons (PAH) in groundwater and wastes. Specifically, Method 8310 is
used to detect the following substances:
Acenaphthene Chrysene
Acenaphthylene Dibenzo(a,h)anthracene
Anthracene Fluoranthene
Benzo(a)anthracene Fluorene
Benzo(a)pyrene Indeno(l,2,3-cd)pyrene
Benzo(b)fluoranthene Naphthalene
Benzo(ghi)perylene Phenanthrene
Benzo(k)fluoranthene Pyrene
1.2 Use of Method 8310 presupposes a high expectation of finding the
specific compounds of interest. If the user is attempting to screen samples
for any or all of the compounds above, he must develop independent protocols
for the verification of identity.
1.3 The detection limits for Method 8310 are listed in Table 1. The
sensitivity of this method usually depends on the level of interferences
rather than instrumental limitations. The limits of detection listed in
Table 1 for the liquid chromatographic approach represent sensitivities that
can be achieved in the absence of interferences. When interferences are
present, the level of sensitivity will be lower.
1.4 This method is recommended for use only by experienced residue
analysts or under the close supervision of such qualified persons.
2.0 Summary of Method
2.1 A 1-liter sample 'of wastewater is extracted with methylene chloride
using separatory funnel techniques. The extract is dried and concentrated to
a volume of 10 ml or less. The compounds in the extract are then measured by
High Performance Liquid Chromatography (HPLC).
2.2 A general purpose cleanup procedure to aid the analyst in eliminating
interferences is described.
3.0 Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpreta-
tion of the chrornatograms. All these materials must be demonstrated to be
free from interferences under the conditions of the analysis by running
-------
2 / ORGANIC ANALYTICAL METHODS - HPLC
TABLE 1. HIGH PERFORMANCE LIQUID CHROMATOGRAPHY OF PAHa
Detection limit (u.g/1)
Compound Retention time (min) UV Fluorescence
Naphthalene 16.17 1.8
Acenaphthylene 18.10 2.3
Acenaphthene 20.14 1.8
Fluorene 20.89 0.21
Phenanthrene 22.32 0.64
Anthracene 23.78 0.66
Fluoranthrene 25.00 0.21
Pyrene 25.94 0.27
Benzo(a)anthracene 29.26 0.013
Chrysene 30.14 0.15
Benzo(b)fluoranthene 32.44 0.018
Benzo(k)fluoranthene 33.91 0.017
Benzo(a)pyrene 34.95 0.023
Dibenzo(a,h)anthracene 37.06 0.030
Benzo(ghi)pery1ene 37.82 0.076
Indeno(l»2,3-cd)pyrene 39.21 0.043
aHPLC conditions: Reverse phase HC-ODS Sil-X 2.6 x 250 mm Perkin-
Elmer column; isocratic elution for 5 min using 40% acetonitrile/60% water,
then linear gradient elution to 100% acetonitrile over 25 min; flow rate is
0,,5 ml/min.
-------
8310 / 3
method blanks. Specific selection of reagents and purification of solvents
by distillation in all-glass systems may be required.
3.2 Interferences coextracted from the samples will vary considerably
from source to source, depending upon the diversity of the industrial complex
or municipality being sampled. While a general cleanup technique is provided
as part of this method, individual samples may require additional cleanup
approaches to achieve the sensitivities stated in Table 1.
3.3 The extent of interferences that may be encountered using liquid
chromatographic techniques has not been fully assessed. Although the chromat-
ographic conditions described allow for a unique resolution of the specific
PAH compounds covered by this method, other PAH compounds may interfere.
3.4 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water or solvent blank that the
entire analytical system is interference-free. Standard quality assurance
practices should be used with this method. Field replicates should be
collected to validate the precision of the sampling technique. Laboratory
replicates should be analyzed to validate the precision of the analysis.
Fortified samples should be analyzed to validate the accuracy of the anal-
yses. Where doubt exists over the identification of a peak, confirmatory
techniques such as mass spectroscopy should be used.
3.5 The analyst should maintain constant surveillance of both the
performance of the analytical system and the effectiveness of the method in
dealing with each sample matrix. This is done by spiking each waste sample
with known amounts of the compounds that the waste is being analyzed for.
Using these spiked waste samples, the sensitivity of the instrument is then
readjusted so that 1 [ig/g of sample can be readily detected. Detection
limits necessary for groundwater monitoring are much lower. The analyst
should adjust instrument sensitivity according to Table 1 when analyzing
groundwater samples.
4.0 Apparatus and Materials
4.1 Sampling equipment, for discrete or composite sampling
4.1.1 Grab sample bottle: Amber glass, 1-liter or 1-quart volume.
French or Boston Round design is recommended. The container must be
washed and solvent rinsed before use to minimize interferences.
4.1.2 Bottle caps: Threaded to screw on to the sample bottles.
Caps must be lined with Teflon. Foil may be substituted if sample is
not corrosive.
4.1.3 Compositing equipment: Automatic or manual compositing
system. Must incorporate glass sample containers for the collection of
a minimum of 250 ml. Sample containers must be kept refrigerated during
sampling. No tygon or rubber tubing may be used in the system.
-------
4 / ORGANIC ANALYTICAL METHODS - HPLC
4.2 Separatory funnel: 2000 ml, with Teflon stopcock.
4.3 Drying column: 20-mm-I.D. pyrex chromatographic column with coarse
frit.
4.4 Kuderna-Danish (K-D) apparatus
4.4.1 Concentrator tube: 10ml, graduated (Kontes K-570050-1025
or equivalent). Calibration must be checked. Ground glass stopper
(size 22 joint) is used to prevent evaporation of extracts.
4.4.2 Evaporative flask: 500 ml (Kontes K-57001-0500 or equivalent).
Attach to concentrator tube with springs (Kontes K-662750-0012).
4.4.3 Snyder column: Three-ball macro (Kontes K503000-0121 or
equivalent).
4.4.4 Snyder column: Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4.5 Boiling chips: Solvent extracted, approximately 10/40
mesh.
4.5 Water bath: Heated, with concentric ring cover, capable of tempera-
ture control (^2° C). The bath should be used in a hood.
4.6 HPLC apparatus
4.6.1 Gradient pumping system, constant flow.
4.6.2 Reverse phase column, 5-micron HC-ODS Sil-X, 250 mm x 2.6 mm
I.D. (Perkin Elmer No. 809-0716 or equivalent).
4.6.3 Fluorescence detector, for excitation at 280 nm and emission
at 380 nm.
4.6:4 UV detector, 254 nm, coupled fluorescence detector.
4.6.5 Strip chart recorder compatible with detectors. (A data
system for measuring peak areas is recommended.)
4.7 Chromatographic column: 250 mm long x 10 mm I.D. with coarse-fritted
disc at bottom and Teflon stopcock.
5.0 Reagents
5.1 Preservatives
5.1.1 Sodium hydroxide: (ACS) 10 N in distilled water.
-------
8310 / 5
5.1.2 Sulfuric acid: (ACS) Mix equal volumes of cone.
with distilled water.
5.1.3 Sodium thiosulfate: (ACS) Granular.
5.2 Methylene chloride, pentane, cyclohexane, high purity water:
HPLC quality, distilled in glass.
5.3 Sodium sulfate: (ACS) Granular, anhydrous (purified by heating
at 400° C for 4 hr in a shallow tray).
5.4 Stock standards: Prepare stock standard solutions at a concentration
of 1.00 ug/ul by dissolving 0.100 g of assayed reference material in pesticide
quality isooctane or other appropriate solvent and diluting to volume in a 100-ml
ground-glass-stoppered volumetric flask. The stock solution is transferred to
ground-glass-stoppered reagent bottles, stored in a refrigerator, and checked
frequently for signs of degradation or evaporation, especially just prior to pre-
paring working standards from them.
5.5 Acetonitrile: Spectral quality.
5.6 Silica gel: 100/120 mesh desiccant (Davison Chemical grade 923 or
equivalent). Before use, activate for at least 16 hr at 130' C in a foil-
covered glass container.
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 Section One of this manual.
6.2 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed, except that the bottle must not be
prewashed with sample before collection. Composite samples should be collected
in refrigerated glass containers in accordance with the requirements of the
program. Automatic sampling equipment must be free of tygon and other
potential sources of contamination.
6.3 The samples must be iced or refrigerated from the time of collection
until extraction. Chemical preservatives should not be used in the field
unless more than 24 hr will elapse before delivery to the laboratory. If the
samples will not be extracted within 48 hr of collection, adjust the sample
to a pH range of 6.0-8.0 with sodium hydroxide or sulfuric acid and add 35 mg
sodium thiosulfate per part per million of free chlorine per liter.
