United States Environmental Protection Agency EPA-902-B-94-001
Region 2 Revised May, 1994
RCRA Outreach Program
TECHNICAL ASSISTANCE DOCUMENT
FOR COMPLYING WITH THE TC RULE
AND IMPLEMENTING THE TOXICITY
CHARACTERISTIC LEACHING
PROCEDURE (TCLP)
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TECHNICAL ASSISTANCE DOCUMENT FOR
COMPLYING WITH THE TC RULE AND
IMPLEMENTING THE TOXICITY
CHARACTERISTIC LEACHING PROCEDURE (TCLP)
The following individuals prepared Chapter 1:
John Hansen
Hazardous Waste Compliance Branch
Air and Waste Management Division
USEPA Region 2
26 Federal Plaza
New York, New York 10278
Claudette Reed
Hazardous Waste Compliance Branch
Air and Waste Management Division
USEPA Region 2
26 Federal Plaza
New York, New York 10278
Michael Scudese
TRC Environmental Corporation
18 World's Fair Drive
Somerset, New Jersey 08873
Edited by: Frank Langone, IBM Corporation
Route 134, Yorktown Heights, New York 10598
The following individuals prepared Chapters 2 to 6:
Leon Lazarus Mitzi Miller
Monitoring Management Branch Environmental Quality Management
Environmental Services Division 10801 Fox Park
USEPA Region 2 Knoxville, Tennessee 37931
2890 Woodbridge Avenue
Edison, New Jersey 08837
Edited by: Frank Langone, IBM Corporation
Route 134, Yorktown Heights, New York 10598
May 1994
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References herein to any specific commercial product, process or service by
trade name, manufacturer, or otherwise does not imply its endorsement or
recommendation by EPA, TRC or EQM.
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Acknowledgements
The authors would like to thank the following individuals
for peer reviewing this document:
Kate Anderson, USEPA Office of Waste Programs Enforcement
Dr. Bill Batchelor, Texas A&M University
Edwin Earth, USEPA Center for Environmental Research
Dr. I la Cote, USEPA Health Effects Research Laboratory
Phil Flax, USEPA Region 2
Oliver Fordham, USEPA Office of Solid Waste
Kathleen Grimes, NJDEPE Bureau of Environmental Measurements
and Quality Assurance
Dr. Larry Jackson, Environmental Quality Management
Kevin Kubik, USEPA Region 2
Frances Liem, USEPA Office of Compliance Monitoring
Davis Jones, USEPA Office of Waste Programs Enforcement
Rose Lew, USEPA Office of Waste Programs Enforcement
Ken Peist, USEPA Region 2
Dr. Roger Spence, Oak Ridge National Laboratories
Gale Sutton, Galson Laboratories
Rock Vitale, Environmental Standards
Dr. Ken Wilkowski, USEPA Office of Research and Development
Dr. Lew Williams, USEPA Environmental Monitoring Systems Laboratory
Appreciation is also expressed for technical contributions from:
Jennifer Bramlett, SAIC Corporation
Dr. Mike Maskarinec, Oak Ridge National Laboratory
Carla Stout, TRC Environmental Corporation
Ted Varouxis, Associated Design and Manufacturing
the supplier of equipment and training tapes for the course
in
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Document Introduction
The goal of this document is to assist the regulated community to make proper utilization of
the Toxicity Characteristic Leaching Procedure (TCLP) to demonstrate compliance with the
Toxicity Characteristic (TC) and Land Ban Regulations. The following issues will be
discussed:
What is TCLP?
When must TCLP be performed?
Which analyte lists should be used to demonstrate compliance with TC and Land Ban
regulations?
How should a sampling strategy be developed?
How much QA/QC and analytical deliverables are appropriate?
How should one use the USEPA Region 2 TCLP data validation criteria?
How should sampling plans be developed for multi-phase and oily materials?
The following topics were added to the 1994 version of this document:
Obtaining CAMU variances from the Land Ban regulations.
Inappropriateness of TCLP method for risk assessments.
Characterizing heterogeneous solid wastes.
Characterizing building demolition debris containing lead based paint.
Implications of classifying non-hazardous wastes as hazardous.
Region 2 State TCLP policy guidances.
IV
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TABLE OF CONTENTS
Chapter Page
1.0 COMPLYING WITH THE TC RULE 1-1
1.1 Introduction 1-2
1.2 RCRA OVERVIEW 1-3
1.2.1 Growth of Hazardous Waste in America: The Case of Love Canal 1-3
1.2.2 RCRA Cradle to Grave Concept 1-5
1.2.3 Definitions of Hazardous Waste 1-8
1.2.4 Making a Hazardous Waste Determination 1-10
1.3 THE TOXICITY CHARACTERISTIC RULE 1-11
1.3.1 EPToxTest 1-11
1.3.2 TCLP Test 1-12
1.3.3 TC Rule's Effect Upon Generators and TSDFs 1-14
1.4 TC RULE'S EFFECT ON INDIVIDUAL RCRA REGULATIONS 1-18
1.4.1 General 1-18
1.4.2 Corrective Action and Closure 1-19
1.4.3 Land Disposal Restrictions (LDR) 1-20
1.4.4 Minimum Technology Requirements for Landfills and Surface
Impoundments 1-21
1.4.5 Exemption for Tanks (Minimum Technology Requirements) 1-22
1.4.6 Mixture Rule Exemption 1-23
1.4.7 Previously Delisted Wastes 1-24
1.4.8 Special Waste Exemptions 1-25
1.4.9 Hazardous Waste Listings 1-26
1.4.10 "Mixture" and "Derived From" Rules 1-27
1.4.11 Excluded Wastes 1-28
1.5 IMPACT OF TC RULE ON OTHER EPA PROGRAMS 1-29
1.5.1 Underground Storage Tanks (USTs) 1-29
1.5.2 Comprehensive Environmental Response and Liability Act (CERCLA) .... 1-31
1.5.3 Clean Water Act (CWA) 1-32
1.5.4 Safe Drinking Water Act (SDWA) 1-34
1.5.5 Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) 1-37
1.5.6 Used Oil Recycling Act 1-38
1.5.7 Toxic Substances Control Act (TSCA) 1-39
1.6 POLLUTION PREVENTION 1-40
1.7 CONCLUSIONS 1-43
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TABLE OF CONTENTS (Continued)
Chapter Page
2.0 APPLICATIONS OF THE TCLP METHOD 2-1
2.1 What is TCLP? 2-4
2.2 When is the Use of TCLP Applicable? 2-3
2.3 When is the Use of TCLP Inappropriate? 2-9
2.4 Sampling and Analysis Design 2-12
3.0 TC AND TCLP PROJECT PLANNING 3-1
3.1 Data Quality Objectives 3-2
3.2 DQO Case Study: Cadmium Contaminated Fly Ash Waste 3-10
3.3 Sampling and Analysis Design 3-18
3.4 Analytical Method Selection 3-22
4.0 OVERVIEW OF THE TCLP METHOD 4-1
4.1 Preliminary Sample Preparation for Leaching 4-2
4.2 Leaching Procedure for Nonvolatiles 4-5
4.3 Leaching Procedure for Volatiles 4-11
4.4 TCLP Method Quality Control 4-15
5.0 DATA VALIDATION AND DELIVERABLES 5-1
5.1 Data Validation 5-2
5.2 Data Deliverables 5-6
6.0 ANALYZING AND ASSESSING MULTI-PHASIC AND OILY WASTES 6-1
6.1 Definition of Oily Waste 6-2
6.2 Problems/Issues 6-3
6.3 Suggestions 6-5
6.4 Most Commonly Asked TCLP Question 6-7
6.5 Analytical Options 6-14
VI
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TABLE OF CONTENTS (Continued)
TABLES
Table Page
1-1 TC Rule Constituents 1-13
1-2 Permit Modifications 1-17
2-1 Toxicity Characteristic Constituents - Alphabetical 2-10
3-1 TCLP Holding Times 3-20
3-2 TC Analytes and Their Regulatory Levels 3-23
3-3 Metals Analysis Method By ICP 3-25
3-4 Metals Analysis Methods by GFAA and Mercury by CVAA 3-25
3-5 Pesticide and Herbicide Quantitation Limits by SW 846 and CLP 3-26
3-6 Quantitation Limits for Volatile TC Constituents 3-27
3-7 Quantitation Limits for Semivolatile TC Constituents 3-28
4-1 Volume of Extract Required for One Nonvolatile Analysis 4-7
VII
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TABLE OF CONTENTS (Continued)
FIGURES
Figure Page
3-1 Overview of the Data Quality Objectives Planning Process 3-5
3-2 Decision Performance Curve for Cadmium Fly-Ash Waste Example 3-17
4-1 TCLP Preliminary Determinations 4-4
4-2 Nonvolatile Extraction 4-6
4-3 Volatiles by ZHE 4-12
4-4 Volatiles by ZHE Continued 4-13
4-5 Standard Addition Plot 4-17
VIII
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TABLE OF CONTENTS (Continued)
APPENDICES
Appendix
I TCLP Method 1311 (July 1992, Revision 0)
II 40 CFR 268 Subpart D Land Ban Treatment Standards
III Associated Design and Larry Jackson's TCLP Bench Sheets and Calculations
IV USEPA Region 2 Organic, Inorganic and TCLP Data Validation SOPs
V References for Multi-phasic and Oily Waste
VI Office of Solid Waste Management Methods Section Memoranda #35, #36
VII Recommendations and Rationale for Analysis of Contaminant Release by the
Environmental Engineering Committee, Science Advisory Board, October 1991
VIII USEPA Region 2 Special Analytical Services Request
IX Required Uses of SW 846
X Stabilization/Solidification: Is It Always Appropriate? and Stabilization/Solidification of
Wastes Containing Volatile Organic Compounds in Commercial Cementitious Waste
Forms from: Stabilization and Solidification of Hazardous, Radioactive, and Mixed
Wastes, Second Volume, ASTM STP 1123
XI Army Waste Classification Guidance for Building Demolition Debris Containing Lead
Based Paint
XII 1992 Workshop on Characterizing Heterogeneous Materials
XIII Improper Hazardous Waste Characterizations: Financial and Compliance
Implications
XIV Region 2 State TCLP Guidances
XV Risk Assessment for Disposal of Solidified/Stabilized Waste and Contaminated Soil
XVI Barbara Metzger's 1992 Speech on Environmental Data Use, "Meeting the
Customer's Need"
IX
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List of Abbreviations and Acronyms
AC Alternating Current
ARARs Applicable or Relevant and Appropriate Requirements
ASTM American Society of Testing and Materials
BOAT Best Demonstrated Available Technology
BNA Base, Neutral and Acid Extractable Organics
CAMU Corrective Action Management Unit
CBEC Concentration Based Exemption Criteria
CCWE Constituent Concentrations in Waste Extracts
CERCLA Comprehensive Environmental Response Compensation and Liability Act of 1980
CESQG Conditionally Exempt Small Quantity Generator
CFR Code of Federal Regulations
CLP Contract Laboratory Program
COC Chain of Custody
CRDL Contract Required Detection Limits
CTRL Chronic Toxicity Reference Levels
CVAA Cold Vapor Atomic Adsorbtion
CWA Clean Water Act
DAF Dilution Attenuation Factor
DC Direct Current
DQO Data Quality Objectives
DQOPP Data Quality Objectives Planning Process
FAA Flame Atomic Adsorbtion
FIFRA Federal Insecticide, Fungicide, and Rodenticide Act
EP Tox Extraction Procedure Toxicity
EQL Estimated Quantitation Limit
GFAA Graphite Furnace Atomic Absorption
HAZWRAP Hazardous Waste Remedial Action Program
HSWA Hazardous Solid Waste Amendments
HWN Hazardous Waste Numbers
P designates Acute Toxicity
U designates Toxic Waste
K designates Process Waste
F designates Generic Source Waste
D designates Characteristic Waste
ICP Inductively Coupled Plasma
LDR Land Disposal Restrictions
LOG Large Quantity Generator
MCL Maximum Contaminant Level
MCLG Maximum Contaminant Level Goals
MS Matrix Spike
MSD Matrix Spike Duplicate
NIPDWS National Interim Primary Drinking Water Standards
NPDES National Pollutant Discharge Elimination System
PCB Polychlorinated Biphenyls
POHC Principal Organic Hazardous Constituent
POTWs Publicly Owned Treatment Works
PPIC Pollution Prevention Information Clearinghouse
PPIES Pollution Prevention Information Exchange System
PQL Practical Quantitation Limit
QA Quality Assurance
QAMS Quality Assurance Management Staff
QC Quality Control
RA Regional Administrator
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List of Abbreviations and Acronyms (Continued)
RCRA Resource Conservation and Recovery Act
RFI RCRA Facility Investigation
RSD Risk Specific Doses
RfD Referenced Doses
SDWA Safe Drinking Water Act
SQG Small Quantity Generator
SW-846 Solid Waste Procedures
TC Toxicity Characteristic
TCLP Toxicity Characteristic Leaching Procedure
TIC Tentatively Identified Compound
TSCA Toxic Substances Control Act
TSDF Treatment Storage and Disposal Facility
DIG Underground Injection Control
USDW Underground Sources of Drinking Water
UST Underground Storage Tank
VOA Volatile Organic Analysis
ZHE Zero Headspace Extraction
XI
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Chapter 1
COMPLYING WITH THE TC RULE
Introduction
RCRA Overview
The Toxicity Characteristic Rule
TC Rule's Effect on Individual RCRA Regulations
Impact on Other RCRA Programs
Pollution Prevention
Conclusions
XII
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1.0 COMPLYING WITH THE TOXICITY CHARACTERISTIC RULE
The purpose of this chapter is to provide an understanding of the Toxicity
Characteristic (TC) Rule, as it relates to hazardous waste management under
the Resource Conservation and Recovery Act (RCRA). The development of
hazardous waste issues in the United States is discussed first, giving the
example of Love Canal, which is a case study of an uncontrolled hazardous
waste site. Then an overview of RCRA is presented, with a comparison of the
Extraction Procedure Toxicity (EP Tox) Test and the TC Rule, including the
Toxicity Characteristic Leaching Procedure (TCLP) is presented. Finally, the
impact of the TC Rule on RCRA and non-RCRA regulations is discussed.
1-1
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1.1 Introduction
Hazardous waste growth in America.
RCRA system to control hazardous waste disposal.
Determination of hazardous waste by testing.
Changes to the testing procedure for hazardous waste. TC Rule replaces
the EP Tox Test.
Purpose of the manual.
In America, about 500,000 companies generate approximately 170,000 metric tons of
hazardous waste annually.
In 1976, the Resource Conservation and Recovery Act (RCRA) was passed for
proper management of hazardous waste to protect human health and the
environment.
The extraction procedure toxicity (EP Tox) test was one of the analytical methods
used to ascertain if a waste was hazardous.
The Toxicity Characteristic Leaching Procedure (TCLP) replaced the EP Tox test
when determining if a solid waste is hazardous because it exhibits the toxicity
characteristic.
1-2
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1.2 RCRA OVERVIEW
1.2.1 Growth of Hazardous Waste in America: The Case of Love Canal
America in the 1890s.
The invention of electricity.
New chemicals.
Clustering of industries around power sources.
Building of Love Canal to connect the lower and upper parts of Niagara
Falls.
DC power versus AC power.
America in the 1890s was undergoing industrialization. With the invention of electric
power, new chemicals were developed. A widely used chemical process was the
electrolysis of sodium chloride (salt) to yield sodium hydroxide (lye), chlorine and
hydrogen. Lye was mixed with waste animal fat from slaughter houses to produce
soap. Ivory soap is still made this way. Chlorine, originally a useless byproduct,
eventually was utilized as a raw material in the production of chlorinated solvents and
pesticides. These chemicals had toxic effects which were not then understood.
Direct current (DC) electricity was used for this electrolysis process. Industries in the
1890s which used significant quantities of electricity had to cluster around their DC
power sources because DC electricity does not travel efficiently.
In Niagara Falls, a hydroelectric dam generated low cost electrical energy. Industries
were clustered in the area to obtain inexpensive DC power. Construction
commenced on the Love Canal industrial transportation network to connect the lower
and upper parts of the Niagara Falls area.
However, when alternating current (AC) electricity was invented, electricity travelled
much further over power lines. Thus, it was no longer necessary to cluster industries
around the Niagara Falls area, and the Love Canal project was abandoned. Love
Canal was subsequently used by industry as a hazardous waste dump, and leached
toxic contaminants into the surrounding ground water and soil. Even after Love
Canal was capped and closed, toxic chemicals continued to leach out.
Most of the discarded hazardous chemicals were contained in the clay-lined Love
Canal until school and highway construction ruptured the walls. This fracturing of the
walls caused chemicals to contaminate local homes and the school built directly over
the dump site. People living in the area started to experience health problems,
including miscarriages, stillbirths, and chromosome damage.
1-3
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In 1980, President Jimmy Carter evacuated approximately 700 families out of the
Love Canal area to protect their health.
The purpose of RCRA is to prevent this type of inadequate hazardous waste
management.
1-4
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1.2.2 RCRA Cradle to Grave Concept
RCRA tracks hazardous waste from cradle to grave:
the manifest system.
Components:
generator
transporter
treatment storage and disposal facility (TSDF).
Anyone generating hazardous waste must notify EPA:
generator definition.
RCRA is considered a "cradle to grave" system because it regulates the handling of
hazardous waste from creation to disposal. This ensures that hazardous waste is
handled properly, and does not contaminate the environment.
There are three hazardous waste handler classifications: the generator, who creates
the hazardous waste; the transporter, who transports the hazardous waste to the
ultimate disposal site; and the ultimate disposal site, which is called a treatment,
storage and disposal facility (TSDF). Final disposition of hazardous waste often
occurs after interim storage/treatment/recycling operations at several sites.
Facilities that generate solid waste must determine if their solid waste is a hazardous
waste.
Facilities that generate hazardous waste must notify EPA or the authorized State
agency, and obtain an EPA facility identification number (EPA ID number).
The EPA or an authorized state agency issues an EPA ID number to make unique
identification of each TSDF which handles hazardous waste.
Hazardous waste generators must manage hazardous waste according to RCRA
regulations. The generator must dispose of hazardous waste properly, and must
complete a manifest enumerating the contents of the waste.
The generator is responsible for using authorized transporters and disposal facilities.
The generator can usually store hazardous waste on site for up to 90 days without a
storage permit.
1-5
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Generator responsibilities:
Determination of hazardous waste
Notify EPA
Obtain EPA ID number
Prepare manifest
Dispose of waste using an authorized transporter and an
authorized TSDF
Accumulation time
Annual reports
Contingency plans/Training requirements
Generator categories - CESQG/SQG/LQG
RCRA enforcement:
State versus Federal
The generator must file bi-annual reports detailing the amount of waste disposed.
EPA generator categories (many states have different generator categories):
LQG - Large quantity generators (LQG) generate more than 1000 kilograms
(kg) of hazardous waste/month or more than 1 kg of acutely hazardous
waste/month. LQGs are fully regulated and must comply with all
generator requirements indicated above.
SQG - Small quantity generators (SQG) are generators which:
Generate between 100 and 1,000 kg/month of hazardous
waste.
Accumulate no more than 6,000 kg of hazardous waste on site
at any one time.
Accumulate hazardous waste on site for up to 180 days or 270
days if the disposal site for the waste is over 200 miles away.
Provide notification of hazardous waste activities, use manifests
to dispose of hazardous waste, and dispose of hazardous
waste at TSDFs, but do not file annual reports.
1-6
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CESQG - Conditionally exempt small quantity generators (CESQG) are
generators which:
Generate less than 100 kg/month non-acute hazardous
waste per calendar month or;
Generate less than 1 kg/month acutely hazardous waste
(P-waste code). There are also several acutely
hazardous F-listed wastes.
May never accumulate more than 1,000 kg of hazardous
waste or greater than 1 kg of acutely hazardous waste at
any time. If they do, they will be regulated as a SQG.
Are subject to reduced requirements. SQGs do not need
to notify EPA or State agencies, use manifests, or
dispose of their hazardous waste in a TSDF (they may
use a municipal or industrial landfill).
RCRA enforcement:
EPA has delegated RCRA enforcement authority to many states. In those
states, the hazardous waste regulations may not be less strict than EPA's
regulations. Some states have regulations which are more stringent than
EPA's.
EPA however, retains overall jurisdiction over all state RCRA programs.
1-7
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1.2.3 Definitions of Hazardous Waste
Only wastes classified as "solid wastes" may be characterized as
"hazardous wastes".
The definition of hazardous waste has four parts:
"Statutory definition"
"Listed waste" - Four lists: F, K, U, P
"Mixture rule" - Defines hazardous waste as being a mixture of a
hazardous waste and a non-hazardous waste.
"Characteristic waste"
Ignitable
Corrosive
Reactive
Toxic - (TC Rule)
Only wastes classified as "solid wastes" may be characterized as "hazardous
wastes." Definition of solid waste:
"The term solid waste means any garbage, refuse, or sludge, from a waste
treatment plant, water supply treatment plant, or air pollution control facility; and
other discarded material, including solid, liquid, semisolid, or contained gaseous
material resulting from industrial, commercial, mining, and agricultural
operations, and from community activities, but does not include solid or dissolved
materials in irrigation return flows or industrial discharges which are point
sources subject to permits under Section 402 of the Federal Water Pollution
Control Act, as amended Statute 880; or source, special nuclear, or byproduct
material as defined by the Atomic Energy Act of 1954, as amended (68 Statute
923).'*
Definition of hazardous waste:
"The term 'hazardous waste' means a solid waste, or combination of solid
wastes, which because of its quantity, concentration, or physical, chemical or
infectious characteristics may:
(A) cause, or significantly contribute to an increase in mortality or an increase
in serious irreversible, or incapacitating reversible, illness; or
(B) pose a substantial present or potential hazard to human health or the
environment when improperly treated, stored, transported, or disposed of,
or otherwise managed.ll2
1 42 United States Code (USC) 6903, Section 1004(27)
2 - Ibid, (5)
1-8
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Regulatory Definitions:
Listed hazardous waste - Wastes classified as hazardous because of how they were
produced. There are four lists of hazardous waste: F, K, U, and P.
Four types of listed waste:
F Waste - List of waste from non-specific sources
K Waste - List of waste from specific sources
U Waste - List of discarded chemical products
P Waste - List of acutely toxic discarded chemical products
Mixture rule - Any mixture of a listed hazardous waste and a non-hazardous waste is
considered hazardous.
Derived from rule - See 40 CFR 261.3c.
Characteristic waste - Four characteristics are utilized to determine if a solid waste,
which is not a listed hazardous waste, is classified as a hazardous waste.
Characteristic of ignitability:
A flashpoint of < 140°F
For non-liquids - if the waste, when ignited, can burn spontaneously
An ignitable compressed gas
An oxidizer as defined in 49 CFR 173.151
Characteristic of corrosivity:
The waste is aqueous and pH < 2 or > 12.5.
The waste corrodes steel at a rate of > 6.35 millimeters/year.
Characteristic of reactivity:
The waste is unstable and undergoes violent reaction.
The waste reacts violently with water.
The waste, when heated, is explosive.
The waste, when mixed with water, releases toxic gases.
The waste contains cyanide or a sulfide, and releases toxic gases when
exposed to pH conditions between 2 and 12.5.
The waste can explode if shocked or heated.
The waste is defined as an explosive by U.S. Department of Transportation
regulations.
Characteristic of toxicity - A waste exhibits the characteristic of toxicity if the
concentration of one or more of the 39 toxicity characteristic analytes in the TCLP
aqueous extract exceeds regulatory action levels. This is known as the TC Rule.
This replaces the EP Tox Test, which contained 8 inorganic and 6 organic
constituents.
