oEPA
United States
Environmental Protection
Agency
Office of
Solid Waste and
Emergency Response
DIRECTIVE NUMBERr9445.04(85)
TITLE: Notes on RCRA Methods and QA Activities
APPROVAL DATE: 6-1-85
EFFECTIVE DATE: 6-i-ss
ORIGINATING OFFICE: office of solid waste
Q FINAL
D DRAFT
STATUS:
[
REFERENCE (other documents):
A- Pending OMB approval
[ 1 B- Pending AA-OSWER approval
[ ] C- For review S/or consent
[ ] D- In development or circulating
headquarters
OSWER OSWER OSWER
VE DIRECTIVE DIRECTIVE Dl
-------
FART 261 - APPENDICES DOC: 9445.04(85)
Key Words: Analytic Methods, QA/QC, Ground-Water Monitoring, Dioxin,
Trial Burn
Regulations:
Subject: - Notes on RCRA Methods and QA Activities
Addressee: N/A
Originator: David Friedman, Manager, Methods Program
Source Doc: #9445.04(85)
Date: 6-1-85
Summary:
The memo adress the following subjects:
o Metal determination in ground water
o Dioxin Method 8280
o Performance audits on gas samplers
o Validation of Method 3540
o Reactivity test methods
o Symposium on solid waste
o Testing and quality assurance
-------
MEMORANDUM 17
9445.04 (85)
DATE:
SUBJECTS
PROM 2
TO*
June 1985
Notes on RCRA Methods and QA Activities
David Friedman* Manager
Methods Program (HH-562B)
Addressees
Today's memo will cover the following subjects:
o Metal Determination in Ground Hater
o Dioxin Method 8280
o Performance Audits on Gas Samplers '
o Validation of Method 3540
o Reactivity Test Methods
o Symposium on Solid Haste Testing and Quality Assurance
Thank you for past comments and suggestions.
Metal Determination in Groundwater
The forthcoming publications, "Ground Hater Technical
Enforcement Document" (OtfPB) and the Third Edition of SW-846,
will pvotride^scpatoer detail on how metals are to be determined in
ground wafc«ffc- !?&• following policy will be implemented in both
documents*. ,IL ,.,,-
o- All.-ground water samples are to be analyzed for total
recoverable metals (unfiltered, mild digestion) and
dissolved metals (filtered, mild digestion) as defined in
the BPA publication "Methods for Chemical Analysis of
Water and Waste* (BPA-600/4-79-020), Section 200 Metals,
paragraphs 3.7 and 3.4. Total recoverable metals and
-1-
-------
dissolved metals are to be Determined by the methods
given in the same publication in Section 200 Metals.
paragraphs 4.1,4 and 4.1.1. (The digestion given in Mote
3 of 4,1.1 is always to be used for ground water samples.)
o Organic determinations are to be made only on ground
water samples that have not been filtered.
o An on-site filtration method will be developed and
evaluated before inclusion in SW-846.
Dioxin Method 8280
The single laboratory evaluation of Method 8280 for analysis
of halogenated dibenxo-p-dioxina and dibenzofurans has been
completed. The method consists of extraction, base and acid
washes, aluaina colusn chrcartography, reverse phase BPLC, carbon
column chromatography and quantitation by high resolution gas
chr cartography low resolution mass spectroreetry (HRGC/LJWS) (see
Table X). Analyses, concentrations and performance data are
given in Table II. Detection limits derived from the single lab
study are given in Table III. These may be higher than lowest
possible detection limits because calculations are based on high
natural and spiked dioxin concentrations. The B*9L-Las Vegas
laboratory is currently investigating method modification* aimed
at lowering the detection limits and is preparing for a multi-
laboratory evaluation of the current method.
Availability of PPB Haaardoua Organic Cylinder Gases for
Performance Audits
In order to minimise the chance of poor data being collected
when performing trial burn* and other combustion process,monitoring,
the BHSL-ftTP laboratory has prepared several audit cylinders for
use in performing performance audits of 3W-846 sampling methods
1.2.1.8 (VOST) and 1.2.1,13 (MM3). These multiconponent organic
cylinder gases have been successfully used in audits during RCRA
hazardous waste- trial burns.