6.4 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
-------
6 / ORGANIC ANALYTICAL METHODS - HPLC
7.0 Procedure
7.1 Sample extraction
7.1.1 Mark the water meniscus on the side of the sample bottle for
later determination of sample volume. Pour the entire sample into a
2-liter separatory funnel. Check the pH of the sample with wide-range
pH paper and adjust to within the range of 5-9 with sodium hydroxide or
sulfuric acid.
7.1.2 Add 60 ml methylene chloride to the sample bottle, seal, and
shake 30 sec to rinse the inner walls. Transfer the solvent into the
separatory funnel, and extract the sample by shaking the funnel for
2 min with periodic venting to release vapor pressure. Allow the
organic layer to separate from the water phase for a minimum of 10 min.
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, but may include stirring, filtration of the emulsion through
glass wool, or centrifugation. Collect the methylene chloride extract
in a 250-ml Erlenmeyer flask.
7.1.3 Add a second 60-ml volume of methylene chloride to the
sample bottle and complete the extraction procedure a second time,
combining the extracts in the Erlenmeyer flask.
7.1.4 Perform a third extraction in the same manner. Pour the
combined extract through a drying column containing 3-4 in. of anhydrous
sodium sulfate, and collect it in a 500-ml Kuderna-Danish (K-D) flask
equipped with a 10-ml concentrator tube. Rinse the Erlenmeyer flask and
column with 20-30 ml methylene chloride to complete the quantitative
transfer.
7.1.5 Add 1 or 2 clean boiling chips to the 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 (60-65° C) so that the concentrator tube is partially immersed in
the hot water, and the entire lower rounded surface of the flask is
bathed in vapor. Adjust the vertical position of the apparatus and the
water temperature as required to complete the concentration in 15-20 min.
At the proper rate of distillation, the balls of the column will
actively chatter but the chambers will not flood. When the apparent
volume of liquid reaches 1 ml, remove the K-D apparatus and allow it to
drain for at least 10 min while cooling. Remove the Snyder column and
rinse the flask and its lower joint into the concentrator tube with
1-2 ml of methylene chloride. A 5-ml syringe is recommended for this
operation. Stopper the concentrator tube and store refrigerated if
further processing will not be performed immediately.
-------
8310 / 7
7.1.6 Determine the original sample volume by refilling the sample
bottle to the mark and transferring the liquid to a 1000-ml graduated
cylinder. Record the sample volume to the nearest 5 ml.
7.1.7 If the sample requires cleanup before chromatographic
analysis, proceed to Section 7.2. If the sample does not require
cleanup, or if the need for cleanup is unknown, analyze an aliquot of
the extract according to Section 7.4.
7.2 Cleanup and separation
7.2.1 Before the silica gel cleanup technique can be utilized, the
extract solvent must be exchanged to cyclohexane. Add a 1- to 10-ml
aliquot of sample extract (in methylene chloride) and a boiling chip to
a clean K-D concentrator tube. Add 4 ml cyclohexane and attach a
micro-Snyder column. Prewet the micro-Snyder column by adding 0.5 ml
methylene chloride to the top. Place the micro K-D apparatus on a
boiling (100° C) 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 concentration in
5-10 min. At the proper rate of distillation, the balls of the column
will actively chatter but the chambers will not flood. When the apparent
volume of the liquid reaches 0.5 ml, remove K-D apparatus and allow it
to drain for at least 10 min while cooling. Remove the micro-Snyder
column and rinse its lower joint into the concentrator tube with a
mimimum of cyclohexane. Adjust the extract volume to about 2 ml.
7.2.2 Prepare a slurry of 10 g activated silical gel in methylene
chloride and place this in a 10-mm-I.D. chromatography column. Gently
tap the column to settle the silica gel and elute the methylene chloride.
Add 1-2 cm of anhydrous sodium sulfate to the top of the silica'gel.
7.2.3 Preelute the column with 40 ml pentane. Discard the eluate
and just prior to exposure to 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.
7.2.4 Just prior ifo exposure of the sodium sulfate layer to the
air, add 25 ml pentane and continue elution of the column. Discard the
pentane eluate.
7.2.5 Elute the column with 25 ml of 40% methylene chloride/60%
pentane and collect the eluate in a 500-ml K-D flask equipped with a
10-ml concentrator tube. Elution of the column should be at a rate of
about 2 ml/min.
7.2.6 Concentrate the collected fraction to less than 10 ml by K-D
techniques as in 7.1.5, using pentane to rinse the walls of the glassware.
Proceed with HPLC or gas chromatographic analysis.
-------
8 / ORGANIC ANALYTICAL METHODS - HPLC
7.2.7 To the extract in the concentrator tube, add 4 ml acetonitrile
and a new boiling chip, then attach a micro-Snyder column. Increase the
temperature of the hot water bath to 95-100° C. Concentrate the solvent
as above. After cooling, remove the micro-Snyder column and rinse its
lower joint into the concentrator tube with about 0.2 ml acetonitrile.
Adjust the extract volume to 1.0 ml.
7.3 Calibration
7.3.1 Prepare calibration standards that contain the compounds of
interest, either singly or mixed together. The standards should be
prepared at concentrations covering two or more orders of magnitude that
will completely bracket the working range of the chromatographic system.
If the sensitivity of the detection system can be calculated from
Table 1 as 100 u.g/1 in the final extract, for example, prepare standards
at 10 u.g/1, 50 ug/1, 100 ug/1, 500 u.g/1, etc. so that injections of
1-5 ul of each calibration standard will define the linearity of the
detector in the working range.
7.3.2 Assemble the necessary HPLC apparatus and establish operating
parameters equivalent to those indicated in Table 1. By injecting
calibration standards, establish the sensitivity limit of the detectors
and the linear range of the analytical systems for each compound.
7.3.3 Before using any cleanup procedure, the analyst must process
a series of calibration standards through the procedure to validate
elution patterns and the absence of interferences from the reagents.
7.4 High Performance Liquid Chrornatography (HPLC)
7.4.1 Table 1 summarizes the recommended HPLC column materials and
operating conditions for the instrument. Included in this table ere
estimated retention times and sensitivities that should be achieved by
this method. An example of the separation achieved by this column is
shown in Figure 1. Calibrate the system daily with a minimum of three
injections of calibration standards.
7.4.2 Inject 2-5 u.1 of the sample extract with a high pressure
syringe or sample injection loop. Record the volume injected to the
nearest 0.05 u.1, and the resulting peak size, in area units.
7.4.3 If the peak area exceeds the linear range of the system,
dilute the extract and reanalyze.
7.4.4 If the peak area measurement is prevented by the pressure of
interference, further cleanup is required.
7.4.5 The UV detector is recommended for the determination of
naphthalene and acenaphthylene, and the fluorescence detector is recom-
mended for the remaining PAH.
-------
8310 / 9
Column: HC-ODSSIL-X
Mobile Phase: 40% to 100% Acetonitrile in Water
Dectector: Fluorescence
20
24
28
32
36
40
RETENTION TIME (MINUTES)
Figure 1. Liquid chromatogram of polynuclear aromatics.
-------
10 / ORGANIC ANALYTICAL METHODS - HPLC
7.5 Calculations
7.5.1 Determine the concentration of individual compounds according
to the formula:
Concentration, ng/1 =
(Vi)(Vs)
where:
A = Calibration factor for chromatographic system (in ng
material per area unit)
B = Peak size in injection of sample extract (in area units)
V.,- = Volume of extract injected (u.1)
Vt = Volume of total extract (u.1)
Vs = Volume of water extracted (ml).
7.5.2 Report results in u.g/1 without correction for recovery data.
When duplicate and spiked samples are analyzed, all data obtained should
be reported.
8.0 Quality Control
8.1 Before processing any samples, the analyst should demonstrate,
through the analysis of a distilled water method blank, that all glassware
and reagents are interference-free. Each time a set of samples is extracted
or there is a change in reagents, a method blank should be processed as a
safeguard against laboratory contamination.
8.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to validate the precision of
the sampling technique. Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified waste samples should be analyzed to
validate the accuracy of the analysis. If the fortified waste samples do not
indicate sufficient sensitivity to detect less than or equal to 1 uxj/g of
sample, then the sensitivity of the instrument should be increased or the
extract subjected to additional cleanup. Detection limits to be used for
groundwater samples are indicated in Table 1. Where doubt exists over the
identification of a peak on the chromatogram, confirmatory techniques such as
fraction collection and GC/MS should be used.
-------
8310 - 11
8.3 The method detection limit (MDL) is defined as the minimum concen-
tration of a substance that can be measured and reported with 99% confidence
that the value is above zero. The MDL concentrations listed in Table 1 were
obtained using reagent water. Similar results were achieved using represen-
tative wastewaters. The MDL actually achieved in a given analysis will vary
depending on instrument sensitivity and matrix effects.
8.4 In a single laboratory, using reagent water and wastewaters spiked
at or near background levels, the average recoveries presented in Table 2
were obtained. The standard deviation of the measurement in percent recovery
is also included in Table 2.