Note: If wastes are listed solely because they exhibit a characteristic, and the
resulting mixture no longer exhibits a characteristic, the material is no longer a
hazardous waste.
1-9
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1.2.4 Making a Hazardous Waste Determination
Does the waste meet the definition of solid and hazardous waste?
Is the waste excluded?
Is the waste listed?
Does the waste exhibit a characteristic of hazardous waste?
Hazardous Waste Determination
Is the waste a solid waste?
Is the solid waste excluded from the RCRA regulations?
If the solid waste is not excluded from the hazardous waste regulations, is it a listed
waste? By definition, listed wastes are hazardous wastes.
If neither excluded nor listed, does this solid waste exhibit any of the characteristics
of hazardous waste? If so, it is a hazardous waste.
Note: Solid waste is determined to be hazardous waste by:
The generator's reasonable knowledge of the characteristics of the waste, or
The generator's testing of the waste.
Listed hazardous waste is hazardous regardless of analyte concentrations in TCLP
extract.
1-10
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1.3 THE TOXICITY CHARACTERISTIC RULE
1.3.1 EPToxTest
What is the Extraction Procedure Toxicity (EP Tox) Test?
What is the EP Tox Test based on?
Landfill leaching,
14 metals and organics form the basis of the EP Tox Test.
Contaminant levels of the EP Tox Test
Relationship to drinking water standards,
Dilution attenuation factor (DAF).
EP Tox Test was utilized prior to TCLP to ascertain if a waste exhibited the
characteristic of toxicity. The EP Tox Test analyzed waste extracts for 14 specified
chemical constituents.
EP Tox Test was based on the assumption that chemicals placed in a landfill will
leach at a uniform rate into the ground water.
EP Tox regulatory action levels are based upon drinking water standards:
(allowable drinking water level) X 100 = EP Tox regulatory level (assumes that
toxic chemicals leaching out of landfill will be diluted by a factor of 100);
The factor of 100 is termed a dilution attenuation factor (DAF).
The 14 metals and organic chemicals regulated by the drinking water program
were assigned EP Tox regulatory levels.
8 metals
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
4 insecticides
2 herbicides
Endrin
Lindane
Methoxychlor
Toxaphene
2,4- D
2,4,5 - TP (silvex)
1-11
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1.3.2 TCLPTest
Why replace the EP Tox Test with the TC Rule?
How is TC different than EP Tox?
How regulatory limits are determined for the TC Rule.
Regulatory level = CTRL X DAF
The EP Tox Test was replaced by the TC Rule because of a Congressional
mandate for aggressive regulation of additional toxic constituents.
The original EP Tox Test was not capable of leaching volatile organic
compounds without unacceptable losses during the leach test.
Major changes:
25 additional organic chemicals
different leaching medium
procedural modifications for leaching volatile compounds
The regulatory limit for the TCLP constituents was determined by multiplying
the Chronic Toxicity Reference Level (CTRL) times the Dilution Attenuation
Factor (DAF):
Regulatory limit = CTRL X DAF
The CTRL is a level below which health effects are not expected to occur.
The CTRL is based on: drinking water standards maximum contaminant level
(MCL); or for carcinogens, the risk specific dose (RSD); or for non-
carcinogens, the reference dose (RfD).
1-12
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TABLE 1-1 - TC RULE CONSTITUENTS
EPA WASTE
NUMBER
D004
D005
D006
D007
D008
D009
D010
D011
D012
D013
D014
D015
D016
D017
HAZARDOUS
CONSTITUENT1
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Lindane
Methoxychlor
Toxaphene
2,4-D
2,4,5-TP (Silvex)
Level
(mg/l)
5.0
100.0
1.0
5.0
5.0
0.2
1.0
5.0
0.02
0.4
10.0
0.5
10.0
1.0
EPA
WASTE
NUMBER
D018
D019
D020
D021
D022
D023
D024
D025
D026
D027
D028
D029
D030
HAZARDOUS
CONSTITUENT2
Benzene
Carbon tetrachloride
Chlordane
Chlorobenzene
Chloroform
o-Cresol
m-Cresol
p-Cresol
Cresol (total)
1 ,4-Dichlorobenzene
1 ,2-Dichloroethane
1,1-Dichloroethylene
2,4-Dinitrotoluene
Level
(mg/l)
0.5
0.5
0.03
100.0
6.0
200.0
200.0
200.0
200.0
7.5
0.5
0.7
0.13
EPA
WASTE
NUMBER
D031
D032
D033
D034
D035
D036
D037
D038
D039
D040
D041
D042
D043
HAZARDOUS
CONSTITUENT2
Heptachlor (& epoxide)
Hexachlorobenzene
Hexachloro-1 ,3-
butadiene
Hexachloroethane
Methyl ethyl ketone
Nitrobenzene
Pentachlorophenol
Pyridine
Tetrachloroethylene
Trichloroethylene
2,3,5-Trichlorophenol
2,4,6-Trichlorophenol
Vinyl chloride
Level
(mg/l)
0.008
0.13
0.5
3.0
200.0
2.0
100.0
5.0
0.7
0.5
400.0
2.0
0.2
1 Original EP Tox constituents.
2 Chemical constituent added by TC Rule (shaded areas).
1-13
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1.3.3 TC Rule's Effect Upon Generators and TSDFs
Generators
Notification
Manifests
Annual report
LDR
In addition to the above requirements, TSDFs must
Obtain a new permit
Modify an existing permit
Close prior to obtaining a permit
Obtain interim status
Make changes to interim status
Meet minimum technology requirements for pretreatment
Generators which produce newly regulated TC hazardous waste not previously
regulated, must submit notification, use manifests, etc., as required by their generator
status. Generator responsibilities are discussed in Section 1.2.2. If the waste was
previously regulated under EP Tox, no additional requirements are applicable.
Options for TSDFs
Obtain a new permit
Land disposal facilities newly regulated by the TC Rule are required to
comply with minimum technology requirements when new units are
added, existing units are replaced, or existing units are laterally
expanded.
New permit requirements are enumerated in 40 CFR 270.
Modify an existing permit (see Table 1-2)
The three classes of permit modifications are based on the significance
of the modification. This three-tiered process, which replaces the two-
tiered major/minor process, is used by the permittee to initiate a permit
change. In contrast, EPA uses the old major/minor process if it initiates
a permit change.
Class 1 - modifications for routine changes;
Class 2 - modifications for changes of moderate complexity that allow
the facility to respond to changing conditions; and
Class 3 - modifications for substantial facility alterations.
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If waste at a permitted Subtitle C facility exhibits the TC for constituents that
were previously identified as EP toxic, the facility continues to comply with its
permit. No permit modification is needed.
Permitted Subtitle C facilities/units handling newly regulated TC wastes must
submit permit modifications to incorporate:
new TC Rule wastes
new regulated units managing TC Rule wastes
TSDF Options
Close the facility prior to obtaining a permit.
Obtain interim status by submitting a Part A application as an interim permitted
TSDF.
Changes to interim status
Change the conditions of the Part A interim status permit application to
reflect the new hazardous waste.
EPA's new procedures for interim status are listed in
40 CFR 270.72 (a)(1)
No prior approval is required for adding newly regulated units to Part A
permit applications if:
Units were managing new wastes (e.g., TC wastes) on or
before effective date.
Amended Part A was submitted by effective date.
Prior to March 7, 1989, new units received approval from EPA.
These new units are not subject to the reconstruction limit,
which restricts cumulative interim status facility changes to less
than 50% of the capital costs of a comparable new facility.
Changes to interim status - Facilities with Surface Impoundments
Implementation of the TC Rule may cause some facilities to alter their
management practices to avoid regulation of certain units under
Subtitle C of RCRA.
Retrofitting surface impoundments to accept TC wastes entails adding
liners and leachate collection systems not installed when the
impoundment was constructed.
Changes to interim status - Land Disposal Units
New land disposal units should have submitted certification of
compliance with ground water monitoring and financial responsibility
requirements by September 25, 1991.
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Land Ban Requirements
Land disposal restrictions refer to restrictions on the land
disposal of hazardous wastes. Restricted wastes must be
treated as specified in the LDR regulations, otherwise they are
banned from disposal on land.
Any TC Rule wastes regulated by the LDR regulations would be
prohibited from land disposal.
Minimum Technology Requirements - Surface Impoundments
Surface impoundments which were newly regulated as a result of the
TC Rule were required to meet minimum technology standards by
March 29, 1994.
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Type of Unit
Involved
TABLE 1-2 - PERMIT MODIFICATIONS
Permit Change Needed
Modification
Class
Tank or Container
Surface
Impoundment,
Landfill, Waste
Pile, or Land
Treatment
Incinerator
Addition of waste codes or units that will not
require additional or different management
practices than specified in the permit.
Addition of waste codes or units that will
require additional or different management
practices than specified in the permit.
Addition of waste codes or units that will not
require additional or different management
practices than specified in the permit.
Addition of waste codes or units that will
require additional or different management
practices than specified in the permit.
Addition of units.
If waste does not contain a principal organic
hazardous constituent (POHC) that is more
difficult to incinerate and no additional
performance standards are needed.
If waste contains POHC that is more difficult
to incinerate.
If different performance standards are
needed in the permit.
3
2
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1.4 TC RULE'S EFFECT ON INDIVIDUAL RCRA REGULATIONS
1.4.1 General
The TC Rule has potential impact on other parts of the RCRA program.
Regulations not impacted
Regulations which are impacted
The TC Rule will not affect wastes already considered hazardous. The following
RCRA regulations are not affected by the TC Rule:
Listed hazardous wastes (i.e., the F, K, P, and U lists)
Wastes that are hazardous by the "Mixture" and "Derived From" rules
Wastes already excluded from regulation
The implementation of the TC Rule increases the categories and volume of solid
waste classified as hazardous waste. The expanded definition causes additional
solid waste to be classified as hazardous wastes. The following RCRA regulations
are affected by the TC Rule:
Corrective action and closure
Land disposal restriction (LDR) regulations
Minimum technology requirements for surface impoundments and landfills
Mixture rule exemptions
Previously delisted wastes
Special waste exclusions
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1.4.2 Corrective Action and Closure
TC increased the universe of regulated facilities.
Number of Subtitle C permitted and interim status facilities subject to
corrective action increased.
Number of regulated units within permitted or interim status
facilities undergoing closure increased.
Excavated material from corrective action and closure that exhibits the TC
must be managed as hazardous waste.
TC levels are not used to set clean-up levels for corrective actions or
clean closures.
The TC Rule added more wastes of concern and brought more facilities under the
RCRA program as hazardous waste management facilities. Therefore, additional
facilities are newly subject to the Subtitle C corrective action and closure
requirements.
Previously unregulated TSDFs managing TC Rule wastes were subject to
RCRA requirements if they did not close or change management practices
(e.g., exempt tanks) before the TC Rule became effective.
Existing RCRA facilities may have to amend their closure plans to reflect
newly regulated units as the TC Rule expands the number of regulated units.
Excavated materials, which did not previously exhibit the toxicity characteristic, may
now have to be managed as hazardous waste because of the addition of newly
added constituents to the regulated list.
The Subtitle C corrective action program addresses remediation of hazardous waste
releases from facilities subject to RCRA permitting. The TC Rule levels are neither
action levels nor cleanup standards, both of which are developed from site-specific
information gathered during the investigatory and evaluation phases of the
remediation process.
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1.4.3 Land Disposal Restrictions (LDR)
LDR standards will continue to affect the 14 wastes previously regulated
under the EP Tox Test.
No LDR standards are currently promulgated for the 25 new TC
constituents.
LDR treatment standards are based on the best demonstrated available
technology (BOAT) standards. The characteristic (regulatory) levels were
developed using a risk-based approach.
For some constituents, LDR treatment standards are set at the regulatory
level.
HSWA requires EPA to make an LDR determination for all newly listed wastes within
six months of publication in the Federal Register, or by the effective date of the TC
Rule ruling. Newly listed or identified wastes were not automatically prohibited from
land disposal under LDRs if EPA failed to make this determination within six months
(i.e., no "hammer" provisions).
EPA set LDR standards for the 14 original EP characteristic constituents,
which EPA does not consider newly identified. These 14 constituents had to
meet LDR treatment standards before land disposal on the effective date of
the TC Rule.
The 25 additional organics identified by the TC Rule are considered newly
identified, and as such have not yet been affected by LDR regulations.
EPA is reviewing the treatability of each TC Rule constituent independently to
determine LDR treatment standards for TC Rule wastes. These standards may differ
from standards set for spent solvent wastes (F001-F005) based on differences in
treatability.
LDR treatment standards are based entirely on technology-based standards
expressed as BOAT. While TC Rule levels are based upon health-based allowable
concentration levels and dilution/attenuation factors, they are not the same as LDR
treatment standards. However, for many TC wastes, EPA has set the LDR treatment
standards at the regulatory level.
This issue is being litigated. Therefore, the LDR treatment standards for TC Rule
wastes may change.
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1.4.4 Minimum Technology Requirements for Landfills and Surface Impoundments
Landfills and surface impoundments newly regulated under RCRA
because of the TC need to comply with minimum technology
requirements
HSWA requires that:
Interim status waste piles, landfills, and surface impoundments
must meet certain minimum technology requirements
Surface impoundments must be retrofitted to meet minimum
technology requirements
Existing land disposal units, except surface impoundments, that already contained
TC Rule wastes will not require retrofitting unless they are expanding, replacing units
or continuing to place TC Rule wastes in these units.
The minimum technology requirements (liners and leachate collection systems) for
interim status surface impoundments are found in 40 CFR 265.221.
Surface impoundments that become regulated under Subtitle C because of the TC
Rule must have met the minimum technology requirements by March 29, 1994. This
extension applied to those impoundments that contain the newly identified or
characteristic wastes.
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1.4.5 Exemption for Tanks (Minimum Technology Requirements)
TC wastes treated in wastewater treatment tanks are exempt from
hazardous waste management standards under 40 CFR 264.1(g) and
265.1(c).
Generators that manage TC wastewaters in on-site surface
impoundments may switch to exempt tanks in order to avoid Subtitle C
requirements.
However, generators and handlers should have converted their surface
impoundments to tanks prior to effective date of the final rule to maintain
the exemption.
Facilities managing TC wastes after the effective date, even
unintentionally, are subject to interim status requirements.
40 CFR 264.1(g) and 265.1(c) exempt wastewater treatment units containing
hazardous waste from Subtitle C regulation.
Generators that continue managing wastewaters in on-site surface impoundments or
non-wastewaters on site will require either interim status or a RCRA permit
modification/change during interim status, depending on whether the facility is
currently a Subtitle C TSDF.
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1.4.6 Mixture Rule Exemption
The mixture rule exemption was not modified by the TC rule; mixtures of
wastewaters and certain listed spent solvents are exempt from Subtitle C
regulations unless the wastewaters:
Exhibit hazardous waste characteristic; or
Contain listed hazardous wastes not specified in the exemption.
TC Rule may regulate currently exempted wastewaters under Subtitle C.
The mixture rule under 40 CFR 261.3(a)(2)(iv) provides an exemption from RCRA
Subtitle C requirements for mixtures of wastewaters and certain listed spent solvents
in low concentrations.
The mixture rule exemption only addresses hazardous waste listings. Therefore, the
mixture rule exemption does not affect the TC Rule.
The mixture rule exemption precludes mixtures of wastewaters and specific listed
spent solvents from hazardous waste regulations, unless they exhibit a characteristic
of hazardous waste.
EPA proposed modifying the mixture rule exemption to make it more consistent with
current risk information.
The TC Rule regulatory levels are based on state-of-the-art toxicological data and
risk assessment methodologies. In contrast, the mixture rule exemption levels are
based upon less current risk information.
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1.4.7 Previously Delisted Wastes
A waste previously "excluded" under Subtitle C regulation may no longer
be delisted if it exhibits a hazardous characteristic (e.g., the characteristic
of toxicity).
TC rule applies to already delisted wastes that now exhibit TC
characteristics.
These wastes are no longer considered "not hazardous"
These wastes must now be managed under Subtitle C
Because delisting levels are generally more stringent than the final TC
levels, the impact of TC rule on previously delisted wastes is expected to
be minimal.
Wastes "excluded" from Subtitle C regulation under the delisting program may
nevertheless be hazardous if they exhibit a hazardous characteristic (see 40 CFR
260.22). Hazardous waste characteristic levels are those above which a waste is
hazardous due to a particular property; delisting levels are those below which a waste
is not hazardous for any reason. Thus, it is reasonable that these two levels do not
coincide.
Although the TC Rule applies to delisted wastes, EPA does not, in general, expect
that such wastes will become hazardous because of application of the revised TC
Rule. However, if a previously delisted waste exhibits the TC Rule, it will again be
subject to Subtitle C requirements, and the facility will have to notify EPA of its
activity.
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1.4.8 Special Waste Exemptions
RCRA defines four special waste categories exempted from Subtitle C
regulation:
Mining wastes
Mineral processing wastes
Oil and gas wastes
Domestic sewage
Subtitle C regulations may apply to these special wastes on a case-by-
case basis.
Special waste exclusions are being reevaluated as mandated by
Congress.
If EPA determines that any special waste should be regulated under RCRA Subtitle
C, the Agency will determine the applicability of the TC Rule to such wastes.
After completing the studies required by RCRA Section 8002, EPA may determine
that one or more special wastes should be regulated under RCRA Subtitle C. Such
wastes would then be listed or the generators required to determine whether the
wastes exhibit a hazardous characteristic, including those specified in the TC Rule.
The TC Rule will have no direct effect on the following types of wastes:
Listed hazardous waste.
Wastes classified as hazardous by the "mixture" and "derived from" rules.
Wastes already excluded from regulation under 40 CFR 261.4
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1.4.9 Listed Hazardous Waste
TC rule has no effect on listings of hazardous waste
Wastes already listed as hazardous are always considered
hazardous, unless they are delisted.
Hazardous waste listings will continue to supplement the revised TC Rule. The TC
Rule revisions do not eliminate any hazardous waste listings.
Listed hazardous wastes continue to be hazardous even if they contain TC Rule
constituents in concentrations below TC regulatory levels.
TC Rule regulatory levels are not designed to identify the full range of wastes that
may be toxic to human beings. Instead, the characteristic levels were established to
protect human health.
Listed wastes that do not exhibit the toxicity characteristic may nevertheless be
hazardous because:
They contain listed hazardous waste constituents; or
They contain hazardous constituents that are not covered by the TC Rule.
Listed wastes frequently contain hazardous constituents other than the ones cited in
Appendix VII of 40 CFR Part 261. These additional hazardous constituents present
in a waste may not be TC Rule constituents. Removing wastes from a hazardous
waste listing without evaluating additional constituents would be inconsistent with the
intent of RCRA §3001 (f).
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1.4.10 "Mixture" and "Derived From" Rules
TC has no effect on the regulatory status of waste "mixtures" or "derived
from" wastes:
Mixtures of listed wastes and solid wastes, and residues derived
from listed wastes, are still hazardous until delisted.
TC alone is not adequate to regulate mixtures and treatment residues.
Problems may result by applying "mixture" and "derived from" rules.
The "mixture" rule (40 CFR 261.2(a)(2)(iv)) states that any mixture of a listed
hazardous waste and a solid waste is a RCRA hazardous waste.
The "derived from" rule (40 CFR 261.3(c)) states that any waste derived from the
treatment, storage, or disposal of a listed hazardous waste is hazardous.
The "mixture" and "derived from" rules creates inequities in the classification of
certain dilute wastes. For example, very low constituent concentrations in listed
wastes may still be considered hazardous even after treatment.
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1.4.11 Excluded Wastes
TC Rule does not apply to wastes that are already excluded from Subtitle
C regulations under 40 CFR 261.4:
For example, household hazardous waste is excluded from
Subtitle C; it remains excluded after the TC effective date.
TC Rule does not add any exclusions to the applicability of previously
promulgated hazardous waste characteristics.
Wastes described in 40 CFR 261.4(b) that are already excluded from Subtitle C
regulations will continue to be exempt from regulation as hazardous wastes, even if
they exhibit the TC Rule.
EPA does not at this time intend to expand the list of exemptions under 40 CFR
261.4(b) to include creosote- and pentachlorophenol-treated wood.
Other wastes that are excluded from Subtitle C in 40 CFR 261.4(b) include:
Household hazardous wastes
Certain mining wastes
Certain solid wastes generated from farming or raising animals
Certain wastes generated from the combustion of coal or other fossil fuels
Wastes associated with the production of crude oil and natural gas
Some chromium containing wastes
Solid waste from extraction and processing of ores and minerals
Cement kiln dust wastes
Certain wood products
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1.5 IMPACT OF TC RULE ON OTHER EPA PROGRAMS
1.5.1 Underground Storage Tanks (USTs)
Two programs currently regulate underground storage tanks (USTs).
Subtitle C (tanks containing hazardous wastes) or Subtitle D
(tanks containing non-hazardous solid wastes),
Subtitle I (tanks containing petroleum product or hazardous
substance products).
The TC Rule may increase the number of tanks regulated under
Subtitle C.
Product (petroleum, hazardous substance) that leaks may become a
hazardous waste and may also exhibit TC.
Petroleum contains several TC constituents. Therefore, it is likely that some
petroleum-contaminated media will exhibit the TC.
The management of any petroleum-contaminated media exhibiting TC would
normally be subject to Subtitle C requirements for hazardous waste management.
However, EPA believes further study of these impacts is necessary before imposing
TC requirements on media and debris contaminated solely by petroleum from USTs.
EPA has insufficient information on the impact of the TC Rule on UST cleanups;
therefore, EPA has deferred a final decision on the application of the TC Rule to
media and debris contaminated with petroleum from USTs exhibiting the D018-D043
waste characteristics that are subject to the 40 CFR Part 280 requirements.
EPA believes deferral of a final decision concerning the application of the TC Rule to
UST cleanups is necessary. Imposition of the Subtitle C requirements is likely to
significantly delay cleanups and severely discourage the self-monitoring and
voluntary reporting essential to implementing the UST program.
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Subtitle I and Subtitle C potentially overlap if a substance exhibits the TC
characteristic and the origin of substance is not known.
The contents of a tank determines which regulatory program (i.e., Subtitle
C or Subtitle I) applies:
Subtitle C regulates hazardous wastes
Subtitle I regulates hazardous products and petroleum
Hazardous product that leaks may become hazardous waste.
Petroleum and hazardous product may exhibit the TC but may not be regulated under
Subtitle C.
Corrective action under Subtitle I addresses releases of product.
Old releases of product not subject to Subtitle I may have occurred:
Via inactive tanks
In areas considered as RCRA solid waste management units
If wastes exhibit the TC for D004-D017, RCRA standards may apply to these old
releases.
TC Rule excludes D018-D043 wastes from RCRA regulation if they are covered
under Subtitle I Corrective Action:
Petroleum-contaminated soil and ground water
Petroleum-contaminated debris (tanks)
EPA is studying impacts of Subtitle C regulation on petroleum-contaminated areas.
Note: Petroleum contaminated media from aboveground storage tanks are also
excluded from TCLP testing requirements where a state has an adequate treatment
mechanism in place.
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1.5.2 Comprehensive Environmental Response and Liability Act (CERCLA)
CERCLA response actions must comply with all applicable, or relevant
and appropriate requirements (ARARs), including RCRA regulations.
TC will cause more Superfund wastes to be classified as RCRA
hazardous wastes.
Thus, more Superfund cleanups will be subject to RCRA
regulations.
TC will not, however, affect CERCLA clean-up levels.
Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA
or Superfund) addresses remediation of inactive waste sites.