As a rsantlt of the success with these cylinders, OSW believes
it is prudent.-f0r all persons performing such sampling to use a
cylinder audit during each sampling episode. If such a level of
Quality Assurance cannot be performed, then cylinder audits should
be performed during all trial burns. The cylinder gas audit can
be< used for all volatile organic sampling that uses either the
VOST or bag techniques. The audit adds an important ingredient
now missing froa such trial burns—assessment of sampling
accuracy. Currently, SPA and State personnel who require trial
-2-
-------
TABLS I. FLOW 3H8BT FOR METHOD 8280 DIOXIN'ANALYSIS
1 - lOg Sample
extract
100 ml
MeOHtPet. Ether,H20 (1,4,5) used
for Ash; Toluene used for Activated
Carbon; MeOH,H2O (7,3) used for soil,
Aqueous
Discard
Organic
Wash with
20% KOH
1
Aqueous
I
Discard
I
Organic
Mash with
cone* H23O4
Aqueous
I
Diacard
I
Organic
Alumina Column (3q)
Clean up
Fraction 1 (M*Cl2iH«xane)
<20i80)
Diacard
Fraction 2 (MeCl2
-------
TABLE II. PRECISION DATA POR REVISED METHOD 8280
Compound
Matrix
Analyte Level
Native +
Spike(ng/g)
N
Mean
Percent Percent
Recovery RSD
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
—
2,3,7,8-TCDD (C-13)
1,2,7,8-TCDP
1,2,3,7,8-PeCDF
1,2,3,4,7,8-HxCDF
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
.still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
5.0
25.0
125
13.9
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
1 X 104
—
—
5.0
25.0
125
5.0
2500
5.0
25.0
125
3.7
2500
5.0
25.0
125
46
178,000
—
25.0
133
17.6
2500
4
4
4
4
2
4
4
4
2
2
4
4
4
2
2
4
4
8
—
-
4
4
6
4
3
4
4
4
4
2
4
4
4
2
2
-
. 4
4
4
2
58.4
62.2
79.2
102.4
81.8
61.7
68.4
81.5
104.9
84.0
46.8
65.0
81.9
125.4
89.1
ND
ND
—
— —
—
64.9
78.8
78.6
88.6
69.7
65.4
71.1
80.4
90.4
104.5
57.4
64.4
84.8
105.8
—
54.2
68.5
82.2
91.0
92.9
3.36
8.92
6.93
10.3
__
23.2
10.8
5.28
—
-._
28.9"^
12.9
9.0
— —
—
—
__
. —
— —
— .
7.58
9.14
3.42
6.74
7.47
6.91
8.40
3.08
11.1
— —
5.18
6.77
9.74
—
— -
—
10.0
5.29
8.71
—
-4-
-------
TABLE III. DETECTION LIMITS (ppb) FOR RCRA METHOD 8280
Analyte
Class Clay Soil Ply Ash Still Bottom Sludge
TCDD
TDCP
PeCOD
PeCDF
UxCDD
HxCDP
1.0
0.5
1.5
1.0
2.0
1.5
5.0
2.5
7.5
5.0
10
7.5
1.0
0.5
1.5
1.0
2.0
1.5
500
250
750
500
1000
750
25
12
38
25
50
38
-5-
-------
vurns tor POHC have little means of knowing the accuracy of
measurements./ Requiring permit applicants to conduct cylinder
audits daring-the trial burn adds an important weapon to the
QA arsenal* XISN strongly recommends instituting this requirement.