TABLE 2. SINGLE OPERATOR ACCURACY AND PRECISION
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(ghi )perylene
Benzo(k)fluoranthene
Chrysene
Di benzo(a ,h )anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Average
percent
recovery
88
93
93
89
94
97
86
94
88
87
116
90
94
78
98
96
Standard Spike Number
deviation range of
percent (ug/1 ) analyses
5.7
6.4
6.3
6.9
7.4
12.9
7.3
9.5
9.0
5.8
9.7
7.9
6.4
8.3
8.4
8.5
11.6-25
250-450
7.9-11.3
0.64-0.66
0.21-0.30
0.24-0.30
0.42-3.4
0.14-6.2
2.0-6.8
0.4-1.7
0.3-2.2
6.1-23
0.96-1.4
20-70
3.8-5.0
2.3-6.9
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
matrix
types
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
-------
SECTION NINE
MISCELLANEOUS ANALYTICAL METHODS
Methods appropriate for analysis by a number of miscellaneous analytical
methods (9000 series) are included on the following pages.
-------
METHOD 9010
TOTAL AND AMENABLE CYANIDE
1.0 Scope and Application
1.1 Method 9010 is used to determine the concentration of inorganic
cyanide in a waste or leachate. The method detects inorganic cyanides that
are present as either simple soluble salts or complex radicals. It is used to
determine values for both total cyanide and cyanide amenable to chlorinatioh.
Method 9010 does not determine the "reactive" cyanide content of wastes
containing iron-cyanide complexes.
2.0 Summary of Method
2.1 The cyanide as hydrocyanic acid (HCN) is released from cyanide
complexes by means of a reflux-distillation operation and absorbed in a
scrubber containing sodium hydroxide solution. The cyanide ion in the
absorbing solution is then determined colorimetrically.
2.2 In the colorimetric measurement, the cyanide is converted to
cyanogen chloride (CNC1) by reaction with chloramine-T at a pH less than 8
without hydrolyzing to the cyanate. After the reaction is complete, color is
formed on the addition of pyridine-barbituric acid reagent. The absorbance is
read at 570 nm for pyridine-barbituric acid reagent. To obtain colors of
comparable intensity, it is essential to have the same salt content in both
the sample and the standards.
3.0 Interferences
3.1 Interferences are eliminated or reduced by using the distillation
procedure described in Procedure 7.2.3, 7.2.4, and 7.2.5.
3.2 Sulfides adversely affect the colorimetric procedures. Samples that
contain hydrogen sulfide, metal sulfides or other compounds that may produce
hydrogen sulfide during the distillation should be distilled by the optional
procedure described in procedure 7.2.3.
3.3. High res.ults may be obtained for samples that contain nitrate
and/or nitrite. During the distillation, nitrate and nitrite will form
nitrous acid which will react with some organic compounds to form oximes.
These comounds formed will decompose under test conditions to generate HCN.
The interference of nitrate and nitrite is eliminated by pretreatment with
sulfamic acid.
Revised 4/84
-------
9010 / 2
Connecting Tubing
Alt inn Condtnser
On«-Liter
Boiling Flask
Suction
Figure 1. Apparatus for cyanide distillation.
-------
9010 / 3
COOLING WATER
INLET TUBE*
SCREW CLAMP
4
TO LOW VACUUM
SOURCE
* ABSORBER
"- DISTILLING FLASK
HEATER-
O
Figure 2. Cyanide distillation apparatus.
Revised 4/84
-------
9010 / 4
4.0 Apparatus
4.1 Reflux distillation apparatus such as shown in Figure 1 or 2. The
boiling flask should be of 1 liter size with inlet tube and provision for
condenser. The gas absorber may be a Fisher-Mi lligan scrubber.
4.2 Spectrophotometer suitable for measurements t 570 nm with a 1.0 cm
cell or larger.
4.3 Flow meter, such as Lab Crest with stainless steel float (Fisher
11-164-50).
4.4 Technicon Auto-Analyzer
4.4.1 Sampler
4.4.2 Cyanide manifold. (See Figure 3.)
4.4.3 Proportioning pump.
4.4.4 Colorimeter equipped with a 15 mm flowcell and 570 nm filter.
4.4.5 Recorder.
5.0 Reagents
5.1 Sodium hydroxide solution, 1.25N: Dissolve 50 g of NaOH in
distilled water, and dilute to 1 liter with distilled water.
5.2 Bismuth nitrate solution: Dissolve 30.0 grams of Bi(N03)3 in 100
mis of distilled water. While stirring, add 250 mis of acetic acid. Stir
until dissolved. Dilute to 1 liter with distilled water.
5.3 Sulfuric acid; 18N: Slowly add 500 ml of concentrated ^$04 to 500
ml of distilled water.
5.4 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of NaHgPO/p^O in 1
liter of distilled water. Refrigerate this solution.
5.5 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in 900
ml of distilled water. Standardize with 0.0192 N AgN03« Dilute to
appropriate concentration so that 1 ml = 1 mg CN.
5.6 Standard cyanide solution, intermediate: Dilute 100.0 ml of stock
(1 ml = 1 mg CN) to 1000 ml with distilled water (1 ml = 100 g).
5.7 Working standard cyanide solution: Prepare fresh daily by diluting
100.0 ml of intermediate cyanide solution to 1000 ml with distilled water and
store in a glass stoppered bottle. 1 ml = 10.0 ug CN.
5.8 Magnesium chloride solution: Weigh 510 g of MgCl2*6H20 into a
1000 ml flask, dissolve and dilute to 1 liter with distilled water.
Revised 4/84
-------
9010 / 5
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-------
9010 / 6
5.9 Sulfamic acid solution: Dissolve 40 g of sulfamic acid in distilled
water. Dilute to 1 liter.
5.10 Calcium Hypochlorite solution: Dissolve 5 g of calcium hypochlorite
(Ca(OCl)2) in 100 ml of distill.ed water.
5.11 Potassium Iodide-starch test paper.
5.12 Reagents for manual colorimetric determination;
5.12.1 Pyridine-Barbituric Acid Reagent: Place 15 g of barbituric
acid in a 250 ml volumetric flask and add just enough distilled water to
wash the sides of the flask and wet barbituric acid. Add 75 ml of
pyridine and mix. Add 15 ml of cone. HC1, mix and cool to room
temperature. Dilute to 250 ml with distilled water and mix., This
reagent is stable for approximately six months if stored in a cool, dark
place.
5.12.2 Chloramine-T solution: Dissolve 1.0 g of white, water
soluble Chloramine-T in 100 ml of distilled water and refrigerate until
ready to use.
5.13 Reagents for automated colorimetric determination:
5.13.1 Distillation agent: Carefully add 250 ml of 85% phosphoric
acid and 50 ml of hypophosphorus acid to 700 ml of distilled water, mix,
and dilute to one liter with distilled water.
5.13.2 Sodium dihydrogenphosphate, 1M (phosphate buffer):
Dissolve 138 g of Na^PO^HgO in 1 liter of distilled water. Refrigerate
this solution.
5.13.3 Chloramine-T: Dissolve 3.0 g of chloramine-T in 500 ml of
distilled water.
5.13.4 Pyradine barb-ituric acid reagent: Refer to (5.12.1).
5.13.5 Sodium hydroxide, 1 N: Dissolve 40 g of NaOH in 500 ml of
distil led water.
5.13.6 Stock cyanide solution: Refer to 5.5.
5.13.7 All working standards should contain 2 ml of 1 N NaOH
(5.13.5) per 100 ml.
5.13.8 Dilution water and recepticle wash water (NaOH, 0.25 N):
Dissolve 10.0 g NaOH in 500 mis of distilled water. Dilute to 1 liter.
Revised 4/84
-------
9010 / 7
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 Section One of this manual.
6.2 Samples should be collected in plastic or glass bottles of 1-liter
size or larger. All bottles must be thoroughly cleaned and thoroughly rinsed
to remove soluble materials from containers.
6.3 Oxidizing agents such as chlorine decompose most cyanides. To
determine whether oxidizing agents are present, test a drop of the sample with
potassium iodide-starch test paper; a blue color indicates the need for
treatment. Add ascorbic acid a few crystals at a time until a drop of sample
produces no color on the indicator paper. Then add an additional 0.6 g of
ascorbic acid for each liter of water.
6.4 Samples must be preserved with 2 ml of 10 N sodium hydroxide per
liter of sample (pH is greater than or equal to 12) at the time of collection.
6.5 Samples should be refrigerated at 4*C when possible and analyzed as
soon as possible.
7.0 Procedure
7.1 Pretreatment for cyanides amenable to chlorination
7.1.1 Two sample aliquots are required to determine
cyanides amenable to chlorination. To one 500 ml aliquot or
a volume diluted to 500 ml, add calcium hypochlorite solution
(5.10) dropwise while agitating and maintaining the pH
between 11 and 12 with sodium hydroxide (5.1).