ARARs are "applicable or relevant and appropriate requirements." CERCLA must
meet other Federal or State environmental requirements whenever they are
applicable or relevant and appropriate to CERCLA actions.
The primary effect of TC Rule on Superfund will be to regulate many organic
constituents found at Superfund sites as RCRA hazardous wastes.
A current problem at many Superfund sites is determining if an organic
constituent is from a listed RCRA hazardous waste.
There is often little evidence about the source of contamination that exists at
Superfund sites to prove a waste is a listed waste. Therefore, a waste may
not be managed under RCRA (but it will be handled in a protective manner
according to risk assessment).
Under the TC regulation, if tetrachloroethylene is found above the TC
regulatory level, the waste is hazardous regardless of its origin.
As in RCRA corrective actions, Superfund response personnel will not use the TC to
determine whether to undertake a clean-up action. The TC will affect decisions
concerning the management of wastes generated during cleanup activities (i.e.,
hazardous wastes generated during cleanup must be managed in accordance with
Subtitle C). For a lower cost Superfund cleanup option, please read the CAMU Rule
discussion in Chapter 2.
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1.5.3 Clean Water Act (CWA)
The CWA regulates discharges of pollutants to surface waters and to
publicly owned treatment works (POTWs).
Regulatory levels of TC are consistent with those of the CWA:
NPDES effluent guidelines
Pretreatment standards
Treated wastewaters that exhibit the TC Rule.
The Clean Water Act (CWA) regulates discharges of hazardous substances to
surface waters through the National Pollutant Discharge Elimination System
(NPDES) permit program, and pretreatment standards for POTWs.
EPA believes TC levels and CWA standards are consistent.
Thus, CWA discharges are exempt from RCRA regulation under 40 CFR Part 261.
Treated wastewaters exhibiting TC are regulated under RCRA unless:
discharged under NPDES permit
treated in POTW
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Objectives of the Clean Water Act
Impact of the Clean Water Act
^^^^^^^m
Objectives of the CWA are:
To restore and maintain the chemical, physical, and biological integrity of the
nation's waters;
To eliminate the discharge of pollutants into surface waters;
To attain water quality that provides for the protection and propagation of fish,
shellfish, and wildlife, and provides for recreation in and on the water.
Impact of the Clean Water Act:
In lieu of retrofitting and obtaining permits for existing surface impoundments
to meet RCRA requirements, hazardous waste management facilities may
utilize tank treatment and storage of hazardous wastewater. NPDES
treatment tanks are exempt from RCRA permitting requirements.
Wastewater treatment facilities using surface impoundments to treat TC waste
may be subject to RCRA regulations.
The Agency expects many owner/operators to replace surface
impoundments with wastewater treatment tanks.
Wastewater treatment tanks are exempt from Subtitle C regulation
under 40 CFR 264.1(g)(6) and 265.1(c).
If a POTW sludge (from wastewater treatment) exhibits TC, the
owner/operator must treat the sludge to remove the characteristic.
Treatment may be through a pre-treatment program (i.e., before POTW
receives discharge); or
After sludge is produced.
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1.5.4 Safe Drinking Water Act (SDWA)
Safe Drinking Water Act (SDWA) establishes maximum levels of
contaminants acceptable in public drinking water supplies.
Maximum Contaminant Levels (MCLs)
Maximum Contaminant Level Goals (MCLGs)
TC fate and transport models assume ingesting contaminated drinking
water, and uses MCLs as the basis for setting regulatory levels for many
TC constituents.
SDWA protects human health from contaminants in drinking water.
The specific objectives are:
To assure that all people served by public water systems be provided with a
high quality water;
To remove contaminants found in water supplies to protect human health; and
To establish programs to protect underground sources of drinking water from
contamination.
SDWA primary drinking water regulations include MCLs for specific contaminants.
Many TC levels are based on SDWA MCLs.
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Underground injection control (UIC) program regulates injection of fluids
to protect underground sources of drinking water (USDWs).
Five classes of wells are regulated under the UIC program:
Class I - municipal or industrial waste discharged beneath
USDWs
Class II - oil and gas production
Class III - mineral recovery
Class IV - hazardous or radioactive waste into or above
USDWs
Class V - all other wells used for injection of fluids,
including septic tanks and sumps.
Class I wells are often used by generators of hazardous waste or owner/operators of
hazardous waste management facilities to inject hazardous waste below USDWs.
The largest user of hazardous waste Class I wells is the chemical industry. Class I is
the smallest class of wells with 554 reported in 1989. There are no Class I
hazardous wells in Region 2.
Class IV wells are banned with the exception of wells used for remediation of aquifers
contaminated with hazardous wastes (40 CFR 144.13).
The largest group of injection wells is Class V, with approximately 180,000 wells.
The second largest group of wells is the Class II group with approximately 150,000
wells, followed by Class III wells with about 20,000 wells.
The Agency is enforcing the ban on shallow injection of hazardous wastes. The
Agency is also developing guidance on best management practices to reduce the
amount and toxicity of wastes injected into Class V wells (40 CFR 144.24).
The TC Rule may increase the number of Class I wells accepting TC waste, and
bring newly identified hazardous Class I wells into the Subtitle C program.
Some Class V wells may be illegally accepting hazardous wastes; the number may
increase as a result of the TC Rule.
Class V wells that may receive TC wastes:
Agricultural drainage wells;
Industrial drainage wells;
Experimental technology wells;
Industrial process water and waste disposal wells;
Automobile service station wells; and
Aquifer remediation-related wells.
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Wastes injected into some Class V wells are exempted from regulation as a
hazardous waste. For example: geothermal electric and direct heat re-injection
wells, several of the domestic wastewater disposal wells, most of the mineral and
fossil fuel recovery-related wells, and certain experimental technology wells.
Many of the facilities that operate Class V wells (e.g., auto service stations) also
generate listed hazardous waste, such as solvents. It is possible that some facilities
are not managing their listed wastes properly, and that hazardous wastes are
entering Class V wells. Of course, when hazardous wastes are injected into Class V
wells, they become Class IV wells.
It is unclear at this time what effects TC will have on the UIC program because the
Class V program is very new.
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1.5.5 Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
FIFRA regulates the sale, distribution, and use of all pesticide products.
RCRA regulates listed wastes, including pesticide product wastes.
TC Rule:
adds one pesticide to the list of TC constituents; and
regulates more "multiple active ingredient" formulations.
Other TC constituents may be ingredients in pesticides.
If pesticide wastes exhibit TC, they are subject to Subtitle C regulation
unless they are exempt.
The following pesticide users are exempt from RCRA requirements:
Household pesticide users.
Farmers who triple rinse their containers, dispose of the containers on their
own farm, and follow the pesticide manufacturer's label instruction for
disposal.
Small quantity generators following reduced requirements. Many pesticide
users are small quantity generators.
Properly emptied containers may be exempted from further RCRA
requirements under 40 CFR 261.7. Many pesticide containers, therefore, may
not be subject to regulation as hazardous waste.
There is no change in listed pesticide wastes that are either pure, technical grade, or
sole active ingredient product wastes; they will continue to be regulated under Subtitle
C (P and U listings).
The exemption for arsenic-treated wood was not expanded in the TC Rule.
This exemption may be reevaluated in the future.
Multiple active ingredient products are usually not regulated as RCRA Subtitle C
wastes, but are instead regulated under RCRA Subtitle D or FIFRA.
TC increases the potential for multiple active ingredient product wastes to be
hazardous.
Adding new pesticide constituents to the TC Rule will primarily affect commercial
applicators, such as aerial applicators and pest control operators. If they use large
quantities of multiple active ingredient pesticide products that have not previously
been regulated, such applicators may be newly subject to RCRA Subtitle C
requirements.
Wastes from multiple active ingredient products that do not exhibit a hazardous waste
characteristic will still be regulated under applicable FIFRA and RCRA Subtitle D
requirements.
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1.5.6 Used Oil Recycling Act
Some used oil exhibits TC or ignitability characteristic.
TC will affect used oil that is
used for road oiling;
that is dumped;
disposed in solid waste landfills and incinerators.
TC will not affect used oil that is:
Managed by do-it-yourselfers (exempt as household hazardous
waste);
Recycled through energy recovery (40 CFR Part 279 regulates
this activity);
Recycled in any other manner (regulated under 40 CFR 279).
Used oil may exhibit the toxicity or ignitability characteristic.
Disposed used oil which exhibits the toxicity characteristic is subject to full RCRA
Subtitle C regulation (40 CFR 279.80).
However, oil that is burned for energy recovery is not regulated as a hazardous
waste.
Used oil generated by household do-it-yourselfers is exempt form RCRA
under 40 CFR 279.20(a)(1).
Used oil that exhibits one or more of the characteristics of hazardous wastes
but is recycled in some other manner than being burned for energy recovery is
exempt under 261.6(a)(43).
Significant quantities of used oil may exhibit EP toxicity for metals, but little used oil is
currently recognized as EP toxic.
Shifts in used oil management practices may result from the TC Rule. Management
practices may shift away from road oiling, dumping, and disposal in solid waste
facilities to burning as fuel, recycling, and disposal in Subtitle C facilities.
Standards for regulating used oil that is recycled were promulgated in the Federal
Register on September 10, 1992 (FR 41566).
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1.5.7 Toxic Substances Control Act (TSCA)
TSCA addresses manufacturing, processing, and distributing hazardous
substances such as PCBs.
If TSCA-regulated products become wastes and contain D004-D017, they
become RCRA regulated.
If Polychlorinated Biphenyls (PCBs) are fully regulated under TSCA, TC
rule exempts those PCB-wastes containing D018-D043 from RCRA
regulations; not all PCB wastes are fully regulated under TSCA (D004-
D017).
Exempt wastes include PCB-containing dielectric fluids removed from:
Electrical transformers; and
Capacitors.
Toxic Substances Control Act (TSCA) regulates toxic substances and specifically
addresses PCB management and disposal.
Dielectric fluids from electrical transformers, capacitors and associated PCB-
contaminated electrical equipment could exhibit the TC because they may contain
chlorinated benzenes.
These wastes exhibiting TC are exempted from Subtitle C management
standards if they exhibit waste codes D018-D043.
The exemption applies only to certain wastes noted above that are fully
regulated under TSCA, not to all PCB wastes.
PCB wastes exhibiting D004-D017 characteristics (i.e., those hazardous under EP
toxicity) remain regulated under RCRA if they are a D004-D017 waste under TC (i.e.,
contain other constituents).
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1.6 POLLUTION PREVENTION
Defining pollution prevention.
Pollution prevention as a national priority for managing hazardous waste.
Priorities of pollution prevention:
Source Reduction
Source Reduction exclusions
Implementation.
The Pollution Prevention Act of 1990 encourages waste reduction at the source
rather than the management of waste already produced.
An integral component of EPA's RCRA program is pollution prevention through waste
minimization.
Therefore, EPA's encourages hazardous waste source reduction rather than "end-of-
pipe" controls.
EPA has produced industry-specific outreach materials to assist industry in their
waste minimization efforts (source reduction, process modifications, recycling, and
the use of less toxic materials).
Pollution prevention allows industry to:
Reduce costs of raw materials, hazardous waste treatment and disposal;
Minimize regulatory burdens of compliance;
Minimize liability for environmental problems and occupational safety
problems;
Enhance efficiency and product quality.
EPA encourages industries affected by this ruling to consider achieving compliance
through pollution prevention.
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Source reduction is:
A practice that reduces the amount of any hazardous waste entering a waste
stream or the environment that occurs prior to recycling, treatment, or
disposal;
A practice that reduces hazards to public health and the environment due to
release of hazardous substances, pollutants, or contaminants.
Source reduction includes:
Equipment/technology modifications;
Process/procedure modifications;
Reformulations/redesign of products;
Substitution of raw materials;
Improvements in housekeeping, maintenance, training.
Source reduction does not include:
Practices that alter the physical, chemical, biological characteristics or volume
of a hazardous substance, pollutant, or contaminant through process or
activity that, itself, is not integral to and necessary for the production of the
product or service.
EPA is implementing the strategy by:
Creating incentives for industry;
Building pollution prevention into their decision-making processes;
Making technical information available to help firms reduce waste generation
through the use of:
The Pollution Prevention Information Clearinghouse (PPIC), a
nationwide network of people and resources with direct experience in
waste reduction strategies in many industries (202-260-1023);
The Pollution Prevention Information Exchange System (PPIES), a
computer electronic bulletin board (703-506-1025) which contains a
database of bulletins, programs, contacts, and reports related to
pollution prevention.
Supporting the development of state programs to assist generators in their
waste reduction efforts;
Initiating specific new regulatory requirements for generators to:
Certify on their hazardous waste manifests and annual permit reports
that are reducing the volume or toxicity of their hazardous wastes as
much as possible;
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Describe on their RCRA biennial reports the efforts undertaken during
the year to reduce the volume and toxicity of their hazardous waste
and compare the efforts to those in previous years;
To require waste minimization/pollution prevention in RCRA permits for
TSDFs that generate hazardous waste.
EPA recommends owners/operators implementing waste minimization programs at
the plant level:
Conduct a waste minimization assessment by selecting a few processes or
waste streams for source reduction or recycling. Accurate records on the rate
of generation and the cost of management should be retained;
Identify waste minimization techniques;
Practice inventory management (substitute less toxic source materials);
Modify equipment (upgrading the performance of process equipment,
reducing leaks and malfunctions, installing conditioning or recovery systems);
Initiate production process changes; and
Recycle and reuse.
Contact the Pollution Prevention Office, U.S. EPA, 401 M Street, SW, Washington,
D.C. 20460 to obtain information or to offer suggestions on how the Agency might
facilitate waste reduction efforts.
Role of the TC Rule in the Pollution Prevention strategy:
By subjecting a larger number of toxic compounds to the RCRA regulations, it
increases the costs to generators of managing solid wastes.
In effect, the TC forces waste managers to rethink their solid waste
management practices due to the high cost of compliance with RCRA Subtitle
C requirements.
The TC will alter the management of previously disposed wastes that might
leach toxic contaminants by restricting their management in land-based units
(surface impoundments, waste piles, lagoons, etc.).
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1.7 CONCLUSIONS
The TC Rule expands the definition of hazardous waste.
The TC Rule adds 25 additional organic analytes.
The TC Rule should encourage facilities to utilize less hazardous
chemicals, to avoid the increased disposal costs associated with the TC
Rule.
By expanding the number of toxicity characteristic constituents from 14 to 39, EPA
has expanded the definition of hazardous waste, and brought more wastes under the
RCRA jurisdiction. This will keep additional wastes within the RCRA "cradle to grave"
system and prevent them from harming human health or the environment.
By adding organics to the EP Tox inorganics, the TC Rule addresses the potential
harm these substances could cause in the environment.
By increasing the costs of disposal for facilities which are now handling hazardous
wastes which were formerly not regulated, facilities are encouraged to find substitutes
or otherwise avoid chemicals which are hazardous.
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Chapter 2
APPLICATIONS OF THE TCLP METHOD
What is TCLP?
When is the Use of TCLP Applicable?
When is the Use of TCLP Inappropriate?
Sampling and Analysis Design
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2.0 APPLICATIONS OF THE TCLP METHOD
Discussions in this chapter include:
What is TCLP?
When is the use of TCLP applicable?
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2.1 What is TCLP?
An analytical method to simulate leaching through a landfill. The leachate
is analyzed for appropriate analytes.
TCLP is comprised of four fundamental procedures:
- sample preparation for leaching
- sample leaching
- preparation of leachate for analysis
- leachate analysis
The Toxicity Characteristic does not equal TCLP.
The toxicity characteristic leaching procedure is located in:
Test Methods for Evaluating Solid Wastes, SW-846 Method 1311, July 1992.
Appendix I of this document contains the July 1992 version of Method 1311. When
regulations specify the use of TCLP, approval to deviate from the method must be obtained
from the State or EPA Region.
The Toxicity Characteristic (TC) is utilized to determine whether a solid waste is classified as
a hazardous waste because it exhibits the characteristic of toxicity. The TC of a waste
material is established by determining the levels of 8 metals and 31 organic chemicals in the
TCLP extract of the waste. TC utilizes the TCLP method to generate leachate under
controlled conditions. The regulatory levels of TC constituents in the TCLP leachate are
listed in Table 2-1.
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2.2 When is the Use of TCLP Applicable?
The most common reasons for performing the TCLP are:
Determining if an unknown waste is hazardous according to 40 CFR
261.24.
Determining what type of disposal (hazardous waste or solid waste) is
appropriate. Solid wastes are not necessarily Hazardous.
Demonstrating the effectiveness of treatment processes to comply with
Land Disposal Restrictions (LDR) or "Land Ban" requirements.
Fulfilling shipping or transportation requirements.
Determining if a Waste is Hazardous
The toxicity characteristic regulations require generators to determine whether a solid waste
is a regulated hazardous waste. Generators of potentially hazardous waste can determine if
a waste is hazardous by one of the following methods:
If a waste is excluded from regulation (40 CFR 261.4), no further determination is
necessary.
If the waste is listed per 40 CFR 261.30-261.35. Listings may be industry and
process-specific (K-wastes) or may encompass all wastes from non-specific
processes (F-wastes). Listings also include commercial chemical and off-
specification products (P and U wastes).
If a waste is not excluded or not listed as a hazardous waste, the generator must
ascertain whether the waste exhibits any hazardous waste characteristic: toxicity,
ignitability, corrosivity, or reactivity.
A solid waste is classified as a hazardous waste because of characteristics,
knowledge, or testing.
If the waste is not listed, and there is not enough information to determine whether
the Toxic Characteristic constituents are present above regulatory action levels, the
TCLP test must be performed.
The waste generator must certify in writing that the waste is not hazardous and must
maintain records to demonstrate exclusion from RCRA requirements by knowledge or
testing results.
Characterizing Waste for Disposal
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The RCRA regulations specify how listed and characteristic hazardous waste must
be treated or disposed.
Hazardous waste disposal facilities are permitted to accept specific categories of
hazardous waste. Hazardous waste disposal facilities cannot accept hazardous
waste without a manifest which lists the constituents or characteristics of the
hazardous waste. TCLP waste characterization may be required by some disposal
facilities.
Disposal facilities may require initial waste testing. After analytical data are collected
from a waste, process knowledge may be used instead of testing.
The Land Disposal Restrictions (LDR) regulate hazardous waste treatment and subsequent
disposal. The following is a synopsis of the LDR regulations and their CFR citations:
40 CFR Part 268 Subpart A
The highlights are:
Definitions of "waste water" (40 CFR 268.2).
Material otherwise prohibited from land disposal may be treated in a surface
impoundment if the residues from that treatment comply with applicable
standards.
Petitions to allow land disposal of 40 CFR Part 268 Subpart C prohibited
wastes must include comprehensive waste and simulation model sampling
and analysis. This typically includes TCLP and other analysis.
Generators of restricted waste must either analyze their waste or its TCLP
extract or use process knowledge to ascertain if the waste complies with 40
CFR Part 268 Subpart D treatment standards for land disposal. The
generators must submit copies of the restricted waste's chemical analysis to
the hazardous waste storage or disposal facility.
Restricted wastes are subject to the treatment standards of 40 CFR Part 268
Subpart D. The generator must notify the disposal company of the restriction
and must supply test data if available.
40 CFR Part 268 Subpart B
This section outlines a timetable for waste disposal prohibitions and establishment of
treatment standards.
40 CFR Part 268 Subpart C
This section outlines waste disposal prohibitions. The following are examples of
hazardous wastes that must meet LDR requirements:
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Solvent waste codes F001-F005, including waste from Comprehensive
Environmental Response, Compensation and Liability Act of 1980 (CERCLA)
actions.
Dioxin containing waste codes F020-F023 and F026-F028, including CERCLA
waste.
California List wastes, including hazardous waste that contain 1,000 mg/L
(liquid) or 1,000 mg/kg (non-liquid) of certain halogenated organic compounds,
liquid hazardous wastes that contain > 50 ppm PCBs, and liquid hazardous
wastes that contain > 134 mg/L nickel or > 130 mg/L thallium.
SW-846 Method 9095 must be used to determine if a waste is liquid.
The initial generator of a California List hazardous waste must test the waste
(not an extract), or use knowledge of the waste, to determine if the
concentration levels in the waste meet the regulatory levels for California
listed waste.
Prohibitions for wastes with D, K, P, and U hazardous waste codes are also
listed with effective dates of prohibition.
40 CFR Part 268 Subpart D
This section outlines LDR treatment standards. 40 CFR Subpart D 268.41 lists
treatment standards expressed as concentrations in the waste extract.
A restricted waste may be land disposed only if the TCLP extract of a waste or
waste treatment residue, does not exceed the values shown in Constituent
Concentrations in Waste Extracts (CCWE) of 268.41 for any TC constituent.
Some wastes require total constituent analysis instead of TCLP (see Appendix
The regulation specifies waste/waste residue TCLP extract concentrations
which may not be exceeded. The following Hazardous Waste Codes are
exceptions: D004, D008 (lead), D031, K084, P010, P011, P012, P036, and
U136 (all arsenic), K101 (o-nitroaniline, arsenic, cadmium, lead, and mercury),
and K102 (o-nitrophenol, arsenic, cadmium, lead, and mercury).
The arsenic and lead regulatory levels are based on the EP Tox Test, not
TCLP. If waste/waste residue does not pass the TCLP test, the EP Tox Test
may be used for these contaminants.
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LDR treatment standards are based entirely on technology-based standards
expressed as Best Demonstrated Available Technology (BOAT). TC levels
are based upon health-based allowable concentration levels and Dilution
Attenuation Factors (DAFs). Therefore, the TC regulatory action levels are
NOT the same as the LDR treatment standards in all cases. For many
characteristic wastes, EPA has set the LDR treatment standards at the
characteristic level. Note that EPA has not yet established LDR standards for
D018 through D043 TC wastes.
LDR Records
40 CFR Part 268.7 requires hazardous waste generators and receivers to maintain
the following records of process knowledge or data regarding:
A determination that a restricted waste does not meet treatment standards.
A determination that a restricted waste can be land disposed without further
treatment.
A determination that waste is exempt under 40 CFR Part 268.5, 268.6 or a
nationwide capacity variance under Subpart C of 40 CFR Part 268.
A determination to manage a prohibited waste in tanks or containers during
waste treatment.
The generator must certify that the waste is not hazardous either by knowledge of
testing or by knowledge of process generation. While records are only required for
hazardous waste, it is prudent to maintain records of non-hazardous waste
classification.
The generator must keep records on site for five years from the date that the waste
was last sent to on-site or off-site treatment, storage, or disposal. The record
retention time is extended if an enforcement action occurs within five years of waste
generation.
In general, the types of information required in all of the aforementioned records
include:
Hazardous waste numbers
Manifest numbers
Waste analysis data if applicable
Treatment standards (including codes for required treatment technologies.)
Certification statements signed by the generator
Any waste analysis plans
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LDR Variances: CAM Us are Designed to Reduce the Cost of On-Site Remediation
Corrective action management unit (CAMU) regulations are enumerated in
40CFR260.10 and 40CFR270.2. CAMU is an area within a facility designated
by the Regional Administrator (RA) for implementing CERCLA or RCRA
corrective action requirements. A CAMU may only be used for the
management of remediation wastes pursuant to corrective action
requirements at a facility.
Placement of hazardous remediation waste into a CAMU will not automatically
trigger LDRs. This variance from the LDRs can result in substantial cost
reductions. CAMU boundaries are not confined to where contamination exists
at the site; CAMU boundaries are based on where remediation waste will be
managed.
Limitations and Conditions Applicable to CAMU Designations
The CAMU shall facilitate the implementation of reliable, effective, protective,
and cost-effective remedies;
Waste management activities associated with the CAMU shall not create
unacceptable risks to humans or to the environment resulting from exposure
to hazardous wastes or hazardous constituents;
The CAMU may only include uncontaminated areas of the facility if the
incorporated area is more protective than management of such wastes at
contaminated areas of the facility;
Areas within the CAMU, where wastes remain in place after closure of the
CAMU, shall be managed and contained so as to minimize future releases to
the extent practicable;
The CAMU shall expedite the timing of remedial activity implementation, when
appropriate and practicable;
The CAMU shall enable the use, when appropriate, of treatment technologies
(including innovative technologies) to enhance the long-term effectiveness of
remedial actions by reducing the toxicity, mobility, or volume of wastes that will
remain in place after closure of the CAMU; and
The CAMU shall, to the extent practicable, minimize the land area of the
facility upon which wastes will remain in place after closure of the CAMU.
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2.3 When is the Use of TCLP Inappropriate?
Risk Assessments
The TCLP model assesses risk to ground water when potentially hazardous TC
waste is co-disposed with garbage into sanitary landfills. The TCLP model does not
assess risk when potentially TC waste is disposed in any other matrix. If a waste is
hazardous because it exhibits the toxicity characteristic for mercury, the hazardous
waste generator could attempt stabilization by adding cement and water to the waste,
in a tank, and the resultant concrete may become non-hazardous. In this example,
the concentration of mercury in the concrete's TCLP extract demonstrates that the
waste is not a risk to the ground water beneath a sanitary landfill. Therefore,
according to Federal regulations, this non-hazardous concrete can now be emplaced
at the disposal site. The resultant concrete may only be emplaced on the disposal
site if it does not exhibit the toxicity characteristic for mercury, unless a CAMU is
obtained. The TCLP model discloses no information about potential risks to
groundwater at the factory site where the mercury immobilized in the concrete is
emplaced. EPA is designing site specific risk assessment models, but these will not
be promulgated for several years.
When determining whether to use the TCLP for risk assessment, it is important to
remember that TCLP simulates worst case management of hazardous waste in a
landfill. Much caution must be used before TCLP data are used in risk assessment
because the TCLP conditions rarely reflect actual site conditions. EPA's Science
Advisory Board Report outlines many limitations of using TCLP for risk assessment at
industrial sites. The Board recommends developing leach tests which are
appropriate to site conditions. There are several excellent discussions on the
inadequacies of TCLP organic analysis of solidified waste in "Stabilization and
Solidification of Hazardous, Radioactive, and Mixed Wastes, ASTM, 1992, edited by
T. Gilliam and C. Wiles (Appendix X of this document).
EPA's 1991 Science Advisory Board report on Leachability Phenomena (Appendix VII
of this document) concluded that:
1. Many of the proposed uses of the EP and TCLP test have been inappropriate
because the waste management scenarios of concern were not within the
range of conditions used in the development of the tests themselves. In most
cases of inappropriate use of the EP or TCLP tests, the justification given was
that it was necessary to cite "standard" or "approved" methods. Even if it is
acknowledged that the tests cannot be applied without significant change in
test protocol itself, the need to use a previously "approved" test has been cited
(page 3).
2. A variety of contaminant release tests and test conditions which incorporate
adequate understanding of the important parameters that affect leaching
should be developed and used to assess the potential release of
contaminants from sources of concern. In scientific terms, no "universal" test
procedure is likely to be developed that will always produce credible and
relevant data for input to all decision making exercises (pages 7-8).
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3. Leach test conditions appropriate to the situations being evaluated should be
used for assessing long-term contaminant release potential. The best way to
estimate the extent of contaminant release from a waste matrix of interest is to
have a test that reflects realistic field conditions (page 13).
4. To facilitate the evaluation of risk implications of environmental releases, the
EPA should coordinate the development of leach tests and the development of
models in which the release terms are used (page 17).
The TCLP test cannot predict the potential for toxic chemicals to leach from oily
waste, through soil, to contaminate ground water. This applies to both sanitary
landfills and industrial sites. EPA and the American Society of Testing and Materials
(ASTM) have formed a work group to develop a site-specific risk assessment model
for oily waste. At a minimum, the model will incorporate physical and chemical
characteristics of the oily waste and the soil. However, this model is not expected to
be approved by EPA for several years. Until EPA approves this site-specific model
for oily waste risk assessments, oily waste site assessments should be based on total
constituent analysis, not TCLP extract analysis.
A percent reduction in organic contaminant concentrations between the original
waste and a TCLP extract of stabilized/solidified waste yields very limited information.
In fact, organic TCLP extract data from stabilized/solidified waste is not realistic
because stabilization/solidification is not an appropriate treatment for organic wastes.
Appendix X lists several papers that describe the problems with measuring organics
in stabilized/solidified wastes. VOA data from stabilized/solidified waste is particularly
ineffectual because concrete curing and concrete particle size reduction (hammering
concrete into small pebbles) both produce heat, which evaporates volatiles from
stabilized/solidified waste. Therefore, all or most of the volatiles will evaporate before
analysis of the stabilized/solidified waste TCLP extract. This
stabilization/solidification treatment will therefore appear to be very effective because
of analyte evaporation. The semivolatile organic data in the TCLP extract of
stabilized/solidified waste is of very limited value because the organic compounds are
not very soluble in the TCLP extraction fluid. This usually results in comparable
TCLP extract analyte concentrations between the original waste and the
stabilized/solidified waste.
If waste is hazardous because it exhibits the toxicity characteristic for both benzene
and mercury, adding cement and water will bind the mercury, and evaporate the
benzene. At the present time, the LDR regulations do not specify how toxicity
characteristic waste must be treated.
Appendix XV discusses risk assessment for disposal of solidified/stabilized waste and
contaminated soils.
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Unnecessary Hazardous Waste Determinations:
Generator's knowledge of waste (e.g. chocolate ice cream).
Exempt waste (e.g. household garbage).
Material is not a solid waste (e.g. clean sand, laundry detergent).
Generator's testing of waste (total constituent analysis).
The solid waste is a listed hazardous waste.
Unnecessary Land Ban Determinations:
Some LDRs are for total constituents, not TCLP extract concentrations.
Generator's testing of waste (total constituent analysis).
Pure liquid waste samples (waste is TCLP extract; waste would fail paint filter
test).
Determination of Corrective Action Clean-up Levels and Clean Closures
TC levels are not used to set clean up levels for corrective actions or clean closures.
Clean up levels are developed from site-specific information.
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2.4 Sampling and Analysis Design
The following issues discussed in this section are critical in sampling and
analysis design:
Total constituents versus TCLP
Specifying sample collection procedures
Total constituents versus TCLP - EPA Memorandum
EPA has several memoranda which address issues such as Characterizing Heterogeneous
Material and Total Analysis Versus TCLP. These are presented in Appendix VI. The Office
of Solid Waste - Methods Section, Notes on RCRA Methods and QA Activities,
Memorandum #36, January 12, 1993, is helpful in delineating sampling design related to the
analysis of samples for total constituents versus leachable constituents. The consequential
portions of Memorandum #36 and a discussion of their significance follows.
Office of Solid Waste Memorandum - Methods Section #36, January 12, 1993
Page 10 Characterizing Heterogeneous Materials
Characterization of a solid waste is essential for determining whether a waste is
hazardous or for developing management and treatment standards for hazardous
materials. Current EPA regulations for characterizing waste includes determining the
average property of the "universe or whole." This task is difficult when applied to
heterogeneous wastes because conventional sampling and compositing techniques are
often inadequate in providing a "representative sample" of the waste. As a result,
analytical results are often biased and imprecise, making compliance decisions difficult.
The above paragraph means that all of the samples collected from a heterogeneous waste
do not have to be below the regulatory action level for the waste to be considered non-
hazardous. What percent of the samples are allowed to be above regulatory action levels
without classifying the waste as hazardous? Chapter 9 of SW-846 recommends utilizing the
student "t" test to determine an appropriate percentage of samples that may be above
regulatory action levels without classifying a solid waste as "hazardous."
Please be aware that the above discussion is only for heterogenous wastes with no obvious
"hot spots" of highly concentrated hazardous wastes. Whenever regulatory agencies collect
samples to determine compliance with the TC regulations, only the most contaminated
media will be sampled. For example, if there is a one-acre mercury waste pile surrounded
by ninety-nine acres of clean sand, TC inspectors will not collect samples of the clean sand.
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The RCRA definition of "average property" is very different than the definition of "average"
which was taught in elementary school. For example, if the TCLP extract regulatory action
level is 50 mg/L, and our sample results are 80 mg/L and 0 mg/L, we can not compute the
numerical average of analytical results as 40 mg/L, and affirm that the waste is not
hazardous. To make proper characterization of the above waste, we would declare the
waste hazardous because 50% of the samples were above regulatory action levels.
Appendix XI discusses characterization of heterogeneous waste.
Pages 19-21 Totals Analysis Versus TCLP
Over the past year, the Agency has received a number of questions concerning the
issue of total constituent analysis with respect to the TCLP. Section 1.2 of the TCLP
allows for a compositional (total) analysis in lieu of the TCLP when the constituent of
concern is absent from the waste, or if present, is at such a low concentration that the
appropriate regulatory level could not be exceeded. A number of persons have
contacted the MICE Service and have requested clarification on this issue with respect
to a number of waste testing scenarios.
Wastes that contain less than 0.5% dry solids do not require extraction. The waste,
after filtration, is defined as the TCLP extract. The filtered extract is then analyzed and
the resulting concentrations are compared directly to the appropriate regulatory
concentration.
For wastes that are 100% solid as defined by the TCLP, the maximum theoretical
leachate concentration can be calculated by dividing the total concentration of the
constituent by 20. The dilution factor of 20 reflects the liquid to solid ratio employed in
the extraction procedure. This value then can be compared to the appropriate
regulatory concentration. If this value is below the regulatory concentration, the TCLP
need not be performed. If the value is above the regulatory concentration, the waste
may then be subjected to the TCLP to determine its regulatory status.
The same principal applies to wastes that are less than 100% solid (i.e., wastes that
have filterable liquid). In this case however, both the liquid and solid portion of the
waste are analyzed for total constituency and the results are combined to determine the
maximum leachable concentration of the waste. The following equation may be used to
calculate this value:
[AxB + [CxD]]
= £
B + [20L/kg x D]
where: A = concentration of the analyte in liquid portion of the sample (mg/L)
B = Volume of the liquid portion of the sample (L)
C = Concentration of analyte in the solid portion of the sample (mg/kg)
D = Weight of the solid portion of the sample (kg)
E = Maximum theoretical concentration in leachate (mg/L)
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To illustrate this point, the following example is provided:
An analyst wishes to determine if a lead processing sludge could fail the TC for lead.
The sludge is reported to have a low concentration of lead, and the analyst decides to
perform a compositional analysis of the waste instead of the TCLP. A preliminary
percent solids determination as described in the TCLP is performed. The percent solids
is found to be 75%. Thus, for each 100 grams of this waste filtered, 25 grams of liquid
and 75 grams of solid are obtained. It is assumed for the purposes of this calculation
that the density of the filterable liquid is equal to one. The liquid and solid portion of the
sample are then analyzed for total lead. The following data are generated:
Percent solids = 75%
Concentration of lead in the liquid phase = 0.023 mg/L
Volume of filtered liquid = 0.025 L
Concentration of lead in the solid phase = 85 mg/kg (wet weight)
Weight of the solid phase = 0.075 kg.
The calculated concentration is as follows:
[0.023 mg/L x .025L1 + [85 mg/kg x .075kg] = 4.18 mg/L
.025 L + [20 L/kg x .075kg]
In this case, the maximum teachable concentration is below the 5 mg/L regulatory
concentration for lead, and the TCLP need not be performed.
Non-aqueous based wastes (i.e., oily waste) may be calculated in the same manner as
described above, except the concentration of constituents from the liquid portion of the
waste (A in the above formula) are expressed in mg/kg units. Volumes also would be
converted to weight units (kg). The final leachate concentration is expressed in mg/kg
unit.
This memorandum should significantly reduce the number of TCLP samples analyzed to
demonstrate compliance with the TC regulations. The profound regulatory impact of Notes
on RCRA Methods and QA Activities Memorandum #36, pages 19-21, are most easily
comprehended with the following uncomplicated monophasic examples. These examples
explain how the calculations are made and evaluated to determine whether to analyze the
total constituents or perform the TCLP.
Example 1. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/L. A soil (with
no liquid phase) contains 10 mg/kg of cadmium. Is the TCLP required?
The TCLP test for a solid matrix leaches one part of waste with twenty parts of an acetic acid
buffer. Therefore, even if all of the cadmium was leached from the soil to the solvent, the
maximum concentration in the TCLP extract would be 0.5 mg/L. Consequently, TCLP is not
required.
Example 2. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/kg. A soil (with
no liquid phase) contains 100 mg/kg of cadmium. Is the TCLP required?
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The TCLP test for a solid matrix leaches one part of waste with twenty parts of acetic acid
buffer. Therefore, if all of the cadmium was leached from the soil to the solvent, the
maximum concentration in the TCLP extract would be 5 mg/L. Consequently, TCLP is
required.
Example 3. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/L. A liquid with
no solid phase contains 0.5 mg/L cadmium. Is the TCLP required?
The TCLP test for a liquid with no solid phase consists of filtration. The filtrate is the TCLP
extract. Therefore, even if all of the cadmium passed through the filter, the maximum
concentration of cadmium in the TCLP extract would 0.5 mg/L. Consequently, TCLP
extraction is not required.
Example 4. The TCLP Extract Regulatory Action Level for cadmium is 1 mg/L. A liquid (with
no solid phase) contains 5 mg/L cadmium. Is the TCLP extraction required?
The TCLP test for a liquid with no solid phase consists of filtration. The filtrate is the TCLP
extract. Therefore, if all of the cadmium passed through the filter, the maximum
concentration of cadmium in the TCLP extract would be 5 mg/L. Since the filtrate equals the
TCLP extract, the waste exceeds the TC level for cadmium and is a hazardous waste.
Therefore, the TCLP extraction is not required.
The following abstract and introduction of a research paper on the relationship between total
mercury and TCLP mercury at Oak Ridge National Lab illustrates how difficult it is to
estimate the mercury concentration in the TCLP extract from the mercury concentration in
the soil.
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Chapter 3
TC AND TCLP PROJECT PLANNING
Data Quality Objectives
DQO Case Study:
Cadmium Contaminated Fly Ash Waste
Sampling and Analysis Design
Analytical Method Selection
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3.0 TC AND TCLP PROJECT PLANNING
Planning a project prior to sampling and analysis promotes successful
implementation. The conclusion of the planning process should result in an
efficient sampling and analysis design which allows the collection of appropriate
data. The data should promote making a correct decision on the storage,
treatment or disposal of the waste. This chapter provides information in the
following areas which are critical to project planning.
Data Quality Objectives (DQOs)
Sampling and analysis design
Sample containers, preservation, and storage
Sample volumes
Sample decontamination
Holding times
Field QC
Documentation
Barbara Metzger's 1992 speech on Environmental Data Use: "Meeting the Customer's
Need", (Appendix XVI) - illustrates how site-specific Data Quality Objectives (DQOs) are
utilized in environmental projects.
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3.1 Data Quality Objectives
Environmental samples are often collected and analyzed without proper
planning. The data collected may not allow a correct decision to be made.
In response to this problem, EPA has developed a planning process to facilitate
clear definition of the decision to be made and the data required to make these
decisions. This process is the Data Quality Objective (DQO) process. Prior to
initiating sampling, the questions to be answered should be listed, prioritized and
one primary question identified. These should be agreed upon by all parties,
including the regulatory agencies and TSDFs, the site owners and
operators/generators, and the technical staff.
The DQO Process should identify:
What question will the data resolve?
Why is a specific type, quantity and quality of data needed?
How will the customer use the data to make a defensible decision?
How much data are required?
What resources are needed?
The information included in the DQO section describes the following information:
DQO definition
DQO Planning Process (DQO-PP) description
Value of DQO-PP
Example of DQO-PP implementation
The American Society of Testing and Materials (ASTM) Committee D34.02.10 is working
with Quality Assurance Management Staff (QAMS) and the Office of Solid Waste to produce
an ASTM Standard Practice which describes the DQO Planning Process (DQO-PP).
Additional guidance is available from the Office of Emergency and Remedial Response, US
EPA, Washington, D.C. 20460 in a document titled: "Data Quality Objectives Process for
Superfund, Interim Final Guidance, EPA/540/G-93/071, Publication 9355.9-01, September
1993.
Many of the following flow charts, definitions and information are derived from these
documents and from the draft ASTM document.
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DQOs are defined by the ASTM document as:
Qualitative and quantitative statements derived from the DQO-PP describing the problems,
decision rules, and the uncertainty of the decisions stated within the context of the problem.
The DQO Planning Process is:
A Total Quality Management tool developed by the US EPA to facilitate the planning of
environmental data collection activities. The DQO Planning Process asks planners to
focus their efforts by specifying the use of the data (the decision), the decision criteria,
and their tolerance to accept an incorrect decision based on the data.
Incorrect decisions can result from many causes. One cause of making incorrect decisions
is insufficient or inadequate data to address the problem. The DQO-PP provides a method
to allow the decision makers and technical specialists to assure that sufficient data of
appropriate quality is collected at the proper time. In order to make the best decisions, the
chance of making an incorrect decision must be understood. In order to examine the
probability of making an incorrect decision, it must be understood that all measurements
have error. Measurement error results from heterogeneity of the waste, errors in sampling
methods and laboratory error. Measurement error is cumulative. The laboratory error is a
small component in the overall measurement error. Decision makers must understand that
there is a balance between resources and decision error. Decision makers must make
informed decisions as to the cost versus the decision error and ultimately the measurement
error.
The goal of this document is to assist the regulated community comply with the TC and
TCLP Rules in a cost effective manner. Therefore, it is essential for the regulated
community to understand the importance of obtaining the most cost effective sampling and
analysis design which provides the appropriate decision error. If an appropriate sampling
and analysis design is not utilized, the data may not allow a waste generator to accurately
determine if a solid waste is a hazardous waste. The DQO-PP is essential for preparing a
sampling and analysis design which balances the resources with the chance of making an
incorrect decision.
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What is the value of using the DQO-PP?
The DQO-PP:
Helps users determine the amount, frequency, and quality of data needed.
Saves resources by making data collection operations more efficient.
Encourages communication between the data users, technical experts, and decision
makers.
Helps focus studies by clarifying vague objectives and narrowing the questions to the
essential issues.
Helps provide a logical process which facilitates documentation.
Additional critical information about the DQO-PP
A statistical design, which may result from the DQO-PP, allows the uncertainty in the
data and ultimately the decision uncertainty to be quantified. Chapter 9 of SW-846
outlines strategies for statistical design. The statistical design must be carefully
applied to assure that the correct assumptions are made and that the assumptions
address the question(s) related to the objectives.
The DQO-PP is iterative. Projects should focus on essential questions and take a
phased approach to answering these questions. This allows reevaluation of the
DQOs as the data collection is completed. This iteration allows the resources to be
efficiently used.
The term "decision maker" used in this document may include owners and managers
of facilities and regulators. Prior to undertaking large projects, the owners and
managers may choose to involve the regulators to assure consensus is reached in
the planning phase.
The following discussion presents summary information about each of the seven steps within
the DQO Planning Process shown in Figure 3-1.
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Figure 3-1
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The DQO Planning Process has a logical problem solving structure which includes the
following seven steps:
1. State the problem
2. Identify the decision(s)
3. Identify inputs to the decision(s)
4. Define the study boundaries
5. Develop decision rule(s)
6. Specify acceptable limits on decision error
7. Optimize the design
1. State the problem
The essential goal of this step is to focus the decision makers and the technical team on one
or more problems. These problems should be as narrowly stated as possible. For waste
generators, these problems may focus on whether a particular waste is hazardous.
2. Identify the decision
Clear and concise potential decision(s) should be agreed upon by the decision makers and
the technical team. One or more decisions should be presented for each problem.
3. Identify the inputs to the decision
The goal is to list the data which are needed to make the decision. Questions such as
whether metals or organic data must be generated should be addressed. Production or
process data may be required if the task is related to a waste generator. Additionally,
knowledge about the homogeneity of the material to be sampled may need to be
determined. This data should also include any time factors, physical limitations, process
data, and resources which may effect the sampling and analysis. The environmental
characteristics such as analytes, method, and process knowledge required should also be
listed.
4. Define the study boundaries
The boundaries are the limitations on the study. Examples include time and budget
constraints, permit requirements, disposal requirements, and exposure levels. Any
physical boundaries such as drum or container size is considered a spatial boundary.
Sampling depth may be considered a boundary. Any changes in the waste concentration
over time must be considered as a temporal boundary. This step is often performed
simultaneously with the previous step.
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5. Develop decision rule(s)
This is a statement which describes how the data will be summarized, collected, and
compared to the decision. The statement should include actions which will be based on
criteria and conclusions from the sampling and analysis. The statement should be an
"if...then..." statement that incorporates the action limits. The statement should include the
parameter to be measured, the mode of comparison (greater than, less than, average, etc.),
action levels and actions to be taken. An example statement: If the average concentration
in drum is greater than 1 mg/L of cadmium, the material will be disposed of as a hazardous
waste.
Instead of statements, a decision logic diagram may be used to present the decisions and
actions, and criteria. When complex decisions are required or when multiple criteria must be
considered, the decision logic diagram is often more easily followed and understood.
6. Specify acceptable limits on decision error
The decision maker should understand that results of all studies have uncertainty and error.
The goal is to quantitate the amount of uncertainty that the decision maker is willing to
accept in making the decision. The key step is to move from a qualitative "feeling" of
uncertainty to a quantitative level of uncertainty. The process for establishing this, in the
case of a hazardous waste determination, includes the following:
i. Identify the consequences of incorrectly deciding the waste is not hazardous.
ii. Identify the consequences of incorrectly deciding the waste is hazardous.
iii. Rank these consequences by severity.
iv. Estimate the health risk and financial risk associated with an incorrect result.
v. Estimate how far below the regulatory limit one wants to be in order to decrease the
consequence of an incorrect decision. Some statistical experience in assessing
decision error and in assessing sampling and analysis design error is needed to
make this assessment.
This information is incorporated into the decision rule. An example decision rule which
incorporates the decision error is:
Three samples per drum are collected and the concentrations from each drum are
averaged. If the within drum average concentration of cadmium is greater than 0.7
mg/L of cadmium, then the material will be disposed of as a hazardous waste.
7. Optimize the design
In order to characterize a site or waste successfully, a sampling and analysis design must be
established. The sampling and analysis design includes development of statistical and
observational design alternatives, and specifies sampling, handling, and analysis methods.
The design indicates the number and locations of samples based on the acceptable decision
error which was agreed on during the DQO development. The most important input from the
DQO process is the degree of decision error which the decision maker will accept. When
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preparing a sampling and analysis design, the time and budgetary constraints should be
evaluated to balance their importance versus the decision error.
The preliminary design may contain the following information:
Spatial areas of interest
Hot spots versus average values of contamination
Particular contaminants of concern
Desired levels of detection
Which matrices will be investigated
Patterns of contamination
Stratification of the contaminants
Contaminant degradation
Temporal considerations (changes of concentration over time)
Quality control samples designed to allow estimation of precision and accuracy, and
background contamination
Health and safety issues
Designs must be practical and achievable. There is no one correct design but rather an
optimum design which balances resources with the data required to make a decision.
Technical staff must work carefully to present several designs to decision makers along with
the probability of decision error, resources, and benefits of each design.
Other factors used to select the appropriate measurement methods include:
DQOs,
required regulatory or risk assessment levels,
method precision and accuracy, and
contaminants of interest.