Caution: The initial reaction product of alkaline
chlorination is the very toxic gas cyanogen chloride;
therefore, it is recommended that this reaction be
performed in a hood. For convenience, the sample may be
agitated in a 1 liter beaker be means of a magnetic
stirring device.
7.1.2 Test for residual chlorine with Kl-starch paper (5.11) and
maintain this excess tor one hour, continuing agitation. A distinct blue
color on the test paper indicates a sufficient chlorine level. If
necesssary, add additional hypochlorite solution.
7.1.3 After one hour, add 0.5 g portions of ascorbic acid until
Kl-starch paper shows no residual chlorine. Add an additional 0.5 g of
ascorbic acid to ensure the presence of excess reducing agent.
7.1.4 Test for total cyanide in both the chlorinated and
unchlorinated aliquots. (The difference of total cyanide in the
chlorinated and unchlorinated aliquots is the cyanide amenable to
chlorionation.)
Revised 4/84
-------
9010 / 8
7.2 Distillation Procedure
7.2.1 Place 500 ml of sample, or an aliquot diluted to 500 ml in
the 1 liter boiling flask. Pi pet 50 ml of sodium hydroxide (5.1) into
the absorbing tube. If the apparatus in Figure 1 is used, add distilled
water until the spiral is covered. Connect the boiling flask, condenser,
absorber and trap in the train. (Figure 1 or 2)
7.2.2 Start a slow stream of air entering the boiling flask by
adjusting the vacuum source. Adjust the vacuum so that approximately two
bubbles of air per second enters the boiling flask through the air inlet
tube.
7.2.3 If samples contain sulfide, add 50 ml of bismuth nitrate
solution (5.2) after the air rate is set through the air inlet tube. Mix
for 3 minutes prior to addition of
7.2.4 If samples contain N03 and/or N0£, add 50 ml of sulfarnic acid
solution (5.9) after the air rate is set through the air inlet tube. Mix
for 3 minutes prior to addition of
7.2.5 Slowly add 50 ml 18 N sulfuric acid (5.3) through the air
inlet tube. Rinse the tube with distilled water and allow the airflow to
mix the flask contents for 3 minutes. Pour 20 ml of magnesium chloride
(5.8) into the air inlet and wash down with a stream of water.
7.2.6 Heat the solution to boiling. Reflux for one hour. Turn
off heat and continue the airflow for at least 15 minutes. After cooling
the boiling flask, disconnect absorber and close off the vacuum source.
7.2.7 Drain the solution from the absorber into a 250 ml volumetric
flask. Wash the absorber with distilled water and add the washings to
the flask. Dilute to the mark with distilled water.
7.3 Manual spectophotometric determination:
7.3.1 Withdraw 50 ml or less of the solution from the flask and
transfer to a 100 ml volumetric flask. If less than 50 ml is taken,
dilute to 50 ml with 0.25 N sodium hydroxide solution (5.13.8).
Add 15.0 ml of sodium phosphate solution (5.4) and mix.
7.3.2 Add 2 ml' of chloramine-T (5.12.2) and mix. See note 1.
After 1 to 2 minutes, add 5 ml of pyridine-barbituric acid
solution (5.12.1) and mix. Dilute to mark with distilled
water and mix again. Allow 8 minutes for color development
and then read absorbance at 570 nm in a 1-cm cell within 15
minutes.
Revised 4/84
-------
9010 / 9
7.4 Standard curve for samples without sulfide
7.4.1 Prepare a series of standards by pipeting suitable volumes of
standard solution (5.7) into 250 ml volumetric flasks. To each standard
add 50 ml of 1.25 N sodium hydroxide and dilute to 250 ml with distilled
water. Prepare as follows:
ML of Working Standard Solution Cone, g CN
(1 ml = 10 g CN) _ per 250 ml
0 BLANK
1.0 10
2.0 20
5.0 50
10.0 100
15.0 150
20.0 200
7.4.2 It is not imperative that all standards be distilled in the
same manner as the samples. It is recommended that at least two
standards (a high and a low) be distilled and compared to similar values
on the curve to insure that the distillation technique is reliable. If
distilled standards do not agree within +_ 10% of the undistilled
standards, the analyst should find the cause of the apparent error before
proceeding.
7.4.3 Prepare a standard curve by plotting absorbance of standard
vs. cyanide concentrations.
7.4.4 To check the efficiency of the sample distillation, add an
increment of cyanide from either the intermediate standard (5.6) or the
wording standard (5.7) to 500 ml of sample in insure a level of 20 u.g/1.
Proceed with the analysis as in Procedure (7.2.1)
7.5 Standard curve for samples with sulfide
7.5.1 It is imperative that all standards be distilled in the same
manner as the samples. Standards distilled by this method will give a
linear curve, but as the concentration increases, the recovery decreases.
It is recommended that at least 3 standards be distilled.
7.5.2 Prepare a standard curve by plotting absorbance of standards
vs. cyanide concentrations.
7.6 Calculation: If the colormetric procedure is used, calculate the
cyanide, in u.g/1, in the original sample as follows:
CN, ng/1 = A x i'000 x 50
B C
Revised 4/84
-------
9010 / 10
where:
A = u,g CN read from standard curve
B = ml of original sample for distillation
C = ml taken for colorimetric analysis
7.7 Automated colorimetric determination
7.7.1 Set up the manifold as shown in Figure 3 in a hood or a
well ventilated area.
7.7.2 Allow colorimeter and recorder to warm up for 30 minutes. Run
a baseline with all reagents, feeding distilled water through the sample
line.
7.7.3 Place appropriate standards in the sampler in order of
decreasing concentration. Complete loading of sampler tray with unknown
samples.
7.7.4 When the baseline becomes steady, begin the analyses.
7.8 Calculation: Prepare standard curve by plotting peak heights of
standards against concentration values. Compute concentrations of samples by
comparing sample peak heights with standards.
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 occuring.
8.3 Analyze check standards after approximately every 15 samples.
8.4 Run one duplicate sample for every 10 samples. A duplicate
sample is a sample brought through the whole sample preparation
process.
8.5 Spiked samples or standard referencee materials shall be
periodically employed to ensure that correct prcedures are being followed
and that all equipment is operating properly.
8.6 The method of standard additions shall be used for the analysis
of all samples that suffer from matrix interferences.
Revised 4/84
-------
METHOD 9020
TOTAL ORGANIC HALIDES (TOX)
1.0 Scope and Application
1.1 Method 9020 determines Total Organic Halides (TOX) as Cl~ in
drinking and ground waters. The method uses carbon adsorption with a
microcoulometric-titration detector. It requires that all samples be run in
duplicate. Under conditions of duplicate analysis, the reliable limit of
sensitivity is 5 u.g/1.
1.2 Method 9020 detects all organic halides containing chlorine, bromine
and iodine that are adsorbed by granular activated carbon under the conditions
of the method. Fluorine-containing species are not determined by this method.
1.3 Method 9020 is applicable to samples whose inorganic-halide concen-
tration does not exceed the organic-halide concentration by more than 20,000
times.
1.4 Method 9020 is restricted to use by, or under the supervision of,
analysts experienced in the operation of a pyrolysis/microcoulometer and in
the interpretation of the results.
1.5 This method is provided as a recommended procedure. It may be used
as a reference for comparing the suitability of other methods thought to be
appropriate for measurement of TOX (i.e., by comparison of sensitivity,
accuracy, and precision data).
2.0 Summary of Method
2.1 A sample of water that has been protected against the loss of
volatiles by the elimination of headspace in the sampling container, and that
is free of undissolved solids, is passed through a column containing 40 mg of
activated carbon. The column is washed to remove any trapped inorganic
halides, and is then analyzed to convert the adsorbed organohalides to a
titratable species that can be measured by a microcoulometric detector.
3.0 Interferences
3.1 Method interferences may be caused by contaminants, reagents,
glassware, and other sample processing hardware. All these materials must be
-------
2 / MISCELLANEOUS ANALYTICAL METHODS
routinely demonstrated to be free from interferences under the conditions of
the analysis by running method blanks.
3.1.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by treating with chromate cleaning solution.
This should be followed by detergent washing in hot water. Rinse with
tap water and distilled water, drain dry, and heat in a muffle furnace at
400° C for 15 to 30 min. Volumetric ware should not be heated in a muffle
furnace. Glassware should be sealed and stored in a clean environment after
drying and cooling to prevent any accumulation of dust or other contaminants.
3.1.2 The use of high purity reagents and gases helps to minimize
interference problems.
3.2 Purity of the activated carbon must be verified before use. Only
carbon samples that register less than 1000 ng/40 mg should be used. The
stock of activated carbon should be stored in its granular form in a glass
container with a Teflon seal. Exposure to the air must be minimized,
especially during and after milling and sieving the activated carbon. No
more than a two-week supply should be prepared in advance. Protect carbon at
all times from all sources of halogenated organic vapors. Store prepared
carbon and packed columns in glass containers with Teflon seals.
4.0 Ap_pa_£eit_u_s_ and Materials
4.1 Adsorption system
4.1.1 Dohrmann adsorption module (AD-2), or equivalent, pressurized,
sample and nitrate-wash reservoirs.
4.1.2 Adsorption columns: Pyrex, 5-cm-long x 6-mm-O.D. x 2-mm-I.D.
4.2.3 Granular activated carbon (GAC): Filtrasorb-400, Calgon-APC
or equivalent, ground or milled, and screened to a 100/200 mesh range.
Upon combustion of 40 mg of GAC, the apparent-halide background should
be 1000 mg Cl~ equivalent or less.
4.1.4 Cerafelt (available from Johns-Manville), or equivalent:
Form this material into plugs using a 2-mm-I.D. stainless-steel borer
with ejection rod (available from Dohrmann) to hold 40 mg of GAC in the
adsorption columns. CAUTION: Do not touch this material with your
fingers.
4.1.5 Column holders (available from Dohrmann).
4.1.6 Volumetric flasks: 100-ml, 50-ml. A general schematic
of the adsorption system is shown in Figure 1.
-------
9020 / 3
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4 / MISCELLANEOUS ANALYTICAL METHODS
4.2 Dohrmann microcoulornetric-titration system (MCTS-20 or DX-20), or
equivalent, containing the following components:
4.2.1 Boat sampler.
4.2.2 Pyrolysis furnace.
4.2.3 Microcoulometer with integrator.
4.2.4 Titration cell: A general description of the analytical
system is shown in Figure 2.
4.3 Strip chart recorder.
5.0 Reagents
5.1 Sodium sulfite: 0.1 M, ACS reagent grade (12.6 g/liter).
5.2 Nitric acid: Concentrated.
5.3 Nitrate-wash solution (5000 mg N03'/l): Prepare a nitrate-wash
solution by transferring approximately 8.2 g of potassium nitrate into a 1-liter
volumetric flask and diluting to volume with reagent water.
5.4 Carbon dioxide: Gas, 99.9% purity.
5.5 Oxygen: 99.9% purity.
5.6 Nitrogen: Prepurified.
5.7 70% acetic acid in water: Dilute 7 volumes of acetic acid with 3
volumes of water.
5.8 Trichlorophenol solution, stock (1 u.1 = 10 u.g Cl~): Prepare a
stock solution by weighing accurately 1.856 g of trichlorophenol into a
100-ml volumetric flask. Dilute to volume with methanol.
5.9 Trichlorophenol solution, calibration (1 u.1 = 500 rig Cl~):
Dilute 5 ml of the trichlorophenol stock solution to 100 ml with methanol.
5.10 Trichlorophenol standard, instrument-calibration: First, nitrate-
wash a single column packed with 40 mg of activated carbon as instructed for
sample analysis, and then inject the column with 10 u.1 of the calibration
solution.
5.11 Trichlorophenol standard, adsorption-efficiency (100 u.g Cl-/liter):
Prepare an adsorption-efficiency standard by injecting 10 u.1 of stock solution
into 1 liter of reagent water.
-------
9020 / 5
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6 / MISCELLANEOUS ANALYTICAL METHODS
5.12 Reagent water: Reagent water is defined as a water in which
an interferent is not observed at the method detection limit of each parameter
of interest.
5.13 Blank standard: The reagent water used to prepare the calibration
standard should be used as the blank standard.
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 Section One of this manual.
6.2 All samples should be collected in bottles with teflon septa
(e.g., Pierce #12722 or equivalent) and be protected from light. If this is
not possible, use amber glass, 250-ml, fitted with teflon-lined caps. Foil
may be substituted for teflon if the sample is not corrosive. Samples must
be protected against loss of volatiles by eliminating headspace in the
container. If amber bottles are not available, protect samples from light.
The container must be washed and muffled at 400° C before use, to minimize
contamination.
6.3 All glassware must be dried prior to use according to the method
discussed in 3.1.1.
7.0 Procedure
7.1 Sample preparation
7.1.1 Special care should be taken in handling the sample in order
to minimize the loss of volatile organohalides. The adsorption procedure
should be performed simultaneously on duplicates.
7.1.2 Reduce residual chlorine by adding sulfite (1 ml of 0.1 M
per liter of sample). Sulfite should be added at the time of sampling
if the analysis is meant to determine the TOX concentration at the time
of sampling. It should be recognized that TOX may increase on storage
of the sample. Samples should be stored at 4° C without headspace.
7.1.3 Adjust the pH of the sample to approximately 2 with concen-
trated HN03 just prior to adding the sample to the reservoir.
7.2 Calibration
7.2.1 Check the adsorption efficiency of each newly-prepared batch
of carbon by analyzing 100 ml of the adsorption-efficiency standard, in
duplicate, along with duplicates of the blank standard. The net recoverv
should be within 5% of the standard value.
-------
9020 / 7
7.2.2 Nitrate-wash blanks (method blanks): Establish the
repeatability of the method background each day by first analyzing
several nitrate-wash blanks. Monitor this background by spacing nitrate-
wash blanks between each group of eight pyrolysis determinations. The
nitrate-wash blank values are obtained on single columns packed with
40 mg of activated carbon. Wash with the nitrate solution as instructed
for sample analysis, and then pyrolyze the carbon.
7.2.3 Pyrolyze duplicate instrument-calibration standards and the
blank standard each day before beginning sample analysis. The net
response to the calibration-standard should be within 3% of the
calibration-standard value. Repeat analysis of the instrument-calibration
standard after each group of eight pyrolysis determinations, and before
resuming sample analysis after cleaning or reconditioning the titration
cell or pyrolysis system.
7.3 Adsorption procedure
7.3.1 Connect two columns in series, each containing 40 mg of
100/200-mesh activated carbon.
7.3.2 Fill the sample reservoir, and pass a metered amount of
sample through the activated-carbon columns at a rate of approximately
3 ml/min. NOTE: 100 ml of sample is the preferred volume for concentra-
tions of TOX between 5 and 500 u.g/1; 50 ml for 501 to 1000 u.g/1, and 25
ml for 1001 to 2000 ug/1.
7.3.3 Wash the columns-in-series with 2 ml of the 5000-mg/l
nitrate solution at a rate of approximately 2 ml/min to displace inorganic
chloride ions.
7.4 Pyrolysis procedure
7.4.1 The contents of each column are pyrolyzed separately. After
rinsing with the nitrate solution, the columns should be protected from
the atmosphere and other sources of contamination until ready for
further analysis.
7.4.2 Pyrolysis of the sample is accomplished in two stages. The
volatile components are pyrolyzed in a CO^-rich atmosphere at a low
temperature to ensure the conversion of brominated trihalomethanes to
a titratable species. The less volatile components are then pyrolyzed
at a high temperature in an 02-rich atmosphere. NOTE: The quartz
sampling boat should have been previously muffled at 800" C for at least
2 to 4 min as in a previous analysis, and should be cleaned of any
residue by vacuuming.
7.4.3 Transfer the contents of each column to the quartz boat for
individual analysis.
-------
8 / MISCELLANEOUS ANALYTICAL METHODS
7.4.4 If the Dohrmann MC-1 is used for pyrolysis, manual instructions
are followed for gas flow regulation. If the MCTS-20 is used, the
information on the diagram in Figure 3 is used for gas flow regulation.
7.4.5 Position the sample for 2 min in the 200° C zone of the
pyrolysis tube. For the MCTS-20, the boat is positioned just outside
the furnace entrance.
7.4.6 After 2 min, advance the boat into the 800° C zone (center)
of the pyrolysis furnace. This second and final stage of pyrolysis may
require from 6 to 10 min to complete.
7.5 Detection: The effluent gases are directly analyzed in the micro-
coulometric-titration cell. Carefully follow manual instructions for optimizing
cell performance.
7.6 Breakthrough. The unpredictable nature of the background bias
makes it especially difficult to recognize the extent of breakthrough of
organohalides from one column to another. All second-column measurements for
a properly operating system should not exceed 10% of the two-column total
measurement. If the 10% figure is exceeded, one of three events can be
happening. Either (1) the first column was overloaded and a legitimate
measure of breakthrough was obtained, in which case taking a smaller sample
may be necessary; or (2) channeling or some other failure occurred, in which
case the sample may need to be rerun; or (3) a high random bias occurred and
the result should be rejected and the sample rerun. Because it may not be
possible to determine which event occurred, a sample analysis should be
repeated often enough to gain confidence in results. As a general rule, any
analysis that is rejected should be repeated whenever sample is available.
If the second-column measurement is equal to or less than the nitrate-wash
blank value, the second-column value should be disregarded.