Improved accuracy, precision, and lower detection limits usually result in higher sampling
and analytical costs because larger numbers of samples, improved instrumentation, and
more field/analytical expertise may be required. The improved accuracy may result in
decreased decision error. If matrix specific accuracy and precision data are not available,
preliminary precision and accuracy studies must be performed. These studies should
measure total error from sample heterogeneity, sampling, and analytical methods.
Regulatory agencies may review these studies prior to method approval.
Prior to sampling design implementation, the decision makers must approve the design.
Several designs may be presented to the regulators and decision makers. The level of
uncertainty, advantages and disadvantages, budgetary and time constraints, and other
relevant factors must be presented for each design. This approach allows the decision
makers to properly assess options and to agree upon the best sampling design. Sampling
designs are implemented after approval by the decision makers.
The technical team must continually evaluate the proposed designs with respect to the
DQOs, health and safety criteria, budget and time constraints. If the proposed design does
not meet the criteria, it may be altered. In extreme cases, the DQOs may be unattainable
and must be altered. The DQOs should only be changed after consultation with the decision
makers and technical team members. The DQOs may need to be reevaluated if a decision
cannot be made.
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References for sampling design strategies are:
U.S. EPA, Test Methods for Evaluating Solid Wastes, SW-846 Third Edition-Chapter
9. August 1993.
Characterizing Heterogeneous Materials, July, 1992 (Appendix XII) .
Chapter 9 of SW 846 outlines several statistical design approaches. Many other design
strategies exist and may be better suited for the situation at hand. It is wise to examine
many statistical options and methods of evaluating the data during the planning phase.
An example of using the DQO-PP is presented in the following pages. This example
demonstrates how to design a sampling program to determine whether fly ash from a
municipal incinerator is a RCRA hazardous waste. This example is from a draft ASTM
standard practice on the use of DQO-PP in waste management activities. The ASTM
document was the product of a cooperative agreement between ASTM, US EPA Quality
Assurance Management Staff and the Office of Solid Waste. The example was written by
the ASTM D.34.02.10 committee.
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3.2 DQO Case Study: Cadmium Contaminated Fly Ash Waste
Background
A municipal waste incineration facility located in the Midwest routinely removes "fly ash" from
its flue gas scrubber system and disposes of it in a sanitary landfill. Previously, it was
determined that the ash was "non-hazardous" under RCRA regulations. However, the
incinerator has recently begun treating a new waste stream. As a result, a local
environmental public interest group has asked that the ash be retested against RCRA
standards before it is dumped. The group is primarily concerned that the ash could contain
hazardous levels of cadmium from the new waste sources. The facility manager has agreed
to test the ash and decides to employ the Data Quality Objectives process to help guide
decision-making throughout the project.
The Code of Federal Regulations (CFR) Part 261 RCRA toxicity characteristic criteria for
determining if a solid waste is hazardous requires collection of a "representative portion" of
the waste and performance of Toxicity Characteristic Leaching Procedure (TCLP). During
this process, the solid fly ash will be "extracted" or mixed in an acid solution for 18 hours.
The extraction liquid will then be subjected to tests for specific metals.
Since the impact of the new waste stream is not known, a preliminary study was conducted
to determine the variability of the concentration of the contaminants. Random samples were
collected from the first 20 truck loads. Since process knowledge of the waste stream
indicated that cadmium was the only toxicity characteristic (TC) constituent in the waste,
these samples were analyzed individually for cadmium using the TCLP. The results were
expressed as the average concentration along with the standard deviation.
DQO Development
The following is an example of the output from each step in the DQO process.
Assemble the Team ~ The Plant Manager assembled a skeletal team consisting of himself
and a representative of the current disposal facility staff. The two of them assembled the
team with the responsibility to deal with this problem.
The decision makers evaluation team will include the incineration plant manager, a
representative of the environmental public interest group, a representative of the community
where the ash is currently being disposed of. The technical staff include a statistician, and a
chemist with sampling experience.
1. State the Problem
The problem is to determine if any loads of fly ash are hazardous for cadmium under the
RCRA TCLP. If so, those loads must be disposed of in a RCRA landfill.
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2. Identify the Decision(s)
i. Decision - Determine whether the concentration of cadmium in the waste fly ash
exceeds the regulatory RCRA standards.
ii. State the Actions That Could Result From the Decision -
a) If the average concentration of cadmium is greater than the action level, then
dispose of the waste fly ash in a RCRA landfill.
b) If the average concentration of cadmium is less than the action level, then
dispose of the waste fly ash in a sanitary landfill.
3. Identify the Inputs Needed for the Decision
List the environmental variables or characteristics which are known from historical and
regulatory information and information which must be obtained in order to make the decision.
Available Inputs
Preliminary Study Information -- Since the concern is with a new waste stream, the team
ordered a pilot study of the fly ash to determine the variability in the concentration of
cadmium between loads of fly-ash leaving the facility. They have determined that each load
is fairly homogeneous. However, there is a high variability between loads due to the nature
of the waste-stream. Most of the fly ash produced is not a RCRA hazardous waste and may
be disposed of in a sanitary landfill. Because of this, the company has decided that testing
each individual waste load before it leaves the facility would be the most economical. In that
way, they could send loads of ash that exceeded the regulated cadmium concentrations to
the higher cost RCRA landfills and continue to send the others to the sanitary landfill.
The study showed that the standard deviation of the cadmium concentration within a load
was Sw = 0.4 mg/L and the standard deviation of the cadmium concentration between loads
was Sb = 1.4 mg/L. Sample and quality control data indicates that a normal distribution can
be assumed.
Identify Contaminants of Concern, Matrix, and Regulatory Limits ~ The team identified the
following factors critical to the problem:
Contaminants of concern: cadmium soluble in the Toxic Characteristic Leaching
Procedure (TCLP) extract.
Sample Matrix: fly ash.
Regulatory Threshold: 1 mg/L.
Specific Project Budget and Time Constraints - The incinerator plant manager has
requested that all stages of the operation be performed in a manner that minimizes the cost
of sampling, chemical analysis and waste disposal. However, no formal cost constraints
have been implemented.
The environmental public interest group has threatened to file a law suit for violation of
environmental regulations if testing does not proceed within a "reasonable time-frame."
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Contained in the trucks, the waste does not pose a threat to humans or the environment.
Additionally, since the fly ash is not subject to change, disintegration or alteration, the
chemical properties of the waste do not warrant any temporal constraints. However, in order
to expedite decision making, the evaluation team has placed deadlines on sampling and
reporting. The fly ash waste will be tested within 48 hours of being loaded on to waste
hauling trailers. The analytical results from each sampling round should be completed and
reported within 5 working days of sampling.
Identification of the testing methods -- In this case, 40 CFR Part 261, Appendix II specified
the TCLP method SW 846 Method 1311. The leachate must be analyzed by an appropriate
method. Potential methods of characterizing the leachate for cadmium include, but are not
limited to, SW 846 methods 6010, 6020, 7130, or 7131.
Inputs To Be Determined
Method validation and QC - The analytical method accuracy and precision and method
detection limits in the fly ash matrix must be determined. The QC samples must be
specified.
Identification of sampling procedure or devices - The following must determined:
- Number of samples
- Sampling methods for composite or grab samples of ash
- QC requirements for sampling
4. Define the Boundaries of the Study
Define a detailed description of the spatial and temporal boundaries of the decision;
characteristics that define the environmental media, objects or people of interest; and any
practical considerations for the study.
i. Specify the Characteristics that Define the Sample Matrix - The fly ash should not be
mixed with any other constituents except the water used for dust control.
ii. Identify Spatial Boundaries - The variability between loads was greater than within a
load therefore, decisions will be made on each load. The waste fly ash will be tested
after it has been deposited in the trailer used by the waste hauler. Separate
decisions about the toxicity of the fly ash will be made for each load of ash leaving the
incinerator facility. Each load of ash should fill the waste trailer at least 70%. In
cases where the trailer is filled less than 70%, the trailer must wait on-site until more
ash is produced and can fill the trailer to the appropriate capacity.
iii. Identify Temporal Boundaries (The temporal boundaries of the study include the time
frame over which the study should be conducted). - The study will be conducted until
at least 30 data points are collected and the action limits, number and frequency of
samples will be reevaluated after that time.
5. Develop a Decision Rule
The arithmetic mean of sample results will be compared to the action level.
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Decision Rule:
a) If the average concentration of cadmium in a truck load is greater than the
action level, then dispose of the waste fly ash in a RCRA landfill.
b) If the average concentration of cadmium in a truck load is less than the action
level, then dispose of the waste fly ash in a sanitary landfill.
Note that the team has decided that the action level will be less than the regulatory level in
order to decrease decision error at the regulatory level of 1 mg/L.
Develop Decision Error Constraints
The decision makers specify acceptable decision errors based on the consequences of
making an incorrect decision. Both error rates have negative consequences.
The team must make a baseline assumption. Based on the initial pilot study each load will
be assumed to be less than the regulatory level and the burden of proof will be to prove that
the load is above the action level. In this example, there are two types of error that the
evaluation team could make:
i. false positive error (declaring the load hazardous when it is not) - If the true cadmium
concentration is below 1 mg/L, but the average measured cadmium concentration is
above the action level, the non-hazardous fly-ash waste will be sent to a RCRA
landfill. The consequence of a false positive error is that the company will have to
pay additional cost to dispose of the waste with a concentration between the action
level and regulatory threshold at a RCRA facility as opposed to a less expensive
method of disposal in a sanitary landfill.
ii. false negative error (declaring the load non-hazardous when it is hazardous) - If the
true cadmium concentration is equal to or greater than 1 mg/L, but the average
measured cadmium concentration is below the action level, the hazardous fly-ash
waste will be sent to a sanitary landfill. The consequence of a false negative error is
that the fly-ash waste may be disposed in a manner that will be harmful to human
health or the environment. Legal consequences and subsequent remedial costs are
also possible consequences.
iii. number of samples - The number of samples will depend on the uncertainty of
estimating the true cadmium concentration for each load and the resources available
to sample and to chemically analyze the samples.
The purpose of this stage of the process is to specify the probabilities of making an incorrect
decision on either side of the "action level" that are acceptable to decision makers. The
team must agree on which type of decision error is of greater concern, false positives or
negatives and must target the level of false positives and negatives.
For this example, the project team is more concerned about false negatives because of the
increased liability due to sending potentially hazardous waste to a sanitary landfill. The team
set a target level of false negatives of 10% when the true concentration is 1 mg/L.
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Decision Performance Curve
The Decision Performance Curve will be calculated to determine the action level and review
the performance of the decision rule. To calculate the Decision Performance Curve,
decision makers use the following steps:
Step 1: Number of samples are calculated with L = 0.2 mg/L, o = Sw = 0.4
mg/L, and a = 0.05 (or Za/2 = 1.960 for a 95% confidence level).
n - ( 1'960 X °'4 I' » 16 .
0.2
where:
L = the limit of error on the average of 0.2 mg/L
Sw or standard deviation = 0.4 mg/L within a load
Za/2 = 1.960 for a 95% confidence level, the a/2 percentile point of normal probability
distribution e.g. Za/2 = Z0005. These are tabled values from a standard normal
distribution at Z0005.
n = number of samples
Step 2: Calculate the action level (AL) from the specified false negative error of
10%. The probability calculations are based on an approximating
normal probability distribution for the cadmium concentration
measurements. This approximating normal probability has a mean =
RT = 1.0 mg/L and a standard deviation = Sw = 0.4 mg/L. The 10%
percentile point for the standardized normal probability distribution is
Z010= 1.282.
False Negative Error = Pr( Average < AL when the true concentration = RT) = 0.10.
or
AL - RT
AL = Action Level
RT = Regulatory Threshold
Z010 = Tabled Z-value from standard normal distribution at 0.10
AL = 1.0mg/L - (1.282)(0.4/T7gr/L) /4 = l.QmgIL - 0.13mg//.
or
AL = 0.87mg/L .
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Therefore, the decision rule is:
a) If (average concentration of cadmium) > 0.87 mg/L, then dispose of the
waste fly ash in a RCRA landfill.
b) If (average concentration of cadmium) < 0.87 mg/L, then dispose of the
waste fly ash in a sanitary landfill.
The decision performance curve for this decision rule would have a probability of
taking action (i.e., sending fly-ash waste to a RCRA landfill) of 0.90 at a possible true
concentration value of RT = 1.0 mg/L.
Step 3: Calculate the true concentration (say, 6 < RT) that corresponds to an
action level of AL = 0.87 mg/L and a false positive error of 20%. The
probability calculations are based on an approximating normal
probability distribution for the cadmium concentration measurements.
This approximating normal probability has a mean = 6 mg/L and a
standard deviation = Sw = 0.4 mg/L. The 20% percentile point for the
standardized normal probability distribution is Z020 = 0.848.
False Positive Error = Pr{ Average < AL when the true concentration = 6} = 0.20.
or
AL - 9 _ 7
+ ^0.20 '
AL = Action Level
6 = True Value
Z020 = Tabled Z-value from standard normal distribution at 0.10
6 = 0.87mg/L - (0.848)(0.4mgr/L) / 4 = Q.87mglL - O.OSmgIL ,
or
6 = 0.79mg/L .
The decision performance curve would have a probability of taking an action (i.e.,
sending fly-ash waste to a RCRA landfill) of 0.20 at a true cadmium concentration of
6 = 0.79 mg/L. The possible true cadmium concentration values in the interval (0.79
mg/L, 1.0 mg/L) represents values that cause the decision rule to send fly-ash waste
to a RCRA landfill even though the true concentration is below the regulatory
threshold. This interval can be reduced by increasing the number of samples, by
changing the false negative error or by changing the false positive error.
Step 4: Draw the decision performance curve by using the standardized
normal probability distribution. The standardized normal probability
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distribution is defined as a normal probability distribution with mean = 0
and standard deviation = 1.0. There are many tables and computer
programs that can be used to calculate probabilities for a standardized
normal random variable, Z. A normal random variable, X, with mean =
u and standard deviation = o can be transformed to a standardized
normal random variable by Z = (X - u)/o.
Prob( Action ) = Pr( Average > AL when the true concentration = 6).
AL-Q }
Prob(Action) = 1.0 - Prob
Z <-
swi
Prob(Action) = 1.0 - Probl Z <- °'87 8
0.1 )
Figure 3-2 plots the decision performance curve of Prob( Action ) versus possible true
concentration values 6.
7. OPTIMIZE THE DESIGN
The decision maker(s) will select the lowest cost sampling design that is expected to achieve
the DQOs. The optimal design(s) for sampling the fly-ash waste will be generated by the
statisticians on the evaluation team. The choice of sampling plan will be decided by
consensus.
Figure 3-2 plots the probability of taking action (disposing of the waste in a RCRA landfill)
versus different possible values for the true concentration in the TCLP extract. Note that
various numbers of samples, n, are used to generate each curve. All of the curves meet the
criteria of 10% false negatives at the regulatory threshold. The differences lie in the false
positives versus the true concentration. If the true concentration value is equal to .87 mg/L
(the action level) then the probability of taking action is .5 or 50% chance of taking action.
The action level is below the regulatory threshold and does insure the agreed upon false
negative rate of 10%. Note that if the regulatory level and the action level were equal, the
likely chance of having a false negative would be 50% at 1 mg/L.
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Cadmium Contaminated Fly-Ash Waste
AL18
1.O 1.1 1.2 1.3
True Cadmium
Concentration (mg/L)
Figure 3-2. Design Performance Curve for Cadmium Example
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Implementation - After completion of the sampling and measurement process, the data
assessment is performed. The concentration measurements from each load of fly-ash waste
are averaged and compared to the action level. Any load with average concentrations less
than the action level will be sent to a sanitary landfill, and those loads with average
concentrations greater or equal to the action level will be sent to a RCRA landfill.
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3.3 Sampling and Analysis Design
Specifying Sample Collection Procedures
The methods and equipment used for sampling waste materials vary with the
physical and chemical properties of the waste materials.
40 CFR Part 261, Appendix I lists several representative sampling methods.
Unfortunately, for most matrices, selecting representative samples is an extremely
difficult objective.
The methods in the above reference are recommended. No prior approval by EPA is
required if alternate sampling methods are used.
All procedures for sampling should be documented and referenced.
Sample Containers, Preservation, and Storage
Prior to Extraction or Filtration
No preservatives are added to the initial waste collected for TCLP filtration and
extraction.
Preservatives used after filtration and extraction are listed in Chapter 4 of this
document.
If organics are being analyzed, samples must be collected in glass containers with
Teflon lid liners.
Metals may be collected in polyethylene or glass containers.
If practical, samples which will undergo Zero Headspace Extraction (ZHE) for
volatiles should be collected in 40 ml_ glass Volatile Organic Analysis (VOA) vials
with Teflon lids. Clay type soil samples, or other large particle size solid matrices
which are difficult to put into narrow-mouth containers, should be collected in 250 ml_
wide mouth glass jars.
Any sample which will undergo ZHE should be collected with minimal head space in
the container.
All samples should be stored at 4°C + 2°C prior to extraction or filtration. Samples
should be placed in coolers immediately after collection.
Sample Volumes
A discussion of required sample volume is presented in Chapter 4 which includes the
following general points:
A minimum of 100g of waste is needed to determine the percentage of solids,
extraction fluid type, and particle size.
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A second aliquot of 100g is the minimum which must be extracted for non-volatiles.
The amount of sample is dependent on the percent wet solids. The lower the percent
wet solids, the greater the sample volume required for leaching.
Another aliquot of at least 25g must be used for volatiles by ZHE. The amount of
sample is dependent on the percent wet solids. The lower the percent wet solids, the
more material which must be collected for leaching.
If multiple phases are collected and the solids appear to be <0.5%, each phase may
have to be analyzed individually. This is especially true of oily waste. If the oil will
not pass through the filter, it will be considered a solid.
Enough sample must be collected to allow for the matrix spike. Each matrix requires
a spike. The same amount of material is required for the spike as for the sample.
Extra sample volume may be needed if vessel leakage or breakage occurs. Multi-
phasic samples require much larger sample volumes than monophasic samples.
Sampling Equipment Decontamination
Acceptable sampling equipment decontamination should be performed before sample
collection. Decontamination may be required in the field if an adequate number of pieces of
sampling equipment is not available to allow equipment to be dedicated to one sampling
point.
Each EPA region and some states have special decontamination requirements. These
decontamination requirements should be verified for compliance in a particular region or
state. The RCRA decontamination procedures may differ from CERCLA decontamination
procedures in some locations. For most TCLP sampling events, there are no sampling
equipment decontamination criteria.
Paint or coatings on sampling equipment must be removed from any part of the equipment
that may contact the sample.
The USEPA Region 2 decontamination procedure for CERCLA sampling and RCRA Facility
Investigation (RFI) sampling is as follows:
a. wash and scrub with low phosphate detergent
b. tap water rinse
c. rinse with 10% HNO3, ultra pure
d. tap water rinse
e. an acetone-only rinse or a methanol followed by hexane rinse (solvents must be
pesticide grade or better)
f. thorough rinse with demonstrated analyte free water*
g. air dry, and
h. wrap in aluminum foil for transport
* The volume of water used during this rinse must be at least five times the volume of
solvent used in Step e.
3-20
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If metal samples are not being collected, the nitric acid rinse may be omitted. If organic
samples are not being collected, the solvent rinse may be omitted.
Holding Times for TCLP
TCLP has three sets of holding times (see Table 3-1). The first holding time
commences with sample collection and ends with TCLP extraction. The second
holding time is from TCLP extraction to preparative extraction. The final holding time
is from preparative extraction to analysis.
Table 3-1 - TCLP Holding Times
Analysis Type
Volatiles
Semivolatiles*
Metals, except
Mercury
Mercury
Days From Field
Collection to TCLP
Extraction
14
14
180
28
Days From TCLP
Extraction to
Preparative
Extraction
NA
7
NA
NA
Days From
Preparative
Extraction to
Determinative
Analysis
14
40
180
28
* Pesticides and herbicides are deemed semivolatiles.
Some regional and state agencies may alter these times. If Contract Laboratory
Program (CLP) methods are used, the holding times from extraction to preparation
and from preparation to determinative analysis will differ from the above times.
However, to demonstrate compliance with the TC or Land Ban regulations, sample
holding times may not exceed the holding times listed in the preceding table.
Field QC Samples
The following field QC samples may be collected during the sampling process:
Trip Blanks are aliquots of analyte-free water brought to the field in sealed containers
and transported back to the lab with the sample containers. Trip blanks, which are
only analyzed for volatiles, are especially useful when aqueous volatiles are
collected. Trip blanks allow one to assess contamination from transport and storage.
Equipment Blanks are analyte-free water which is poured over the sampling
equipment in the field after the final rinsing of equipment. Equipment blanks allow
one to assess cross contamination and decontamination procedures.
Several key issues must be understood when evaluating the need for equipment
blanks. Equipment blanks are analyzed for total constituents while waste undergoes
extraction. The TCLP leaching process uses 20 grams of leaching fluid per gram of
3-21
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wet weight sample. Therefore, TCLP equipment blanks may not be cost effective for
some types of TCLP sampling. However, if sampling is being done for legal
purposes, such as enforcement actions or potential litigation, equipment blanks
should be collected to assure that the data are legally defensible.
Field Duplicates are samples collected from the same location and waste source at
the same time. The goal is to determine variability in the waste or sample matrix.
The frequency of these depends on the sampling design. Most agencies recommend
at least 5%. Duplicates provide information about sampling and analysis precision.
Laboratory Duplicates are samples which have sufficient volume to allow the
laboratory to homogenize the sample, split the sample and prepare and analyze both
aliquots as separate samples. The purpose is to assess precision between two
laboratory analyses on the matrix.
Enough sample volume must be collected for the lab to generate matrix spikes and
laboratory duplicates. The frequency of these samples varies, and depends on the different
types of waste collected, the time over which they are collected, and the regulatory
requirements.
Sampling Documentation
All sample locations should be identified in a log book. Locations should be from a
surveyed point when applicable. Both horizontal and vertical coordinates should be
documented. Each sampling point should be assigned a unique number or other
identifier.
Unique sample numbers, collector, date and time of collection, container types,
matrix and analysis required (including TCLP and the extract/filtrate analysis) should
be documented in field log books, chain-of-custody (COC) forms, and on sample
labels.
In most cases, a COC should be used to document the collection and transport of
samples to the laboratory. The chain of custody form should be signed and dated by
individuals who collect, transport or receive the samples. Copies of COCs should be
kept by sending and receiving parties.
Any deviations from the sampling plan should be documented in the log books.
The type of sampling equipment utilized must be documented in the log book.
Ambient weather conditions at the sampling location(s) should be documented in the
log book.
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3.4 Analytical Method Selection
Strategy for Analytical Method Selection:
Determine the analytes
Determine the methods of analysis
Specify detection limits and regulatory action levels
Specify quality control samples and requirements
To specify appropriate analytes to demonstrate compliance with the TC regulations, the data
requester needs to understand the basic groupings of analytes which are performed by each
analytical method. The data requester also must understand the typical detection limits and
the issues which revolve around not being able to achieve these limits. The following tables
outline the TC constituent, the category of the analyte, and the potential methods of sample
preparation and analysis. The current CLP contract required detection limits/quantitation
limits and the SW-846 practical quantitation limits are also presented in this section.
The analytical method information should be used in conjunction with process knowledge
and Table 3-2, which lists the TC constituents and regulatory levels, to plan the sampling
and analysis.