7.7
formula:
Calculations: TOX as Cl~ is calculated using the following
(crc3)
(C2 -c3)
= u.g/1 Total Organic Halide
where:
'1 = U-9 Cl~ on the first column in series
^2 = u.g Cl~ on the second column in series
^3 = predetermined, daily, average, method-blank value
(nitrate-wash blank for a 40-mg carbon column)
V = the sample volume in liters.
-------
9020 / 9
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-------
10 / MISCELLANEOUS ANALYTICAL METHODS
8.0 Quality Control
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Before performing any analyses, the analyst must demonstrate the
ability to generate acceptable accuracy and precision with this procedure by
analyzing appropriate quality-control check samples.
8.3 The laboratory must develop and maintain a statement of method
accuracy for their laboratory. The laboratory should update the accuracy
statement regularly as new recovery measurements are made.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Run check standard after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparations process.
8.7 It is recommended that the laboratory adopt additional quality-
assurance practices for use with this method. The specific practices that
would be most productive will depend upon the needs of the laboratory and the
nature of the samples. Field duplicates may be analyzed to monitor the
precision of the sampling technique. Whenever possible, the laboratory
should perform analysis of standard reference materials and participate in
relevant performance-evaluation studies.
-------
METHOD 9030
SULFIDES
1.0 Scope and Application
1.1 Method 9030 is used to measure the concentration of total and
dissolved sulfides in drinking, surface and saline waters, and domestic and
industrial wastes. The method does not measure acid-insoluble sulfides;
copper sulfide is the only common acid-insoluble sulfide. Method 9030 is
suitable for measuring sulfide in concentrations above 1 mg/1.
2.0 Summary of Method
2.1 Excess iodine is added to a sample which may or may not have been
treated with zinc acetate to produce zinc sulfide. The iodine oxidizes the
sulfide to sulfur under acidic conditions. The excess iodine is back-titrated
with sodium thiosulfate or phenylarsine oxide.
3.0 Interferences
3.1 Reduced sulfur compounds that decompose in acid, such as sulfite,
thiosulfate and hydrosulfite, may yield erratic results. Also, volatile
iodine-consuming substances will give high results.
3.2 Samples must be taken with a minimum of aeration in order to avoid
volatilization of sulfides and reaction with oxygen which may convert sulfide
to unmeasurable forms.
3.3 If the sample is not preserved with zinc acetate, analysis must
start immediately.
4.0 Apparatus and Materials
4.1 Ordinary laboratory glassware.
5.0 Reagents
5.1 Hydrochloric acid, HC1, 6 N.
5.2 Phenylarsine oxide 0.0250 N: Commercially available.
5.3 Starch indicator: Commercially available.
-------
2 / MISCELLANEOUS ANALYTICAL METHODS
5.4 Potassium iodide, KI crystals.
5.5 Amylose indicator.
5.6 Standard iodine solution, 0.0250 N: Dissolve 20 to 25 g KI in a
little water in a liter volumetric flask and add 3.2 g iodine. Allow to
dissolve. Dilute to 1 liter and standardize against 0.0250 N sodium
thiosulfate or phenylarsine oxide using a starch indicator, as follows.
5.6.1 Dissolve approximately 2 g (+1 g) KI crystals in 100 to
150 ml distilled water.
5.6.2 Add 20 ml of the iodine solution to be standardized and
dilute to 300 ml.
5.6.3 Titrate with 0.0250 N phenylarsine oxide (PAO) until a pale
straw color occurs.
5.6.4 Add a small amount of amylose indicator and wait until a
homogeneous blue color develops.
5.6.5 Continue titration drop by drop until the color disappears.
5.6.6 Run in duplicate.
5.6.7 Calculate normality by the following equation:
NT = ml PAO x 0.0250
'* I o "•'
* 20
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 Section One of this manual.
6.2 Aqueous samples must be preserved with zinc acetate or the analysis
must be started immediately.
7.0 Procedure
7.1 Unprecipitated sample
7.1.1 Place a known amount of standard iodine solution into a
500-rnl flask. The amount should exceed the amount of sulfide expected.
7.1.2 Add distilled water, if necessary, to bring the volume to
approximately 20 ml.
-------
9030 /3
7.1.3 Add 2 ml of 6 N HC1.
7.1.4 Pipet 200 ml of sample into the flask, keeping the tip of
the pi pet below the surface of the sample.
7.1.5 If the iodine color disappears, add more iodine until
the color remains. Record the total number of ml of the standard iodine
used in performing steps 7.1.1 and 7.1.5.
7.1.6 Titrate with reducing solution (0.0250 N sodium thiosulfate
of 0.0250 N phenylarsine oxide solution) using the starch indicator until
the blue color disappears. Record the number of ml used.
7.2 Precipitated samples
7.2.1 Add the reagents to the sample in the original bottle.
Perform steps 7.1.1, 7.1.3, 7.1.5, and 7.1.6.
7.3 Dewatered samples
7.3.1 Return the glass-fiber filter paper that contains the sample
to the original bottle. Add 200 ml of distilled water. Perform steps
7.1.1, 7.1.3, 7.1.5, and 7.1.6.
7.3.2 The calculations (Section 7.4) should be based on the
original sample put through the filter.
7.4 Calculations. One ml of 0.0250 N standard iodine solution reacts
with 0.4 mg of sulfide present in the titration vessel. Thus, the following
equation should be used to calculate sulfide concentration:
mg/1 sulfide = 400(A-B)/ml sample
where:
A = ml of 0.0250 N standard iodine solution
B = ml of 0.0250 N standard reducing sodium thiosulfate or
phenylarsine oxide solution.
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.
-------
4 / MISCELLANEOUS ANALYTICAL METHODS
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination has occurred.
8.5 Analyze check standards after approximately every 15 samples.
8.6 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation process.
8.7 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
-------
METHOD 9040
pH MEASUREMENT
1.0 Scope and Application
1.1 Method 9040 is used to measure the pH of aqueous wastes and
those multiphasic wastes where the aqueous phase comprises at least 20% of
the total volume of the waste.
2.0 Summary
2.1 The pH of the sample is determined electrometrically using either
a glass electrode in combination with a reference potential or a combination
electrode. The measuring device is calibrated using a series of solutions of
known pH.
3.0 Interferences
3.1 The glass electrode, in general, is not subject to solution inter-
ferences from color, turbidity, colloidal matter, oxidants, reductants or
high salinity.
3.2 Sodium error at pH levels greater than 10 can be reduced or elim-
inated by using a "low sodium error" electrode.
3.3 Coatings of oily material or particulate matter can impair electrode
response. These coatings can usually be removed by gentle wiping or detergent
washing, followed by distilled water rinsing. An additional treatment with
hydrochloric acid (1:9) may be necessary to remove any remaining film.
3.4 Temperature effects on the electrometric determination of pH
arise from two sources. The first is caused by the change in electrode
output at various temperatures. This interference can be controlled with
instruments having temperature compensation or by calibrating the electrode-
instrument system at the temperature of the samples. The second source of
temperature effects is the change of pH due to changes in the sample as the
temperature changes. This error is sample-dependent and cannot be controlled.
It should, therefore, be noted by reporting both the pH and temperature at
the time of analysis.
4.0 Apparatus and Materials
4.1 pH Meter: Laboratory or field model. A wide variety of instruments
are commercially available with various specifications and optional equipment.
4.2 Glass electrode.
-------
2 / MISCELLANEOUS ANALYTICAL METHODS
4.3 Reference electrode: A silver-silver chloride or other reference
electrode of constant potential may be used. NOTE: Combination electrodes
incorporating both measuring and referenced functions are convenient to use
and are available with solid, gel-type filling materials that require minimal
maintenance.
4.4 Magnetic stirrer and Teflon-coated stirring bar.
4.5 Thermometer or temperature sensor for automatic compensation.
5.0 Reagents
5.1 Primary standard buffer salts are available from the National
Bureau of Standards and should be used in situations where extreme accuracy
is necessary. Preparation of reference solutions from these salts requires
some special precautions and handling! such as low-conductivity dilution
water, drying ovens, and carbon-dioxide-free purge gas. These solutions
should be replaced at least once each month.
5.2 Secondary standard buffers may be prepared from NBS salts or
purchased as a solution from commercial vendors. These commercially available
solutions have been validated by comparison to NBS standards and are recommended
for routine use.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Section One of this manual.
6.2 Samples should be analyzed as soon as possible.
7.0 Procedure
7.1 Calibration
7.1.1 Because of the wide variety of pH meters and accessories,
detailed operation procedures cannot be incorporated into this method.
Each analyst must be acquainted with the operation of each system and
familiar with all instrument functions. Special attention to care of
the electrodes is recommended.
iNational Bureau of Standards Special Publication 260.