3-23
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TABLE 3-2 - TC ANALYTES AND THEIR REGULATORY LEVELS
Constituent1
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
Endrin
Lindane
Methoxy-
chlor
Toxaphene
2,4-D
2,4,5-TP
(Silvex)
Regulatory
Level
(mg/l)
5.0
100.0
1.0
5.0
5.0
0.2
1.0
5.0
0.02
0.4
10.0
0.5
10.0
1.0
Constituent2
Benzene
Carbon
tetrachloride
Chlordane
Chlorobenzene
Chloroform
o-Cresol
m-Cresol
p-Cresol
Cresol (total)
1,4-Dichloro-
benzene
1,2-
Dichloroethane
1,1-Dichloro-
ethylene
2,4-
Dinitrotoluene
Regulatory
Level
(mg/l)
0.5
0.5
0.03
100.0
6.0
200.0
200.0
200.0
200.0
7.5
0.5
0.7
0.13
Constituent2
Heptachlor
Hexachloro-
benzene
Hexachloro-
1,3-
butadiene
Hexachloro-
ethane
Methyl ethyl
ketone
Nitro-
benzene
Pentachloro-
phenol
Pyridine
Tetrachloro-
ethylene
Trichloro-
ethylene
2,3,5-
Trichloro-
phenol
2,4,6-
Trichloro-
phenol
Vinyl
chloride
Regulatory
Level
(mg/l)
0.008
0.13
0.5
3.0
200.0
2.0
100.0
5.0
0.7
0.5
400.0
2.0
0.2
1 Original EP Tox constituents.
2 Chemical constituent added by TC Rule (shaded areas).
3-24
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General Method Information
There are two categories of permissible methods used to analyze TCLP extracts:
1. Many state environmental agencies mandate the use of SW-846 methods for
hazardous waste determinations. SW-846 methods are sometimes also required to
demonstrate compliance with the RCRA regulations. Several different SW-846
methods may be used to analyze TC analytes. Appendix IX explains when SW-846
methods are mandatory.
2. Any appropriate EPA approved method may be used to demonstrate compliance with
the TC regulations. However, if the data are going to be validated, CLP methods are
recommended. Two semi-volatile TC analytes (m-cresol, pyridine) are not included in
the CLP target compound list of analytes. Therefore, the method must be slightly
modified to incorporate these two compounds.
Specifying detection limits and regulatory action levels
The method or contract detection limits must be evaluated versus the regulatory TC
limits. The method or contract limits must be lower than the regulatory limits.
There are three compounds which have quantitation limits that exceed the regulatory
limits: 2,4-dinitrotoluene, hexachlorobenzene, and pyridine. In these cases, the
quantitation limit becomes the regulatory limit.
The EPA Region 2 TCLP SAS Request (Appendix VIII), shows recommended TC
detection limits which are increased in order to minimize matrix effects.
Metals Analysis Information
Metals analysis can be performed by three methods: Inductively Coupled Plasma
(ICP), Flame Atomic Absorption (FAA) and Graphite Furnace Atomic Absorption
(GFAA).
Laboratories usually analyze metals, except mercury, in the TCLP extract by
ICP.
Mercury is usually analyzed by Cold Vapor Atomic Absorption (CVAA).
The GFAA generates lower detection limits than ICP method.
The CLP Contract Required Detection Limits (CRDLs) are the same for both ICP and
GFAA.
3-25
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Table 3-3 Metals Analysis Method By ICP
Analyte
Arsenic
Barium
Cadmium
Chromium
Lead
Selenium
Silver
SW846
Preparation/
Analysis
3010/6010
3010/6010
3010/6010
3010/6010
3010/6010
3010/6010
7760 (prep
only)/6010
SW 846 PQL,
mg/L(1)
.05
.002
.004
.007
.04
.07
.007
CLPCRDLs,
mg/L (2)
.01
.2
.005
.01
.003
.005
.01
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Contract Laboratory Program, Statement of Work for Inorganic Analysis, ILM03.0
Table 3-4 Metals Analysis Methods by GFAA and Mercury by CVAA
Analyte
Arsenic
Barium
Cadmium
Chromium
Lead
Selenium
Silver
Mercury
SW846
Preparation/
Analysis
7060/7060
3020/7080
3020/7131
3020/7191
3020/7421
7740/7740
7760 (prep
only)/7760
7470
SW 846 PQL,
mg/L(1)
.001
.1
.001
.001
.001
.002
.01
.0002
CLPCRDLs,
mg/L (2)
.01
.2
.005
.01
.003
.005
.01
.0002
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Contract Laboratory Program, Statement of Work for Inorganic Analysis, ILM03.0
3-26
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Table 3-5 Pesticide and Herbicide Quantitation Limits by SW 846 and CLP
Analyte
SW846
Preparation/
Analysis
SW 846 PQL,
ug/L(1)
CLP CRQL,
ug/L (2)
Pesticides
endrin
lindane
(gamma BHC)
methoxychlor
heptachlor
toxaphene
chlordane (4)
35 10 or 35207
8080B
35 10 or 35207
8080B
35 10 or 35207
8080B
35 10 or 35207
8080B
35 10 or 35207
8080B
35 10 or 35207
8080B
0.06
0.04
1.76
0.03
2.4
0.14
0.10
0.05
0.05
0.05
5.0
0.05
Herbicides
2,4-D
2,4,5-TP (Silvex)
8150A
8150A
12
2.0
(3)
(3)
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Contract Laboratory Program, Statement of Work for Organic Analysis, OLM01.8
(3) No CLP methods exist for these compounds.
(4) SW-846 quantitation limits are for "technical" chlordane. CLP quantitation limits are for alpha and gamma
chlordane.
3-27
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Table 3-6 Quantitation Limits for Volatile TC Constituents
Volatiles
benzene
carbon tetrachloride
chloroform
chlorobenzene
1 ,2-dichloroethane
1,1-dichloroethylene
(1,1-dichloroethene)
methyl ethyl ketone
(2-butanone)
tetrachloroethylene
(tetrachloroethene)
trichloroethylene
(trichloroethene)
vinyl chloride
SW 846 Preparation/
Analysis
8240B or 8020B
8240Bor8010B
8240Bor8010B
8240Bor8010or
8020B
8240Bor8010B
8240Bor8010B
82406(2) or 801 5
8240Bor8010B
8240Bor8010B
8240Bor8010B
SW846
8240 PQL,
ug/L(1)
5
5
5
5
5
5
100
5
5
10
CLP
CRQL,
ug/L (3)
10
10
10
10
10
10
10
10
10
10
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) Poor purging efficiency by this method produces a high detection limit.
(3) Contract Laboratory Program (CLP) Statement of Work for Organic Analysis, OLM01.8
3-28
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Table 3-7 Quantitation Limits for Semivolatile TC Constituents
Semivolatiles (BNAs)
o-cresol
(2-methylphenol)
m-cresol
(3-methylphenol)
p-cresol
(4-methylphenol)
1 ,4-dichlorobenzene
2,4-dinitrotoluene
hexachlorobutadiene
(hexachloro-1,3-butadiene) (4)
hexachloroethane
hexachlorobenzene
nitrobenzene
pentachlorophenol
pyridine
2,4,5-trichlorophenol
2,4,6-trichlorophenol
SW846
Preparation/
Analysis
3510/8270B
3510/8270B
3510/8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
3510or8270B
35 10 or 35207
8270B
35 10 or 35207
8270B
SW846
PQL,
ug/L(1)
10
10
10
10
10
10
10
10
10
50
ND(2)
10
10
CLP CRQL,
ug/L (5)
10
(3)
10
10
10
10
10
10
10
25
(3)
25
10
(1) PQL = Practical Quantitation Limit = EQL = Estimated Quantitation Limit
(2) ND = Not Determined. If these methods are used, the method detection limits must be determined.
(3) These analytes are not routinely part of the CLP method. If required for TC, these analytes must be specially
requested. The CLP 2/88 extraction procedure must be used for the TC semivolatile analytes if these
analytes are desired.
(4) Other methods quantitate this in the volatile fraction.
(5) Contract Laboratory Program, Statement of Work for Organic Analysis, OLM01.8
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Chapter 4
OVERVIEW OF THE TCLP METHOD
Preliminary Sample Preparation
Leaching Procedure for Non-Volatiles
Leaching Procedure for Volatiles
TCLP Method Quality Control
-------
4.0 OVERVIEW OF THE TCLP METHOD
This chapter provides an overview of the TCLP method. Appendix I of this
document includes a copy of the method and Appendix III provides worksheets
which will be useful in understanding method calculations. The following topics
are covered in this chapter:
Preliminary sample preparation for leaching
Leaching procedure for non-volatiles
Leaching procedure for volatiles
TCLP method QC
4-1
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4.1 Preliminary Sample Preparation for Leaching
Prior to performing the leaching procedure, several preliminary determinations
must be made. These include:
Are there enough solids present for the leaching process?
Is particle size reduction required?
Are immiscible liquids present?
Which leaching fluid should be used for non-volatile analytes?
Figure 4-1 provides a flow chart which delineates preliminary determinations. The first step
is to take 100g of the waste, pass it through a 0.6 to 0.8 urn filter up to 50 psi and determine
the percent solids. If the percent solids are greater than or equal to 0.5% on a dry weight
basis, the solid must be leached. Any material which remains in the filtration apparatus is
considered a solid. When liquids remain on the filtration apparatus because they are too
viscous to pass through the filter, they are treated as solids. Any material which passes
through the filter is the filtrate and considered a liquid. Therefore, viscous oils which do not
pass through the filter are classified as solids. Oily waste will be discussed further at the end
of this document. If the percent solids are less than 0.5%, the filtrate is the TCLP extract,
and the laboratory analyzes the filtrate.
Particle Size
If the percent solids is > 0.5%, the laboratory analyst must determine whether particle size
reduction will be required.
The requirement is not to measure the size. However, the surface area and particle
size must conform with one of the following criteria:
The solid must have a surface area per gram of material equal to or greater
than 3.1 square centimeters.
The solid must be smaller than 1 cm in its narrowest dimension (i.e., pass
through a 9.5 mm (0.375 inch) standard sieve).
If the particle size is too large, cutting, grinding, or crushing may be utilized to
decrease particle size.
Choosing the Leaching Solution
Figure 4-1 shows the determination of the type of leaching fluid for use. If the solid content
is greater than or equal to 0.5%, and if the sample is being analyzed for metals or
semivolatiles, the type of leaching solution must be determined. Note that the leaching
solution determination step requires a smaller (1 mm) particle size than the analytical
method because the leaching solution determination allows much less contact time between
the leaching solution and the sample.
4-2
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After weighing a 5.0 g subsample of the solid, adding 96.5 ml_ of reagent water, and stirring
for 5 minutes, the pH is measured. If the pH is <_ 5.0, fluid #1 is used. If the pH is > 5.0, 3.5
ml_ of 1N HCI is added. The mixture is heated to 50°C for 10 minutes and cooled. If the
measured pH is less than 5.0, fluid # 1 is used. If the pH is greater than 5.0, extraction fluid
#2 is used.
The heating cycle is a critical step. After the sample has been heated, it should be cooled to
room temperature. The pH must be measured immediately after the sample has reached
room temperature. If the solid waste does not remain in contact with the acidic solution
under specified time and temperature conditions, an erroneous pH may be measured.
The leaching fluid for all volatiles is fluid #1. Fluid #1 is an acetic acid and sodium hydroxide
buffer of pH 4.93 + 0.05. Fluid #2 is an acetic acid solution of pH 2.88 + 0.05.
4-3
-------
Figure 4-1
4-4
-------
4.2 Leaching Procedure for Non-Volatiles
The non-volatiles include semivolatile organics, which are also called base,
neutral, and acid extractables (BNAs), pesticides, herbicides, and metals. If the
percent solids exceeds 0.5%, the solid is leached with the appropriate extraction
fluid after any required particle size reduction. The following topics are discussed
in this section:
Determination of extraction fluid weight
Sample and QC sample volumes
Extract volumes required
Issues when dealing with multi-phasic waste
Initial filtrate versus TCLP leachate
The non-volatile extraction or leaching process is outlined in Figure 4-2. The extraction
process includes placing the sample and appropriate fluid in the bottle extraction vessel and
tumbling for 18 + 2 hours and filtering the extract for subsequent analysis. The bottle
extraction vessel is described in Section 4.2.2 of Method 1311, which is Appendix I of this
document. In order to generate scientifically valid and legally defensible data, appropriate
weights of environmental samples and leaching fluids must be used.
4-5
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Figure 4-2
4-6
-------
Determination of Extraction Fluid Weight
The following formula is used to compute the required weight of TCLP extraction fluid:
Weight of Extraction = 20 x %Solids x Weight of Waste Filtered
Fluid 100
The amount of extraction fluid required per extraction is 20 times the weight of wet filtered
solids used in the extraction.
A minimum of 100g of waste material must be filtered to generate the solids utilized in the
extraction. If the sample is 100% solids, a minimum of 100g must be used in the extraction.
When aqueous environmental samples contain between one-half and ten percent solids,
several kilograms of sample are required for analysis.
Sample and QC Sample Volumes
The generation of sufficient extract volume to perform all analysis is critical.
The required volumes vary with the laboratory. Check with the laboratory for actual
volumes.
Depending on which metal analytes are selected, two or three digestions may be
required.
If matrix spikes or duplicates are performed, additional volume will be required. Labs
may charge additional fees for these QC samples.
Table 4-1 Volume of Extract Required for One Nonvolatile Analysis
Analysis Type
BNA
Chlorinated Pesticides
Herbicides
Metals
Volume of TCLP Leachate Typically
Required per Test
1 L
1 L
1 L
300 mL/digestion
The previous table outlines the "typical" volumes of extract or total leachate required for non-
volatile analysis. These volumes may vary with the laboratory. It is imperative that you check
with the lab as to the amount of waste required for their analysis process. The amount of
waste varies with the percent solids. The lower the percent solids, the more waste will be
needed for TCLP preliminary and final testing. If the waste sample is a filterable liquid with
less than 0.5% solids, the volume listed in the previous table can be used as a guide for the
minimum volume needed for the analysis.
4-7
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Issues When Dealing with Multi-phasic Waste
Subsampling stratified waste is difficult. Therefore, the analyst should consider
calculating percent solids from the same sample container used for the TCLP
extraction instead of compositing all the sample containers. This is the largest source
of error in the TCLP leaching process. The laboratory must consider the amount of
each phase present in each bottle and adjust the calculations accordingly.
The particle size of multi-phasic material may be difficult to assess. The lab should
identify procedures to classify multi-phasic samples which are not amenable to size
measurement.
Five grams of sample are usually used to determine the appropriate TCLP leaching
fluid. If there is not enough volume of any individual phase, less material may be
used.
The pH of the filtrate should be recorded. This provides useful information when
validating field or laboratory duplicates.
The filtrate volume should also be measured. This information will be needed if the
multiple phases must be mathematically combined.
Initial Filtrate Versus TCLP Leachate
Two liquids are generated when a multi-phasic waste is analyzed.
Initial filtrate
Leachate
If the filtrate is miscible with the leachate, the two solutions are mixed prior to
analysis.
If the two solutions are not miscible, they are analyzed separately, and the results
combined mathematically.
The mathematical calculations are performed via the following equation if the TCLP filtrate
and extract are not miscible.
Final analyte = (V1) (CD + (V2) (C2)
Concentration V1 + V2
where:
V1 = The volume of the first phase (L).
C1 = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase (mg/L).
4-8
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After generating the TCLP extract, the pH of the extract should be recorded. If the filtrate
and TCLP extract are mixed, record the pH of the mixture as well as the original TCLP
extract and filtrate. The TCLP extract or filtrate/extract mixture should be aliquoted for each
analysis. Matrix spikes for all subsequent analyses must be added at this time.
The metals aliquot should be preserved to a pH<2 with nitric acid. Adjust the pH of a small
portion of the TCLP extract or mixture prior to adjusting the entire metals aliquot. If a
precipitate forms, do not adjust the pH of the sample extract. If nitric acid is not added, the
sample should be analyzed as soon as possible after TCLP extraction. Metals analysis must
include digestion prior to analysis. Aliquots for BNAs, herbicides and pesticides do not
require chemical preservation. All aliquots must be stored at 4°C + 2°C prior to analysis.
Example
The following example demonstrates how to calculate the weight of extraction fluid required
to perform a TCLP extraction. In this example, the environmental sample contains 40%
solids. Only metals will be analyzed since the waste is from a metals finishing shop.
In order to determine the total amount of waste required to generate 100g of solids, the
following equation is used:
Amount of multi-phasic material = (10,000)7 (weight percent wet solids)
If 100g of original waste yields 40g of solid, the total amount of waste required to generate
100g of solid is 250g.
250g of total waste required = 10,000/40
Using the equation in Section 7.2.11 of Method 1311 (Appendix I):
Weight of extraction = 20 x % solids x weight of waste material filtered
fluid 100
20x_40 x250g = 2,OOOg of extraction fluid
100
Labs typically assume a density of 1 g/mL for the extraction fluid. Also, note that 40% is
used, not 0.40, for the percent solids. Since 300 mL of extraction fluid is required for one
complete metals digestion, using 250g of the multi-phasic waste will provide enough volume
for the metals analysis. This allows enough volume to analyze one matrix spike. The use of
matrix spikes will be discussed in the QC section of this chapter. The matrix spike sample
size requirement is the same as for original environmental sample analysis.
4-9
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If organic analysis were required, at least three times as much waste would have been used
in the TCLP extraction. For matrix spikes analyses, a triple volume of TCLP leachate will be
required. The terms analytical batch and waste type are not defined in the TCLP regulation.
Most methods, including CLP and SW-846, indicate that a batch is the number of samples
processed through preparation and analysis simultaneously, and should not exceed 20
samples of the same matrix. Most methods require that matrix spikes and matrix spike
duplicates (MS/MSD) for organics be performed at 1 MS/MSD per processed batch, with a
batch containing no more than 20 samples.
4-10
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4.3 Leaching Procedure for Volatiles
Volatile organics are leached using different equipment than non-volatiles.
Figures 4-3 and 4-4 are the flow charts describing the volatile leaching procedure using the
Zero Headspace Extractor (ZHE). The ZHE must be used when leaching volatiles. In order
to minimize evaporation of volatiles, the volatile leaching procedure is performed on a
separate aliquot of waste. Once the percent solids has been determined in the preliminary
sample preparation phase, a second aliquot of the waste is used to generate the volatile
analysis extract. In all cases, no more than 25g of solids should be placed in the ZHE
because the total volume of the ZHE is 500-600 ml_s. In order to prevent the loss of volatile
compounds, heating or excessive sample manipulation must be kept to a minimum. The
samples and equipment used in the process should be cooled to 4°C when possible to
prevent loss of volatiles.
If the sample contains less than 0.5% dry solids, the filtrate is defined as the TCLP extract.
The solid is discarded in this instance. The filtrate is collected in either a Tedlar bag or a
glass syringe which is described in the equipment section of the procedures in Appendix I of
this document. This filtrate becomes the TCLP extract.
Weight of Waste Charged to the ZHE
If the solids are > 0.5% dry solids, the material must be extracted.
If the solids are > 0.5% and < 5.0 %, a 500 g subsample of the waste is weighed
and recorded.
If the solids are > 5.0%, the following formula is used to determine the amount of
waste to place in the ZHE:
Weight of Waste = 25x100
Charged in ZHE Percent wet solids
If the solids are greater than 0.5% and the sample is multi-phasic, any solids must be
examined for particle size prior to filtration. The sieve is not used to verify particle size for
the volatile sample. Particles are measured with a ruler and should be less than 1 cm
diameter. Any particle size reduction should be done with minimal exposure to air and
without heat production. All apparatus used in this process should be cooled to 4°C.
4-11
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figure 4-3
4-12
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Figure 4-4
4-13
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All waste which remains in the ZHE after reaching a pressure of 50 pounds per square inch
(psi) is considered solid phase and undergoes leaching. Any liquid which is removed during
filtration is considered liquid phase filtrate. The filtrate is captured in either a Tedlar bag or
glass syringe. The solids are leached with fluid #1.
If the percent solids is 100%, a 25g sample of the solid is placed in the ZHE after any
necessary particle size reduction is performed. The particle size reduction follows the same
protocol requirements as volatile extraction of waste with solids content greater than 0.5%
but less than 100%. The extraction is similar to the TCLP extraction of multi-phasic material.
When performing TCLP extraction for volatile analysis, extraction fluid #1 is always used.
The quantity of extraction fluid is 20 times the solid waste weight used in the extraction.
The extraction is performed by placing the ZHE in the rotary agitator at 30 + 2 rpm for
18+2 hours. The ambient temperature is maintained at 23 +2°C during agitation. At the end
of the agitation period, the ZHE piston pressure must be measured to verify that pressure
was maintained during the extraction. If pressure was not maintained, the extraction must
be repeated after the ZHE is examined for mechanical problems. If the pressure was
maintained, the material in the ZHE is separated into solid and liquid phases by pressure
filtration. A small amount of the liquid extract should be examined for miscibility with the
previously captured filtrate. If these fluids are miscible, the liquid extract and the filtrate may
be stored in the same container (Tedlar bag or syringe) with minimal or no headspace. This
mixture becomes the TCLP extract for volatile analysis. If the two fluids are not miscible,
they are stored in separate containers with minimal or no headspace. The volatile analysis
are performed separately and combined mathematically using the same equation as for the
non-volatile analysis. All extracts and fluids are kept at 4°C +2°C prior to analysis.
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4.4 TCLP Method Quality Control
TCLP extraction blank
Method preparation blanks
Calibration
Matrix spikes
BIAS CORRECTION IS NO LONGER REQUIRED.
Method of standard additions
TCLP Extraction Blanks
A minimum of one TCLP extraction blank is generated for every 20 extractions
processed in a given extraction vessel using the same fluid. Most labs have multiple
extraction vessels. The common industry strategy is to generate one TCLP
extraction blank for each group of samples processed simultaneously using the same
batch of fluid.
Calibration
Calibration should follow the respective method requirements. Typically a three to
five point initial calibration followed by a single point continuing calibration is
specified.
Method Preparation Blanks
Preparation blanks performed for a specific analysis should follow the frequency and
requirements of the method. Typical requirements are one per preparative batch
from similar matrix for every 20 samples.
Matrix Spikes
Matrix spikes are used to monitor the performance of the analytical methods on the
matrix and to assess the presence of interferences.
A matrix spike shall be performed for each waste type (waste water, soil, etc.) unless
the result exceeds the regulatory level and the data are being used solely to indicate
that the regulatory level is exceeded.
A minimum of one sample from each "analytical batch" must be spiked. For spike
samples, a double or triple volume of TCLP leachate will be required. The term
analytical batch is not defined in the regulation. Most methods, such as CLP and
SW846, indicate that a batch is no more than 20 samples of the same matrix
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processed through preparation and analysis simultaneously. Based on this criteria,
the minimal matrix spike frequency of analysis is one per 20 samples. However,
many process batches may include from one to 19 samples and the frequency may
increase with fewer samples processed. Some EPA Regions define each type of
waste as a matrix, and require matrix spikes for each matrix.
Matrix spikes (MS) are to be added after leaching and filtration but prior to
preservation. Spikes are NOT to be added prior to the TCLP leaching.
The spike should be added to the same nominal volume of TCLP extract as the
unspiked sample.
The spike concentration "should" be added at the regulatory level. If the expected
concentration in the sample is as low as half the regulatory level, the spike
concentration can be decreased to half the regulatory level. In all cases, the spike
must be greater than 5 times the method detection limits.
Matrix Spike Recoveries are calculated by:
%Recovery = 100 ( Measured value for the spiked sample minus measured
value of the unspiked sample)/ known value of the spike
When the matrix spike recovery falls below the expected analytical performance,
alternate methods of analysis may be required to measure analyte concentration in
the TCLP extract. The matrix spike recovery limits from the Contract Laboratory
Protocol methods are used when the method is used.