-------
9040 / 3
7.1.2 Each instrument/electrode system must be calibrated at a
minimum of two points that bracket the expected pH of the samples and
are approximately three pH units or more apart. Various instrument
designs may involve use of a "balance" or "standardize" dial or slope
adjustment as outlined in the manufacturer's instructions. Repeat
adjustments on successive portions of the two buffer solutions until
readings are within 0.05 pH units of the buffer solution value.
7.2 Place the sample or buffer solution in a clean glass beaker using
a sufficient volume to cover the sensing elements of the electrodes and to
give adequate clearance for the magnetic stirring bar. If field measurements
are being made, the electrodes may be immersed directly in the sample stream
to an adequate depth and moved in a manner to ensure sufficient sample
movement across the electrode-sensing element as indicated by drift-free
(less than 0.1 pH) readings.
7.3 If the sample temperature differs by more than 2°C from the buffer
solution, the measured pH values must be corrected. Instruments are equipped
with automatic or manual compensators that electronically adjust for tempera-
ture differences. Refer to manufacturer's instructions.
7.4 Thoroughly rinse and gently wipe the electrodes prior to measuring
pH of samples. Immerse the electrodes into the sample beaker or sample stream
and gently stir at a constant rate to provide homogeneity and suspension of
solids. Note and record sample pH and temperature. Repeat measurement on
successive volumes of sample until values differ by less than 0.1 pH units.
Two or three volume changes are usually sufficient.
8.0 Quality Control
8.1 Duplicate samples and check standards should be analyzed routinely.
8.2 Electrodes must be thoroughly rinsed between samples.
-------
METHOD 9095
PAINT FILTER LIQUIDS TEST
l.O Scope and Application
1.1 This method is used to determine the presence and/or concentration of
free liquids in a representative sample of waste, or to separate the liquid and
solid portions of a sample.
1.2 The method is used to determine compliance with 40 CFR 261.21, 261.22,
264.314, and 265.314.
2.0 Summary of Method
2.1 A predetermined amount of material is placed in a paint filter and the
free liquid portion of the material is that portion which passes through and
drops from the filter.
3.0 Interferences
3.1 Filter media was observed to separate from the filter cone on exposure
to alkaline materials. This development causes no problem if the sample is not
disturbed.
4.0 Apparatus and Materials
4.1 Conical paint filter - mesh number 60. Available at local paint stores
such as Sherwin-Williams and Glidden for an approximate cost of $0.07 each.
4.2 Glass Funnel [If the paint filter, with the waste, cannot sustain its
weight on the ring stand, then a fluted glass funnel or glass funnel with a mouth
large enough to allow at least one inch of the filter mesh to protrude should he
used to support the filter. The funnel is to be fluted or have a large open
mouth in order to support the paint filter yet not interfere with the movement,
to the graduated cylinder, of the liquid that passes through the filter raesh.]
4.3 Metal Ring or Tripod
4.4 Ring Stand
4.5 Graduated Cylinder, 100 ml.
iiC Qlaoo nad, 0" fU
fc>Uoh Claoa (£ui usa IE iJUiuenL Hee liijub'l -m. Cmy liquid yuiiLian ia
"9 • 1 Mui M •
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9095/2
6.0 Sampfe Collection, Preservation/ and Handling
6.1
One of this'
.1 samples must be collegted according to the directions in section
lual.
6.2 A 1GK) ml or lOOg n
it is not possible to obtain
representative Vf the waste,
of 100 ml or 100V i.e., 200
are used, analysttb shall
each portion separately.
is considered to have free
needs to be determi
it
7.0 Procedure
[In order to determine
7.1 through 7.4 should
7.1 Assemble test
tative sample is required for the test. [If
le of 100 ml or lOOg that is sufficiently
.nalyst may use larger size samples in multiples
400 ml or g. However, when larger samples
divide I/he sample into 100 ml or lOOg portions and test
portion contains free liquids the entire sample
,s. If the percent of free liquid in the sample
be the average of the sub-samples tested.]
pliance with 40 CFR 264.314 or 265.314 only Steps
used/]
7.2 Place sample in
for the paint filter.
tus as shown in Figure 1.
filter. A funnel may be used to provide support
7.3 Allow sample to drjki\j for 5 minutes into the graduated cylinder.
7.4 Note any free liq/iid generated after this five minute period, if any
liquids collect in the graduatedViylinder then the material is deemed to contain
free liquids, for purposes/of 40 $FR 264.314 or 265.314.
Continue with Steps
to prepare the liquid ph
'.5 through 7.7 to determine the percent free liquid or
for furflher testing, if appropriate.
7.5 Pead and record volume of lYquid phase in graduated cylinder. Stir
sample with glass rod, ^et stand undisturbed for an additional 15 minutes.
7.6 Read and recqtd volume of liquid phase.
7.7 Calculate %/change between theVwo 15 minute readings. If the difference
is less than 10%, the/test is complete. Vf the change is greater than 10%,
repeat steps 7.5 thrgugh 7.7 until the change between successive readings is
less than 10%.
Calculations:
Current Readiy
Pre
(ml) - Preceding Reading \ml) x 100 = % Change
ling Reading (ml)
Total Liquiy Phase (ml) x 100 = % Free Lie
Sample Sifze (ml)
8.0 Quality Cyntrol
8.1 Duplicate samples should be analyzed on a routine basis.
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9095/2
open mouth in order to support the paint filter yet not inter-
fere with the movement, to the graduated cylinder, of the
material that passes through the filter mesh.]
4.3 Ring Stand and Ring, or Tripod.
4.4 Beaker or Graduated Cylinder, 100 ml.
5.0 Reagents
5.1 None.
6.0 Sample Collection, Preservation, and Handling
6.1 All samples must be collected according to the directions
in Section One of this manual.
6.2 A 100 ml or lOOg representative sample is required for
the test. [If it is not possible to obtain a sample of 100 ml
or lOOg that is sufficiently representative of the waste, the
analyst may use larger size samples in multiples of 100 ml or
lOOg, i.e., 200, 300, 400 ml or g. However, when larger samples
are used, analysts shall divide the sample into 100 ml or lOOg
portions and test each portion separately. If any portion contains
free liquids the entire sample is considered to have free liquids.
If the percent of free liquid in the sample needs to be determined,
it shall be the average of the sub-samples tested.]
7.0 Procedure
7.1 Assemble test apparatus as shown in Figure 1.
7.2 Place sample in the filter. A funnel may be used to
provide support for the paint filter.
7.3 Allow sample to drain for 5 minutes into the graduated
cylinder.
Revised 3/85
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METHOD 9095
PAINT FILTER LIQUIDS TEST
1.O Scope and Application
1.1 This method is used to determine the presence of
free liquids in a representative sample of waste.
1.2 The method is used to determine compliance with 40 CFR
264.314 and 265.314.
2«0 Summary of Method
2.1 A predetermined amount of material is placed in a
paint filter. If any portion of the material passes through and
drops from the filter within the 5 minute test period, the mate-
rial is deemed to contain free liquids.
3,0 Interferences
3.1 Filter media was observed to separate from the filter
cone on exposure to alkaline materials. This development causes
no problem if the sample is not disturbed.
4.0 Apparat us and MateriaIs
4.1 Conical paint filter - mesh number 6,0. Available at
local paint stores such as Sherwin-Williams and Glidden for an
approximate cost of $0,07 each.
4.2 Glass Funnel [If the paint filter, with the waste, r
cannot sustain its weight on the ring stand, then a fluted glass
funnel or glass funnel with a mouth large enough to allow at
least one inch of the filter mesh to protrude should be used to
support the filter. The funnel is t,o be fluted or have a large
Revised 3/85
-------
7.4 If any portion of the test material collects in the
graduated cylinder in the 5 minute period, then the material is
deemed to contain free liquids for purposes of 40 CFR 26.4,314
and 265.314.
8.0 Quality Control
8.1 Duplicate samples should be analyzed on a routine basis.
Revised 3/85
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9095/4
ftlNfi STAND
PAINT
-6KAOUATEO CVUNDC*
. Prat Liquid A««tr«
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SECTION TEN
QUALITY CONTROL/QUALITY ASSURANCE
Section 10.1 defines Quality Control (QC) and Quality Assurance (QA).
Section 10.2 discusses how QC/QA procedures can be used to ensure achievement
of program goals. The various QC/QA aspects of sampling are discussed in
Section 10.1.3 while Section 10.1.4 discusses and lists appropriate laboratory
QC/QA activities. Section 10.1.5 discusses the criteria with which acceptable
data must comply and methods of data evaluation.
10.1 Introduction
Quality assurance (QA) is a system for ensuring that all information,
data, and resulting decisions compiled under a specific task are technically
sound, statistically valid, and properly documented. Quality control is the
mechanism through which quality assurance achieves its goals. Quality
control programs define the frequency and methods of checks, audits, and
reviews necessary to identify problems and dictate corrective action, thus
verifying product quality.