If the matrix spike recoveries exceed limits, other analytical methods such as isotopic
dilution may be used to deal with the matrix effects. Typically, the holding times will
be exceeded or near the limits when this occurs. If possible, resampling of the waste
may be required to assure that the appropriate method is used and holding times are
met.
Bias correction is no longer required.
Surrogate Spikes
Surrogates are compounds which are not expected to be in the samples but are chemically
similar to those being determined. The concentrations and specific compounds are listed in
the appropriate methods. The recovery of the compounds are monitored with specific
criteria either being found in the method or determined by statistical quality control in the
laboratory.
Method of Standard Addition
Four equal volume pre-digestion aliquots of sample are measured and known amounts of
standards are added to three aliquots. The fourth aliquot is the unknown and no standard is
added to it. The concentration of standard added to the first aliquot should be 50% of the
expected concentration. The concentration of standard added to the second aliquot should
be 100% of the expected concentration and the concentration of standard added to the third
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aliquot should be 150% of the expected concentration. The volume of the unspiked and
spiked standard should be the same.
In order to determine the concentration of analyte in the sample, the analytical value of each
solution is determined and a plot or linear regression performed. On the vertical axis the
analytical value is plotted versus the concentrations of the standards on the horizontal axis.
An example plot is shown in Figure 4-5. When the resulting line is extrapolated back to zero
absorbance, the point of interception of the horizontal axis is the concentration of the
unknown.
Fig 4-5
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When must Standard Addition be used?
The method of standard additions is used for metallic contaminant determinations if both of
the following criteria are met:
1. The matrix spike recovery from the TCLP extract is less than 50% and the unspiked
sample concentration is less than the regulatory level.
2. The contaminant measured in the sample is within 20% of the regulatory level.
For the method of standard additions to be correctly applied, the following limitations must be
taken into consideration:
The plot of sample and standards must be linear over the concentration range of
concern. For best results, the slope of the line should be similar to that of a plot of
the aqueous standard.
The effect of the interference should not vary as the ratio of the standard added to the
sample matrix changes.
Holding Times
As previously discussed in Section 3, the holding times must be met. Sample data which
exceed holding times are not acceptable for verifying that a waste does not exceed
regulatory levels. However, if TCLP extract concentrations exceed regulatory action levels,
and holding times are exceeded, the data are considered minimum values, and the data are
considered valid.
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Chapter 5
DATA VALIDATION AND
DATA DELIVERABLES
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5.0 DATA VALIDATION AND DELIVERABLES
This chapter addresses the following questions:
What is data validation?
When must TCLP data be validated in EPA Region 2?
Which analytical deliverables are needed to validate TCLP data when
utilizing the USEPA Region 2 Organic, Inorganic, and TCLP Data
Validation Protocols?
Which analytical deliverables are recommended for TCLP data which will
not be validated?
How should these deliverables be utilized to assess data quality and
usability?
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5.1 Data Validation
What is Data Validation?
"Data validation is a systematic process for reviewing a body of
data against a set of criteria to provide assurance that the data are
adequate for their intended use. Data validation consists of data
editing, screening, checking, auditing, verifying, certifying and
reviewing." (EPA Region 2 CERCLA QA Manual)
The most important criteria which the data reviewer evaluates are:
1. Holding times
2. Instrument tuning
3. Calibration and retention time windows
4. Blank contaminants
5. Surrogates (a measure of extraction efficiency)
6. Chromatographic performance (baseline, interference, retention time shift and peak
resolution)
7. Emission interferences or spectral interference from other elements when reviewing
metals data
8. Calculations
9. Transcription of numerical values to the required forms in the data package
10. Matrix effect errors; interference from the sample itself
11. Degradation of compounds during analysis
There is a substantial amount of uncertainty in all chemical data. In addition to lab error,
there are field sampling errors, such as improper decontamination of field equipment, air
bubbles in VOA vials, loss of samples, and failure to ship samples in a timely manner after
collection. Different analytes have varying degrees of uncertainty.
TCLP data are expected to have significantly more inherent error than routine chemical
analysis because additional procedures are performed by the laboratory analyst.
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What is data qualification?
Qualifying data is a method of notifying the data user that some data have additional
uncertainty. The Region 2 TCLP data validation protocol qualifies analytical data with the
following flags:
R Rejected (unusable)
J Estimated
UJ Estimated detection limit
N Presumptively present (cannot positively identify an analyte)
JN Presumptively present at an estimated concentration
The above qualification "flags" provide QC information to the data user. The Region 2 TCLP
data validation protocol qualifies analytical data as unusable, estimated, presumptively
present, or presumptively present at an estimated concentration.
Unusable data are rejected and qualified with an "R". When data are rejected, it doesn't
mean that the analyte wasn't there - it means that either the test was not correctly performed
or that the test was not appropriate for the matrix. Examples of reasons for rejecting data
include: poor calibration, low surrogate recoveries, and air bubbles in volatile sample vials.
If the data are needed, resampling and reanalysis must be performed. For example, the
holding time for TCLP VOAs is 14 days from sampling until TCLP leaching, and then 14 days
until analysis. If a sample is held for 30 days from collection until leaching, all non-detects
and positive results below regulatory action levels will be rejected because analytes could
have been present above regulatory action levels. Results above the regulatory action
levels would be accepted. However, the site owner may still want resampling and reanalysis
to assure that a false positive did not occur.
When data are qualified as estimated with a "J", it means that the data should be used with
caution. The data are significantly imprecise, and the reported value given is little more than
an estimate. Estimated means that the compound is present, but the exact concentration is
uncertain.
When data are qualified with a "UJ", it means that the detection levels are uncertain. For
example, this qualifier would be used when surrogate recoveries in organics are greater than
10% but not within the method criteria. The "UJ" notifies the data user that the detection
limits are estimated.
When the analyte identity is uncertain, the qualifier "N" is used to indicate that it is
presumptively present. This is used in data validation when a mass spectrum differs slightly
from the required spectral criteria. Data validators use the qualifier "JN", presumptively
present at an estimated concentration, much more often than the qualifier "N". The"JN" flag
denotes both qualitative and quantitative uncertainty. This is typically used when tentatively
identified compounds (TICs) from semivolatile gas chromatography/mass spectrometry
analysis are presented. The concentration and identities of the TICs are uncertain and are
flagged with "JN".
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When Must TCLP Data Be Validated?
EPA Region 2 requires TCLP data for RCRA RFIs and many types of CERCLA sampling
events to be validated. The RCRA program does not explicitly require the validation of
routine TCLP analysis of waste materials to determine compliance with TC or LDR
regulations.
Data validation reduces false negatives, false positives, and misquantitation in reported data.
Misquantitation includes both laboratory arithmetic errors, and data qualified as estimated or
presumptively present because of analytical problems. The costs for TCLP validation are
quite variable, and depend specifically on which tasks the data user instructs the data
validator to perform, and the quality of the laboratory analyzing the environmental samples.
The cost of validating a single sample containing the 39 TC analytes is about $300-$500 per
sample analyzed by a competent laboratory. In addition to the data validation cost, the
laboratory will charge an additional fee, estimated at $200-$400 per sample, for generating
analytical deliverables. The more a data user knows about a specific waste, the less useful
data validation becomes. For example, if the data user knows which raw materials, final
products, and by-products are in a waste, and has historical data that demonstrates that the
TC analytes in the TCLP extract are far below regulatory action levels, TCLP validation
would not be cost effective. Alternatively, when the data user has very limited knowledge of
a waste's characteristics, decisions based on that data can result in significant disposal cost
for management. Therefore, many businesses believe that it is prudent and cost effective to
validate this type of TCLP data.
Some regulatory agencies, especially in the CERCLA program, do not allow laboratories to
validate their own data. All laboratories review their own data for contractual compliance
and analytical problems. Unfortunately, this assessment of contractual compliance may also
be called data validation. Many laboratories now call their contractual compliance review
"data review" to differentiate this review from data validation.
Contractual compliance is NOT the same as data validation. A lab can contractually fail and
still produce technically valid data. An example of this occurrence is when contractual
requirements for metals data indicated that results would be delivered to the client 40 days
from receipt of the sample. If the laboratory did not deliver for 60 days, the laboratory failed
the contract criteria, but the technical criteria were still met. Alternatively, a laboratory can
contractually meet criteria but produce data which is not useable.
In order to validate TCLP data, the following must be ascertained:
Are any specific data validation protocols required by a regulatory agency?
What are the regulatory action levels?
The TC regulatory action levels are listed in Table 1. The Land Disposal Restrictions
regulatory action levels are listed in Appendix II.
The EPA Region 2 TCLP, Inorganic and Organic Validation protocols are included in
Appendix IV. If your region or state does not have a TCLP validation procedure, the Region
2 data validation protocol may be used. If the applicable sampling and analysis plan
requires regulatory approval, the data user, lab and regulator must agree on validation
criteria prior to sample collection.
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Phenols
When validating TCLP phenols, the TCLP extraction fluid may cause a matrix effect. This
matrix effect may lower surrogate and matrix spike recoveries for phenols. As long as the
matrix spike and surrogate recoveries are above 10%, the data should not be rejected. If a
matrix effect precludes acceptable pyridene or phenols surrogate and matrix spike
recoveries, a facility should request a meeting with the appropriate regulatory agency to
discuss alternate methods for determining whether a solid waste exhibits TC.
After determining whether the project will require validation, the appropriate deliverables
must be specified to allow the validation to occur. For example, if the validation requires
calibration verification, raw instrument calibration data must be present for the validation to
be performed.
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5.2 Data Deliverables
General TCLP Data Deliverables
In order to validate and assess TCLP data, appropriate deliverables must be
specified. Deliverables will differ depending on whether validation is required.
These analytical deliverables must be specified before samples are collected.
The following topics are discussed:
Deliverables when no validation is required
Additional deliverables which may assist in review
USEPA Region 2 analytical deliverables
Specifying data deliverables
Deliverables When No Validation is Required
When TCLP data are not validated, we recommend that the laboratory furnish the data user
the following deliverables:
1. Sample description and sample identification numbers.
2. Analytes, concentrations, and units.
3. Level of contaminant(s) in method and TCLP blanks.
4. Matrix spike, QC check sample when applicable, and surrogate recoveries.
5. A description of matrix problems and analytical problems observed during analysis,
and an assessment of how those problems will affect data usability.
6. A certification that samples were analyzed within method holding times (from the date
of sample collection). This certification must include the sampling date, TCLP
extraction dates, preparatory extraction dates, and analysis dates.
The laboratory staff are not always familiar with data validation protocols or with data
usability on a project specific level. Therefore, in addition to information about the QC
supplied by the laboratory, it may be beneficial to work with a specialist in this area. Some
firms specialize in validating and assessing data quality.
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Additional Deliverables Which May Assist in Review
While the data is the key factor, some information is not always captured in the analytical
result. For example, if a procedure is modified due to a matrix problem, the procedure must
be documented and the validator provided this information. The following information may
facilitate validation.
Chain of Custody records
Analytical procedures used by the laboratory
An example of a data calculation
The data user must specify the information (analytical deliverables) desired from the
laboratory. If this is not done, only the final result, or the final result plus a QC summary, will
be provided.
Region 2 Analytical Deliverables
The following TCLP analytical deliverables are required by the Region 2 TCLP data
validation protocol:
1. The TCLP and preparative extraction dates and analysis dates.
2. Selection of extraction fluid data.
3. A physical description of the samples.
4. The sample weights and the extraction fluids weights.
5. The final volume of TCLP extract and the volume of extract analyzed.
6. The data used to compute percent dry solids and the weight of the liquid phase (if
applicable).
7. Extraction logs for each sample, indicating the volume and pH of acid added. Were
inorganic sample extracts properly preserved?
8. A description of the materials of construction for extraction vessels, filtration devices,
and ZHE extraction devices (i.e. glass, Teflon, PVC, stainless steel, etc.).
9. The data used to compute TCLP extract concentrations for multi-phasic samples.
10. When VOA samples consist of oily waste that cannot be filtered, describe how the
TCLP aqueous extract is separate from the oily waste.
11. A copy of the sampling log or trip report.*
12. Any evidence of leakage in the ZHE device.
*ltem 11, which requires the presentation of the sampling log, may not be available from the
laboratory. The sampling team may supply this information.
In order to facilitate analysis and validation, Associated Design and Manufacturing
Corporation and Dr. Larry Jackson have developed work sheets (Appendix III) which may be
used by the analytical laboratory to generate the above listed analytical deliverables.
Additional descriptions of requirements and deliverables for modification of CLP analysis of
leachate is presented in Appendix VIII.
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Specifying Data Deliverables
EPA Region 2 requires TCLP data to be validated for RCRA RFIs and many types of
CERCLA sampling events.
Specific regulations, as noted in Appendix IX, require SW-846. Many state environmental
agencies require the use of SW-846 methods for hazardous waste determinations.
SW-846 methods cannot be validated by CLP validation criteria because SW-846 methods
do not specify analytical deliverables, and have different QC criteria than CLP methods.
Therefore, validation protocols must be prepared for non-CLP methods such as those in
SW-846.
For non-CLP methods, data validation criteria must include:
Holding times for sample preparation and analysis
Preparation logs
Calibration
Method and instrument blank data review
Calculations
Matrix spike data
Duplicate results
For organic analysis, the following additional items must be included:
Instrument tuning if GC/MS is used
Surrogate recoveries
Chromatographic performance (baseline, interference, shift and peak resolution)
Mass spectral interpretation or compound identification
For metals analysis, the following additional items must be included:
Whether method of standard addition or serial dilution were needed and performed
correctly. The November 24, 1992 modification to the TCLP procedure mandates the
use of method of standard additions under certain circumstances.
Post digestion spike recoveries versus pre-digestion spike recoveries.
The frequency of analysis of QC samples must be validated.
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Chapter 6
ANALYZING AND ASSESSING MULTI-PHASIC
AND OILY WASTES
Definition of Oily Waste
Problems/Issues
Suggestions
Most Commonly Asked TCLP Question
Analytical Options
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6.0 ANALYZING AND ASSESSING MULTI-PHASIC AND OILY WASTES
Analyzing and Assessing Multi-Phasic and Oily Wastes
This chapter provides strategies which may be beneficial in characterizing oily
wastes. There is no single correct method to analyze these wastes.
Definition of oily waste
Problems/Issues
Suggestions
Most commonly asked TCLP question
Analytical options
This chapter outlines the current issues and difficulties in performing TCLP on multiple
phase and oily waste. This chapter is not meant to provide unequivocal answers, but to
provide suggestions and strategies which may be successful. There is no single correct
method in dealing with these materials. The initial discussion in this chapter provides
references and information indicating that EPA understands the difficulties in applying the
TCLP to multi-phasic and oily wastes. Subsequent discussions summarize possible
strategies which may be used in leaching and analysis.
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6.1 Definition of Oily Waste
Appendix VI contains several papers presented at the EPA's 1992 Waste
Testing & Quality Assurance Symposium Work Shop on oily waste. The
following is Clifford Marquis's of BP Research, definition of oily waste (see
Appendix VII):
Although it is nearly impossible to precisely define the term "oily waste", the
following analysis can provide a basis for further discussion:
a) An oil is generally an immiscible or relatively insoluble liquid,
varying in composition but consisting of organic constituents.
Petroleum oil principally consist of hydrocarbons; vegetable and
animal oils are glycerides, and fatty acids; and essential oils are
terpenes, alkaloids, etc.
b) An oily waste is an industrial process waste or residual
bearing oil in a visual and/or measurable proportions.
c) Oil in oily wastes can occur in any matrix, including: sorbed
to dry solids; in sludges or slurries; multi-phasic liquids or
sludges/slurries with multi-phasic liquids, if water is present. Proper
treatment and disposal of all such matrices is a concern of the
petroleum industry.
d) Oily wastes possess a wide variety of compositions and
physical and toxicological properties.
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6.2 Problems/Issues
Problems with the TC Model
The model does not differentiate between oily and aqueous liquids.
The model assumes a person drinks 2 liters a day of well water for 70
years. This assumption is not applicable for oily wastes.
The disposal scenario depicted by EPA is not an accurate description of
today's practices. For example, liquids are no longer accepted in
municipal landfills.
The model does not correct for absorption of oily waste on soils. Oil may
also adhere to other landfill matrices instead of mixing with the aqueous
phases.
The difficulty in analyzing oily wastes by TCLP may be categorized as modeling, analytical
and regulatory problems.
The Leachability Subcommittee of the EPA Science Advisory Board's Environmental
Engineering Committee has published its recommendations. A copy of this report is in
Appendix VII of this document. This document outlines the properties of an optimum leach
test.
Issues with Oily and Multi-phasic Waste and TCLP
It is difficult to separate the phases.
Volatiles may evaporate during handling.
The tumbling action of the two liter extraction vessel can form emulsions which are
difficult to separate.
The oily material may obstruct the filter. When this happens with the ZHE, the test
must be repeated.
Oily materials often yield oil and aqueous leachate which must be analyzed
separately. This increases costs and time of analysis.
The method requires determination of dry weight percent solids. When the "solid" is
actually oil or organic, drying can be hazardous and inappropriate. It may be
impossible to achieve a constant weight when performing a percent solids
determination.
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When multiple phases and multiple bottles are used in sampling, each container will
show different amounts of each phase.
It may be impossible to separate solids from oil. If volatiles are analyzed, additional
sample manipulation to remove solids will result in loss of volatiles.
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6.3 Suggestions
Suggestions for performing TCLP extractions on oily wastes include the
following:
Planning
Regulatory approval
Separate phases for analysis
Documentation of phase type and volumes
As previously indicated, these are suggestions. There are no consistently and absolutely
appropriate methods when performing TCLP extractions on oily wastes.
Planning is more critical when oily or multi-phasic samples are collected and
analyzed. Discuss the sample matrix with the laboratory before collecting samples.
Once an approach is formulated, regulatory approval may be needed. This approval
is of greater importance if deviations from the TCLP extraction method are required
due to the matrix.
If two liquid phases are present, each phase should be separated and analyzed
individually.
The SW-846 Methods specify several procedures for analyzing oily waste. BNA
methods include 3580B for preparation followed by 8270B. The pesticides method
includes 3580B using hexane as the extraction solvent followed by 8080B. The
VOAs are analyzed by 8240B. Metals can be prepared by method 3040B and
analyzed by appropriate analytical methods.
The number, appearance, and volume of each phase should be documented before
collection of the sample. The phase volume can be estimated by measuring the
height of the phase in the container and the diameter of the container. This
information can be used to estimate the amounts of material available for testing.
Phase volume should be estimated after sample collection and prior to analysis.
In multi-phasic liquid samples, the relative density of each phase should be
documented.
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When multiple containers of multi-phasic waste are received, each container will have
different amounts of each phase. If multiple sample containers are collected and
each container is multi-phasic, the number, appearance, volume and relative density
should be documented for each container.
If regional and state regulators will allow, one container can be mixed and analyzed.
By knowing the volumes in the other sample containers, the total composition can be
mathematically calculated.
If one phase is organic and contains < 0.5% solids, this may be directly characterized
by the appropriate analytical method after filtration without TCLP extraction.
Subsampling increases the possibility of sampling error.
The percent solids should be determined in multi-phasic samples before filling the
ZHE. This prevents overfilling the ZHE.
The TCLP method requires drying the solids at 100°C + 20°C to determine percent
dry solids. This may not be achievable for organic multi-phasic material because of
safety considerations. If this cannot be done, the reason should be documented.
The percent wet solids is used to calculate the weight of extraction fluid. If this
occurs, the lab should discuss this with the client prior to using the percent wet solids
as the solids content. This will greatly effect the final analyte concentrations.
Particle size reduction is difficult on oily material because the solids congeal. This is
especially true if the material cannot be dried.
Extreme caution should be taken when adding acid to organic waste. Heating the
organic waste in the presence of acid to 50°C should be done with great caution.
This may be required in order to determine which extraction fluid is used.
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6.4 Most Commonly Asked TCLP Question
I have an oily waste, which flows through a filter. My detection limits are higher
than the regulatory action levels. What should I do?
You have four options:
1. Recycle or burn.
2. Classify by prior knowledge as non-hazardous.
3. Treat the waste as hazardous.
4. If the oil passes through the filter, analyze the TCLP leachate.
1. If the oily waste can be classified as used oil, it can be burned or recycled and a
TCLP analysis is not needed (40 CFR 266.40; 261.6(a)).
2. The waste can be treated as hazardous if no information is available to allow
classification by prior knowledge.
3. By knowledge of the generation of the oily waste, the generator may be able to certify
that the waste could not contain any of the TC analytes at concentrations above the
regulatory action levels. (40 CFR 262.11c(2)). The waste may be a regulated
hazardous waste under other EPA waste code classifications.
4. The liquid which passes through the filter can be analyzed to determine whether it
contains TC analytes. If the SW 846 methods are not appropriate for TC analytes,
any method which is sensitive enough to meet regulatory limits and has documented
QC may be used.
The following pages include correspondence on oily waste explaining EPA's strategy for
classifying oily wastes as hazardous or non-hazardous.
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6.5 Analytical Options
The methods discussed from SW 846 may not provide adequate identification
and quantification of the waste. Inadequate method performance may be
caused by matrix interferences. The following methods may assist in dealing
with organic matrix problems. This list is not exhaustive. Method development
may be required to accommodate specific interferences. If development is
required, method validation should be performed and approvals may be required
when SW 846 is required by the regulations.
Isotopic dilution
High resolution GC/MS
Isotopic Dilution
One option outlined by EPA in the memoranda is the use of isotopic dilution methods. The
isotopic dilution methods use stable isotopically-labeled analogs of the compounds of
interest. These labeled compounds are added prior to sample preparation and analysis. In
the case of volatiles and semivolatile analyses by GC/MS, they are added prior to purging or
extraction. Two methods are currently listed in 40 CFR Part 136 Appendix A which use the
isotopic dilution technique. One is a purge and trap capillary GC/MS, method 1624, and the
other is semivolatile extraction followed by capillary GC/MS, method 1625.
In both methods, the calibration is established by relative responses based on a ratio of the
isotopically-labeled compound versus the unlabeled compound over five concentration
ranges. The relative response of the labeled versus unlabeled compound in the sample is
compared to the calibration curve or average response factor to quantitate the analyte in the
sample.
An example of a labeled compound is toluene-d8, which is deuterated toluene (all hydrogens
are replaced by deuterium). Carbon-13 labeled compounds may also be used.
The advantages of isotopic labeling are greater accuracy in quantitation and the ability to
quantitate despite interferences. The disadvantages are the expense and difficulty in
obtaining labeled analogs of the compounds of interest, and the time needed to develop the
procedure. Laboratories which have experienced GC/MS staff who have done dioxin
analyses or who have many years of GC/MS experience should be capable of providing
these analyses.
High Resolution GC/MS
High resolution GC/MS could also be used to quantitative the compounds. There are no
published methods for waste analysis by high resolution GC/MS. However, this technique
should provide greater sensitivity, lower detection limits and the ability to deal with
interferences. The disadvantages are the same as isotope detection. Regulatory approval
should be obtained before utilizing expensive isotope dilution or high resolution GC/MS
analyses.