The soundness of an organization's QC/QA program has a direct bearing on
the integrity of its sampling and laboratory work. Results of sampling or
analysis conducted without adequate quality control and assurance may be
deemed unacceptable for RCRA evaluation purposes. The following section
discusses some minimum standards for QC/QA programs. Generators who are
choosing contractors to perform sampling or analytical work should make their
choice only after evaluating the contractor's QC/QA program against the
procedures presented in these sections. Likewise, contractors that currently
sample and/or analyze solid wastes should similarly evaluate their QC/QA
programs.
10.2 Program Design
The initial step for any sampling or analytical work should be to
strictly define the program goals. Once the goals have been defined, a
program must be designed that will meet these program goals. QC and QA
measures will be the mechanisms used to monitor the program and to ensure
that all data generated are suitable for their intended use. A knowledgeable
person who is not directly involved in the sampling or analysis must be
assigned the responsibility of ensuring that the QC/QA measures are properly
employed.
As a minimum, a proper QC/QA program would include the following:
1. The intended use(s) for the data, and the necessary level of
precision and accuracy of the data for these intended uses.
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2 / QUALITY CONTROL/QUALITY ASSURANCE
2. A representative sampling plan that includes provisions for:
- selecting appropriate sampling locations, depths, etc.
- providing a statistically sufficient number of sampling sites.
- measuring all necessary ancillary data.
- determining climatic flow or other conditions under which
sampling should be conducted.
- determining which media are to be sampled (e.g., wastewater,
sediment, effluent, soil).
- determining which parameters are to be measured (and where).
- selecting appropriate sample containers.
- selecting the frequency of sampling and length of sampling
period.
- selecting the types of sample (e.g., composites vs. grabs) to be
collected.
- sample preservation.
- chain-of-custody.
3. An analytical plan that includes:
- chain-of-custody procedures.
- appropriate sample preparation methods.
- appropriate analytical methods.
- appropriate calibration and analytical procedures.
- data handling, review and reporting.
4. Planning for the inclusion of proper and sufficient QC/QA activities,
including the use of QC samples throughout all phases of the study
to ensure that the level of quality of the data will meet the
requirements of the intended use(s) of the data.
All program details should be put in writing and assignments made to
appropriate personnel.
If the above procedures are followed (i.e., an appropriate program is
designed, tasks are assigned to knowledgeable personnel, and sufficient QC/QA
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QC/QA / 3
steps are employed), the program should meet and possibly surpass its goals
in most cases; at worst the failure to meet the program goals will be detected
and the usefulness of any data will be quantified.
10.3 Sampling
The quality of a sampling program has a direct bearing on the legal,
physical, and chemical integrity of the samples. If the representativeness
of the samples cannot be verified due to inadequate attention to sampling
procedures, then the usefulness of the analytical data will be limited,
regardless of the refinement of the analytical program. It is imperative,
therefore, that no analytical program be conducted without an adequate
sampling plan which does or will document the degree of representativeness
of the parameters of interest.
10.3.1 Design of a Sampling Plan
Section One of this manual discusses the considerations involved in
designing a representative sampling plan. For each specific project, a
sampling plan should be designed prior to commencement of sampling. If the
plan addresses the considerations discussed in Section One, then the resulting
samples should be representative of the waste of interest and therefore
suitable for evaluation of the waste according to RCRA criteria.
10.3.2 Sample Collection
A variety of different sampling devices are used in sampling depending
on the type of sample (solid, liquid, multiphased), the type of sample
container, and the sampling location. Section One and portions of Section
Three of this manual describe different devices that are available. The
appropriate sampling device must be selected and its use supervised by a
person thoroughly familiar with both the sampling and analytical requirements.
This familiarity is essential since (1) certain sampling devices are made of
materials that may contaminate samples, (2) cross contamination of samples
can occur if the sampling device is not cleaned properly, (3) routine sampling
methods may not be applicable when the waste is to be analyzed for a different
parameter (e.g., volatile organic compounds), and (3) the method of employing
the sampling devices may affect the integrity of the sample.
10.3.3 Sample Preservation
Some form of preservation is usually required for all samples. The type of
sample preservation required will vary depending on the sample type and the
parameter to be measured. Therefore, more than one container of the same
waste may be necessary if the waste is to be analyzed for more than one
parameter type.
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4 / QUALITY CONTROL/QUALITY ASSURANCE
The analytical methods included in this manual refer to the optimum
means of preservation. Since the chemical make-up of certain samples can
alter the effectiveness of preservation measures, all sample analyses should
be performed as soon as possible after sampling and before any recommended
holding time has expired.
10.3.4 Chain of Custody
Although chain-of-custody procedures may not be required in all cases,
they often are an essential part of sampling/analytical schemes since these
procedures can document the history of samples. Chain of custody establishes
the documentation and control necessary to identify and trace a sample from
sample collection to final analysis. Such documentation includes labeling to
prevent mix-up, container seals to detect unauthorized tampering with
contents of the sample containers, secure custody, and the necessary records
to support potential litigation."
A sample is considered to be under a person's custody if (1) it is in the
person's physical possession, (2) in view of the person, (3) secured by
that person so that no one can tamper with the sample, or (4) secured by that
person in an area that is restricted to authorized personnel.
Refer to Section One for details of how to implement chain-of-custody
procedures.
10.4 Analysis
An analytical program defines standard operating procedures to be used
in waste analysis, appropriate QC/QA procedures, means for detecting out-of-
control situations, and remedial actions. A separate analytical program
should be developed for each different waste to be analyzed. The program
should be thoroughly specified before sampling is begun, since the analytical
procedures to be used may affect the choice of sampling devices and procedures.
The program should select methods that will provide data at the level of
accuracy and precision that will be required by users of the data for decision-
making purposes under RCRA. Once the appropriate method(s) have been selected
it is imperative that the accuracy and precision of all analytical data be
thoroughly documented by means of a well-designed QC/QA program.
Laboratory QC/QA activities normally include:
1. Use of EPA-acceptable sample preparation and analytical methods.
2. Calibration of laboratory instruments to within acceptable limits
according to EPA or manufacturer's specifications before, after,
and during (as acceptable) use. Reference standards must be used
when necessary.
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QC/QA / 5
3. Periodic inspection, maintenance, and servicing (as necessary) of
all laboratory instruments and equipment.
4. The use of reference standards and QC samples (e.g., checks,
spikes, laboratory blanks, duplicates, splits) as necessary to
determine the accuracy and precision of procedures, instruments,
and operators.
5. The use of adequate statistical procedures (e.g., QC charts) to
monitor the precision and accuracy of the data and to establish
acceptable limits.
6. A continuous review of results to identify and correct problems
within'the measurement system (e.g., instrumentation problems,
inadequate operator training, inaccurate measurement methodologies).
7. Documenting the performance of systems and operators.
8. Regular participation in external laboratory evaluations (including
the EPA Performance Audit Program) to determine the accuracy and
overall performance of the laboratory. This should include performance
evaluation and interlaboratory comparison studies, and formal
field unit/laboratory evaluations and inspections.
9. Use of acceptable sample identification and, as necessary, formal
chain-of-custody procedures in the laboratory.
10. Maintenance and storage of complete records, charts, and logs of
all pertinent laboratory calibration, analytical, and QC activities
and data.
11. Ensuring all data outputs are presented in their prescribed format.
Specific Quality Control measures for each method can be found by
referring to the individual analytical methods included in this manual.
10.5 Data Handling
The quality of all data must be assessed before the data are used.
Assessment should focus on five basic points.
1. Accuracy - Can the data's accuracy be determined, and is it
acceptable for the planned use? QC/QA procedures will be designed
to measure the accuracy of all analytical data.
2. Precision - Can the data's precision be determined, and is it
acceptable for the planned use? QC/QA should demonstrate the
reproducibility of the measurement process.
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6 / QUALITY CONTROL/QUALITY ASSURANCE
3. Completeness - Are a sufficient amount of data available for the
planned use? QC/QA shall identify the quantity of data needed to
meet the program goals.
4. Representativeness - How well do the data represent actual
conditions at the sampling location, considering the original
study design, sampling methods, analytical methods, etc., which
were used?
5. Comparability - How comparable are data with respect to several
factors, including:
- consistency of reporting units?
- standardized siting, sampling, and methods of analysis?
- standardized data format?
All these factors must be considered when designing a study, and QC/QA
procedures must specify a reviewing process for all data.
Statistical procedures applicable to data evaluation include:
1. Central tendency and dispersion
- Arithmetic mean
- Range
- Standard deviation
- Relative standard deviation
- Pooled standard deviation
- Geometric mean
2. Measures of variability
- Accuracy
- Bias
- Precision; within laboratory and between laboratories
3. Significance test
- u-test
- t-test
- F-test
- Chi-square test
Specific data handling precautions are noted in the individual methods
described in this manual.
4JU.S. GOVERNMENT PRINTING OFFICE: 1982-361-082/315
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