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Appendix I
TCLP Methods From
40CFR261 Appendix II
SW 846 Method 1311
(Method Without Typographical Errors)
July 1992
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Appendix II
40 CFR 268 Subpart D Land Ban Treatment Standards
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Appendix III
Associated Design and
Larry Jackson's
TCLP Bench Sheets
and Calculations
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Appendix IV
USEPA Region 2
Organic, Inorganic and TCLP Data Validation
Methods
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Appendix V
References for Multi-phasic and Oily Waste
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Appendix VI
Office of Solid Waste Methods Section
Memoranda #35, #36
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Appendix VII
Recommendations and Rationale for Analysis of
Contaminant Release by the Environmental Engineering
Committee
Science Advisory Board
October 1991
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Appendix VIII
USEPA Region 2
Special Analytical Services Request
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Appendix IX
Office of Solid Waste Methods Section
Required Uses of SW 846
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Appendix X
Stabilization/Solidification: Is It Always Appropriate?
and
Stabilization/Solidification of Wastes Containing Volatile
Organic Compounds in Commercial Cementitious
Waste Forms
Printed with permission from STP 1123 Stabilization and Solidification of Hazardous,
Radioactive, and Mixed Wastes, 2nd Volume, copyright American Society for Testing and
Materials, 1916 Race Street, Philadelphia, PA 19103
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Appendix XI
Army Waste Classification Guidance for Building
Demolition Debris Containing Lead Based Paint
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Appendix XII
1992 Workshop on Characterizing Heterogeneous
Materials
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Appendix XI11
Improper Hazardous Waste Characterizations:
Financial and Compliance Implications
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Appendix XIV
Region 2 State TCLP Guidances
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Appendix XV
Risk Assessment for Disposal of Solidified/Stabilized
Waste and Contaminated Soil
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Appendix XVI
Barbara Metzger's 1992 Speech on
Environmental Data Use -
Meeting the Customer's Need
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Guidelines for the Conduct of the
Toxicity Characteristic Leaching Procedure
These guidelines have been prepared by Associated Design and Manufacturing Company
for the informational use of environmetal professionals engaged in the conduct of the
Toxicity Characteristic Leaching Procedure (TCLP). They are intended to focus attention on
important data collection activities associated with the TCLP. They are for guidance only and
are not intended to replace sound professional judgment or regulatory requirements.
The guidelines are presented in the form of laboratory worksheets that can be used to
document some of the most important points of the procedure. Each worksheet is supported
by a discussion and recommendations of the data that should be recorded to document of
the TCLP. The discussion is keyed to the worksheet for easy reference.
The paragraph references flj x.x.x.x) given in this document refer to the version of the TCLP
which appeared in the July 29, 1990, Federal Register, p. 26986.
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TCLP Worksheet No. 1
Sample Description
• •••••••• • •• •• • •
• • ••• ••••• ••••••••••
• «•• M*
• MM* • M
• • • • •• •
• • • • • • M •••• • • •• • •• •
• • • • M • ••• •••«•• •
• • • • M • ••• ••• ••••• •«•
• • • • M • ••• •••«••• ••
• • • • W • ••• • ••• • •••• M* •••• •••'
• ••«•••• ••« WW «• •••••• ••«••• ••
1 . The weight percent wet solids is given by
3ight of subsample - weight of filtrate
weight of subsample
/eight of dry waste + filter) - weight c
the equation:
X1
2. The weight percent dry solids is
»f filter y * given by the equation:
weight of subsample
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Discussion and Recommendations
TCLP Worksheet No. 1
Sample Description
This worksheet documents important information regarding the general description of the
sample and the number of phases observed in the sample as received from the field. This
information is used to determine the amount of leaching fluid used to leach solid materials
and the weighting factors used when calculating final analyte concentrations from multi-
phasic samples.
A. Sample Description
Number of phases - The number of phases present in the sample determine how the
TCLP is conducted. Solid materials having no visible liquid phase are extracted as
received from the field and the analyte concentration found in the leachate is the reported
value. Liquid materials having no measurable solids content ( < 0.5 wt. % dry solids) are
defined as the TCLP extract (U 2.1) and are filtered and analyzed directly.
Multi-phase samples must be separated (U 7.1.1.2) and each phase treated individually.
Aqueous phases may be combined with the leachate from solid phase materials before
analysis if the two aqueous materials are compatible (U 7.2.13.2). If the two aqueous
materials are not compatible, than each liquid must be analyzed by the appropriate
methods and the results combined numerically to determine the final reported value (
F-2.14).
A.1. Solid - record the visible presence of a solid material heavier than water. If the
sample contains more than one solid phase ( example, wood chips and sediment
mixed with water) record the information in the laboratory notebook.
A.2. Liquid - record the number of liquid phases observed in the sample according to their
apparent density. It may be impossible to distinguish apparent density if only one
liquid phase is observed and there is no indication on the accompanying chain-of-
custody form (COC). If this is the case, record it as aqueous material and let the
subsequent analytical record show if the liquid is organic after the container is
opened at the appropriate time.
B. Percent of Solid / Liquid Phase(s) - paragraphs 7.1.1 through 7.1.2.3 of the method
describe the procedure to follow for the determination of the percent solids of the
samples. It is also convenient to measure the percent of any non-miscible liquid phases
at this point because the information is required in U 7.2.14.
Laboratory subsampling of the material delivered to the laboratory must be thoroughly
documented. The total contents of the sample container should be considered as "the
sample" and care must be taken to ensure the representativeness of any subsample.
Heterogeneous and multi-phasic materials can be difficult to subsample properly and
frequently require significant judgment on the part of the analyst.
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Discussion - At this point, it is important to review the COC and confirm the number of
containers of each sample provided to the laboratory and the types of analyses requested.
If the analysis of volatile components is requested, the determination of percent solids in
multi-phasic samples must be completed before proceeding to the leaching of the solid
material in the zero headspace extractor (ZHE) to prevent overfilling the ZHE. It is best if a
separate sample has been provided for this purpose flj 6.2). The laboratory should establish
an SOP to address how to proceed if only one container is available.
It is common that when more than one container of multi-phasic materials is received from
the field, each container will show different amounts of each phase. This provides a
challenge to the laboratory which must report the data based on percent phase composition
of the sample. A practical solution is to record the depth (measured from outside the
container) of the layers in the each container after the contents have been allowed to settle
and determine the combined volume of each phase in all the containers. Then measure the
phase composition on a single container (after thorough mixing to obtain a representative
subsample). Combine these two sets of values to determine the correct volume/mass
adjustments on the TCLP results.
The laboratory should also establish an SOP on how to proceed when only a limited amount
of sample is available and the analyses requested exceed the amount of sample provided.
B.1. Weight of filter -- This value must be measured before loading the filter into the filter
holder because the mass of the filter is used in performing the calculation for percent
dry solids.
B.2 Weight of sample aliquote - a representative 100 gram sample (U 7.1.1.5) is
withdrawn from the sample container for filtration. If liquid material is decanted from
the sample before subsampling, its volume/weight must be recorded and factored
into the calculations of percent solids.
Discussion - Many multi-phasic samples are difficult to filter. This is especially true of
oily wastes and sludges. The method directs that any material retained by the filter after
following the instructions is defined as solid waste fl\7.1.18). Experience has shown that
the reproducibility of the percent solids determination with these types of samples is
highly variable. Subsequent steps in the extraction procedure flj 7.2.5 and 7.3.4.2) use
the % solids value to estimate the mass of the original waste used to obtain an
appropriate sized subsample of the solid for extraction.
The method directs that the material retained by the filter be dried at 100 ± 20 °C fl]
7.1.2.2) to determine the percent dry solids. This may not be achievable for organic
multi-phasic materials because of safety considerations and the fact that many organic
liquids boil considerably higher than water and it may be impossible to achieve a
constant weight for successive weighings (± 1%).
The laboratory should establish a standard operating procedure (SOP) addressing these
types of samples. Basically, the laboratory has three choices of how to proceed. It may
• attempt to dry all samples as directed by the method;
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• dry samples containing only water as the liquid phase; and/or
• define the retained material as a dry solid for the purpose of further testing.
This decision may have significant impact on the amount of material selected for leach
testing and on the reported analyte values. The laboratory should consider discussing
this issue with their clients and any regulatory groups to whom the data will be
submitted.
B. 4 Weight percent solids(wet) equals:
weight of subsample - weight of filtrate „ 10Q
weight of subsample
The procedure defines the material retained by the filter as the solid phase of the
waste flf 7.1.1.8). This value is used to calculate the volume of the original multi-
phasic material which must be filtered to yield the proper amount of solid waste for
the extraction procedure.
B.5 Weight percent solids (dry) - the total mass of the filtered solids and the filter are
removed from the filtration apparatus and dried at 100 + 20 °C until a constant weight
is achieved (1f 7.1.2.2). This value is used to calculate the dry solids content of the
waste. Use caution when drying samples that may contain flammable material. It is
important to factor in the tare weight of the filter for samples that have low solids
values.
The weight percent solids (dry) is calculated by the equation:
(weight of dry waste + filter) - weight of filter
weight of subsample
If the weight percent dry solids is > 0.5%, the total waste is defined as a solid waste
and steps must be taken to collect the appropriate weight of solid material for
extraction (If 7.1.2.4).
B.6 Volume of initial aqueous filtrate -- this value is used in 1f 7.2.14 and 7.3.14 in the final
calculation of analyte concentration.
B.7 Volume of initial organic filtrate - this value is used in 1f 7.2.14 and 7.3.14 in the final
calculation of analyte concentration.
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TCLP Worksheet No. 2
Selection of Extraction Fluid
• •• • • •• ••• • •• •• ./ •
••••••• ./ •
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Discussion and Recommendations
TCLP Worksheet No. 2
Selection of Extraction Fluid
for
Metals, Semi-volatile Organic Components, and Pesticides/Herbicides
This worksheet documents the important steps which should be followed to correctly
determine the appropriate extraction fluid for leaching solid wastes for the analysis of metals,
semi-volatile organic components, and pesticides/herbicides. This procedure does not apply
to the determination of volatiles using the zero headspace extractor (ZHE).
Discussion - the Environmental Protection Agency's "worst case" waste disposal model
assumes mismanaged wastes will be co-disposed with municipal solid waste in a 5:95 ratio.
These wastes will be exposed to leaching by the acidic fluids formed in municipal landfills. The
EPA's model further assumes the acid/base characteristics of the waste will be dominated by
the landfill fluids. The TCLP laboratory procedure directs that alkaline wastes be extracted with
a stronger acidic leach fluid than acid or neutral wastes so that the alkaline nature of the waste
will not control the leaching chemistry of the TCLP test. This is in keeping with the waste
disposal model's assumption that the acid fluids in the landfill will dominate leaching chemistry
over time.
The procedure described in If 7.1.4 of the method addresses the determination of the
appropriate extraction fluid. It is a short term test whose results can have a significant impact on
the final analytical results if the wrong extraction fluid is selected. This is especially true for
metals determinations because of their sensitivity to the pH of the leach medium. The following
discussion examines each step of the procedure and points out some sensitive technical points
and how they can affect the results.
^7.1.4.1 Particle size of test material -- The requirement to use 1mm particle size material in
the test recognizes the fact that in a short term reaction between a liquid and a solid, high
surface area is the most important characteristic of the solid. The rate of the reaction is
controlled by the rate of diffusion of the liquid into the pores of the solid so a high surface area
is necessary if the results of a short term test are to be reliable. Therefore, failure to take a
representative subsample of the solid material and perform the necessary particle size
reduction can result in significant bias. This is especially true if the waste contains a wide range
of particle sizes and only the fines are selected for testing.
If 7.1.4.3 Heating of the reaction mixture - The method specifies that the waste/acid slurry is to
be held at 50°C for ten (10) minutes. Care should be taken to heat the sample to 50 °C as
rapidly as possible without overheating. When the sample has completed the ten minute period
at temperature, it should be allowed to cool and the pH determined as soon as possible. The
longer the reaction between the acid solution and the solid waste is allowed to continue, the
more likely that a falsely high pH reading will result. This will result in improper selection of the
more acidic extraction fluid. Failure to reach and hold the required temperature can result in an
artificially low pH reading for the test solution, leading the incorrect selection of the less acidic
extraction fluid.
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C. Extraction Fluid Determination (U 7.1.4)
C.1. Indicate if particle size reduction is required for the sample.
Discussion - the laboratory should consider establishing an SOP to address the particle
size reduction requirements for the TCLP procedure. Most solid samples will not be
received from the field with a particle size of 1mm as required for this step of the
procedure flj 7.1.4.1). Many multi-phasic samples will not be amenable to size reduction
because of the nature of the sample. Samples containing pebbles, rocks, or debris may
be difficult to size reduce if the larger particles are hard. Proper subsampling of the
waste may be difficult if the waste is heterogeneous.
C.2. Sample weight -- check the box if 5.0g of sample is used in the test. Record the
actual weight if a different sized sample is used.
C.3. Volume of water - the volume of water used in the test is dependant on the weight of
sample being tested. If the sample weight (above) is 5g and 96.5 ml_ of water is
added, check the box. If the weight is not 5g, record the volume of water added.
(# of grams X 19.3ml_).
C.4. Initial pH - record the pH of the slurry after a five minute mixing period. Use narrow
range pH indicator paper if organic material is observed floating on the top of the
slurry to avoid damage to pH electrodes.
C.5. Procedure for alkaline wastes - if the initial pH of the slurry is > 5.0, add 3.5 ml_ of 1N
HCI to determine if the alkalinity of the waste is sufficient to require the use of the
stronger acid extraction fluid.
C.6. Neutralization reaction conditions -- the slurry should be heated to 50 °C and held for
ten minutes.The laboratory should consider validating their procedure to confirm
these conditions are met. A bench procedure specifying the hot plate setting (or other
source of heat), the time required to reach the desired temperature, the ten minute
time at temperature, and the time required to return to room temperature should be
established. This will assure the maximum degree of reproducibility in the
determination of the alkaline potential of the wastes tested.
C.7. Secondary pH - record the pH of the slurry after it has completed the cooling cycle.
D. Selection of Extraction Fluid
D. 1. If either the initial pH or the secondary pH is < 5.0, select Extraction Fluid #1 as the
leaching medium.
D.2. If the secondary pH is >5.0, select Extraction Fluid #2 as the leaching medium.
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TCLP Worksheet No. 3
Determination of Extraction Fluid Volume
for
Metals, Semi-Volatile Organic Components and Pesticides/Herbicides
Laboratory Sample No.
Field Sample No.
E. Determination of Sample Size for Leach Testing - the method requires a minimum 1 00 gram
sample size for extraction (If 7.2.5).
1 . particle size reduction? yes/no
2. amount of dry solids (100g min.)
3. amount of multi-phasic sample1
a. weight of material
b. weight of filtrate
c. weight of solid material
F. Determination of Amount of Extraction Fluid - the selection of the correct extraction fluid is
found in Section D, Worksheet No. 2.
1 . for dry solids (20X sample wt.)
2. for multi-phasic samples2
G. Record of Extraction Test ~ the extraction period is specified as 18 ± 2 hours.
1 . extraction start time
2. extraction stop time
3. filtration complete time
4. pH of filtrate
5. volume of filtrate
1. The theoretical
Amount of multi-phasic material = (104)(wf. percent wet solids) amount of multi-
phasic waste
necessary to yield a 100g sample is given by:
2. The amount of extraction fluid needed to extract the solid material from a filtered multi-
phasic waste is given by:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate
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Discussion and Recommendations
TCLP Worksheet No. 3
TCLP Extraction Procedure
for
Metals, Semi-volatile Organic Components, and Pesticides/Herbicides
This worksheet documents the performance of the TCLP extraction procedure for metals,
semi-volatile organic compounds and pesticides/herbicides.
E. Determination of Sample Size for Leaching ~ the specified size of sample for the
leaching test is a minimum of 100g (U 7.2.5). The regulatory control limit for defining if the
waste is hazardous is based on the levels of analytes reported in the leachate based on
this size sample and a twenty to one (20:1) liquid to solid ratio. If the amount of waste
subjected to extraction is not 100g, than the volume of extraction fluid must be adjusted
to preserve the liquid to solid ratio.
E. 1. Amount of dry solids ~ record the weight of dry solids.
E.2. Amount of multi-phasic sample - the amount of multi-phasic waste material
necessary to produce a 100g sample after filtration can be estimated by the equation:
Amount of multi-phasic material = (104)(wf. percent wet solids)
F. Determination of the Amount of Leaching Fluid
F. 1. Dry solids ~ for dry solids containing no filtrable fluids, the calculation of the correct
volume of leaching fluid is straightforward. The amount is equal to twenty (20) times
the mass of solid being leached. Note that the method specifies a 20:1 ratio based on
the weight of extraction fluid required (U 7.2.1.1). If the laboratory elects to use
extraction fluid volume, rigorous adherence to the method requires a one time
specific gravity correction to convert the required weight into the appropriate volume.
F.2. Multi-phasic samples ~ the method says flj 7.2.11) the percent wet solids can be
used to calculate the weight of extraction fluid used to extract the solid waste
resulting from the filtration of a known weight of multi-phasic waste. The equation for
this calculation is:
Amount of extraction fluid = 0.2 (percent wet solids) (weight of waste filtered)
This assumes there is no subsampling error between the original determination of the
weight percent solid phase (wet) and the subsequent selection of a weight of the
multi-phasic waste for filtration and extraction. This is frequently not so. The nature of
many multi-phasic wastes and/or the necessity to use more than one sample
container for the two determinations means that subsamplng error can be significant.
This error can be eliminated if the actual weight of filtered solids is determined at the
time the material is separated for extraction. The equation for this calculation is:
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Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
The actual filtration procedure is detailed in U's 7.2.2 though 7.2.8. Requirements for
sample particle size reduction are given in 1J7.1.3 and 7.2.10. These should be
followed as closely as the nature of the samples will allow and all departures from the
instructions should be described in the laboratory notebook.
G. Record of the TCLP Extraction Test - the period of the extraction test is given as
18 ± 2 hours (U 7.2.12). Extraction should be started so the resulting slurry can be filtered
as soon as possible after the 18 hours has past. The filtration effectively stops the
extraction process. If the extraction fluid is left in contact with the waste for longer than
the specified period (overnight or over the weekend), the extraction process continues
and may lead to elevated levels of contaminants.
G.1. Extraction start time -- record the time and date the extraction begins.
G.2. Extraction stop time -- record the time and date the extraction is completed.
G.3. Filtration completion time -- record the time and date the filtration is complete.
G.4. pH of filtrate - while not required by the method, this is a good indicator of test
performance when performing duplicate laboratory analysis or analyzing field
replicates. It can be a reliable measure of sample heterogeneity.
G.5. Volume of filtrate - record the total volume of filtrate collected from the sample. This
value is required to make the appropriate volume corrections when reporting the
results from multi-phasic wastes.
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TCLP Worksheet No. 4
Zero Headspace Extraction (ZHE)
Laboratory Sample No.
Field Sample No.
H. Determination of Sample Size for Leach Testing - maximum 25 grams
1. amount of dry solids
2. amount of multi-phasic sample1
I. Determination of Amount of Extraction Fluid No. 1
1 . for dry solids (20X sample wt.)
2. for multi-phasic samples2
a. weight of material
b. weight of filtrate
c. weight of solid material
J. Record of ZHE Extraction Test - the extraction period is as 18 ± 2 hours (If 7.3.12.3).
1 . extraction start time
2. starting pressure
3. extraction stop time
4. / if positive pressure
5. filtration completion time
6. pH of filtrate
7. volume of filtrate
1. Determination of amount of multi-phasic sample for extraction:
a. if weight percent dry solids is < 5% (from Worksheet No. 1, B. 5), the waste is filtered
and the filtrate is defined as the TCLP leachate (U 7.3.4).
b. if weight percent dry solids is > 5% (from Worksheet No. 1, B. 5), the amount of multi-
phasic material which should be filtered to yield a 25 gram sample is given by:
Amount of multi-phasic material = (2.5 x 103)(wf. percent dry solids)
2. The amount of extraction fluid #1 needed to extract the solid material from the filtered
multi-phasic waste (H.2) is given by:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
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Discussion and Recommendations
TCLP Worksheet No. 4
Zero Headspace Extraction
for
Determination of Volatile Organic Compounds
This worksheet describes the important information regarding the conduct of the zero
headspace extraction (ZHE) of solid waste materials for volatile organic compounds.
Samples containing < 5.0 % dry solids are NOT subjected to ZHE leaching procedure. They
are filtered in the ZHE device and the resulting filtrate is defined as the TCLP leachate and
analyzed directly flj 7.3.4).
H. Determination of Sample Size for Leach Testing -- the maximum sample size for this test
is limited by the volume of the ZHE to approximately 25g (U 7.3).
H.1. Amount of dry solids -- record the weight of dry solids charged to the ZHE but do not
exceed 25g.
H.2. Amount of multi-phasic sample - the amount of multi-phasic waste material
necessary to produce a 25g sample after filtration can be estimated by the equation:
Amount of multi-phasic material = (2.5 x 103)(wf. percent wet solids)
I. Determination of the Amount of Leaching Fluid #1
1.1. Dry solids ~ for dry solids containing no filterable fluids, the calculation of the correct
volume of leaching fluid is straightforward. The amount is equal to twenty (20) times
the mass of solid being leached. Note that the method specifies a 20:1 ratio based on
the weight of extraction fluid required (U 7.3.11). If the laboratory elects to use
extraction fluid volume, rigorous adherence to the method requires a one time
specific gravity correction to convert the required weight into the appropriate volume.
1.2. Multi-phasic samples ~ the method indicates flj 7.3.11) that the percent wet solids
can be used to calculate the weight of extraction fluid used to extract the solid waste
resulting from the filtration of a known weight of multi-phasic waste. The equation for
this calculation is:
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Amount of extraction fluid = 20 (percent wet solids) (wei^ht of waste filtered)
100
This assumes there is no subsampling error between the original determination of the
weight percent solid phase (wet) and the subsequent selection of a weight of the
multi-phasic waste for filtration and extraction. This is frequently not the case. The
nature of many multi-phasic wastes and/or the necessity to use more than one
sample container for the two determinations means that subsamplng error can be
significant. This error can be eliminated if the actual weight of filtered solids is
determined at the time the material is separated for extraction. The equation for this
calculation is:
Amount of extraction fluid = 20 (weight of material filtered - weight of filtrate)
The actual filtration procedure is detailed in U's 7.3.7 though 7.3.9. Requirements for
sample particle size reduction are given in U 7.3.5 and 7.3.6. These should be
followed as closely as the nature of the samples will allow and all departures from the
instructions should be described in the laboratory notebook.
The addition of extraction fluid #1 to the ZHE is described in detail in U 7.3.12.
J. Record of the ZHE Extraction Test ~ the period of the extraction test is given as
18 ± 2 hours (U 7.3.12.3). Extraction should be started so the resulting slurry can be
filtered as soon as possible after the 18 hours has past. The filtration effectively stops the
extraction process. If the extraction fluid is left in contact with the waste for longer than
the specified extraction period (overnight or over the weekend), the extraction process
continues and may lead to elevated levels of contaminants.
J.1. Extraction start time ~ record the time and date the extraction begins.
J.2. Starting pressure ~ the method requires the ZHE be pressurized to approximately 10
psi at the beginning of the test.
J.3. Extraction stop time ~ record the time and date the extraction is completed.
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J.4. Positive final pressure - the method requires that the ZHE retain positive pressure at
the conclusion of the extraction period or the test must be repeated flj 7.3.13). Loss
of pressure is an indication the ZHE leaked during the test resulting in a loss of
volatile components.
J.5. Filtration completion time -- record the time and date the filtration is complete.
J.6. pH of filtrate - while not required by the method, this is a good indicator of test
performance when performing duplicate laboratory analysis or analyzing field
replicates. It can be a reliable measure of sample heterogeneity.
J.7. Volume of filtrate - record the total volume of filtrate collected from the sample. This
value is required to make the appropriate volume corrections when reporting the
results from multi-phasic wastes. The filtration of oily wastes may be especially
difficult.
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