These; grinders are available, at no cost, from the BMSL-
RTP laboratdry. Bach audit cylinder contains 5 to 9 hazardous
organic*. Audit cylinders are available in two concentration
ranges. The concentration of each hazardous organic in the low
audit cylinders is between 7 and 90 ppb. The concentration of
each hazardous organic in the high audit cylinders is between 90
and 430 ppb. Groups I and II cylinders are currently available
for audits. Group III cylinders will be available in the Fall,
1985. Groups I, II and III cylinders contain the following
hazardous organiess
Group I Cylinders
Group II Cylinders
Carbon tetrachloride Trichloroethylene
Chloroform
Perchloroethylene
Vinyl chloride
Benzene
1,2-Dichloroethane
1,2-Dibromoethane
Acetonitrile
Trichlorofluoromethane
(Preon-11)
Dichlorodifluoromethane
(Preon-12)
Bromoethane
Methyl ethyl ketone
1,1,1-Trichloroethane
Group III Cylinders
Pyridine
Vinylidene chloride
1,1,2-Trichloro-l,2,2-
trifluoroethane
(Preon-113)
1,2-Dichloro-l ,1,2,2-
tetrafluoroethane
(Preon-114)
Acetone
1,4-Oioxane
Toluene
Chlorobenzene
-6-
-------
All audit cylinders are.periodically analyzed to assure
»d»r concentrations have remained stable. Also", all
stability analyses in Appendix A include quality control analyses
or-ppb hasardAis organic gas standards prepared by the National
Bureau of standards for EMSL-RTP/QAD.
i.33 • ••' '
Audit C3pl4»n4*rs may be obtained by contacting:
Robert L. Lanpe
U3BPA, Environmental Monitoring Systems Laboratory
Quality Assurance Division (MD-77B)
Research Triangle Park, North Carolina 27711
Telephonoi Commercial (919) 541-4531 or PTS 629-4531
Validation of Method 3540
The development and evaluation of fortification/homogenization
procedures for preparing uniform distributions of analytes in
diatomaceous earth showed no appreciable differences between
fortification solvents, between mechanisms of homogenization,
or between duration of homogenization. Uniformity of distribution
o£ analytea in the diatomaceous earth was essentially independent
o£ these parameters. Consequently, the most facile approach
(i.e. fortifying using methylene chloride followed by tumbling
for 30 min) was applied to subsequent experiments.
The evaluation of the Soxhlet Extraction Procedure (Method 3540,
SW-846) using reagent diatomaceous earth demonstrated that this
procedure provides accurate and precise measurements on nonvolatile
components. Recoveries of such species from fortified diatomaceous
earth was approximately 85 percent, with relative standard deviations
of less than 11 percent. Recoveries of the three volatile analytes,
toluene, p-xylene, and o-xylene were considerably lower (-40%).
Loss of these volatile compounds during evaporation of gross
solvent in the fortification step was considered the most probable
cause of this poor performance. Extraction and K-D evaporation
were also minor contributors. No effect of using diatomaceous
earth from.different sources on recovery of target analytes was
noted.
".••-.- Precision of determination of unknown components of diatomaceous
earth' fortifled with actual pesticide industry waste was somewhat
lower (approximately 27% RSO). This observation was attributed
to the difficulty of homogenizing a mixture of two solid materials.
Reactivity Test Methods
Development of reactivity test methods for those waste
materials which are capable of detonation is underway. In an
interagency agreement with the Bureau of Mines Laboratory (BOM)
in Pittsburgh, Pennsylvania, OSW sponsored a study that evaluated
-7-
-------
the U.S. Card Gap Test and the U.S. Internal Ignition Teat as
tools for determining if a given waste is an explosive that could
undergo detonation under reasonable mismanagement conditions.
Samples of sludge from several explosives processing waste treat-
ment facilities were collected and analyzed as well as a series
of standard explosives for calibration use. Because of the
inconclusive nature of the results of the BOM work, further
evaluation is needed before any decision is reached as to the
applicability of these tests to RCRA wastes.
In the interim, OSW has supported the use of a battery of
tests to determine reactivity due to explosive properties. This
battery is outlined in a test plan submitted by the U.S. Army.
Please contact Florence Richardson (PTS 382-4770) for
additional information on this aspect of reactivity.
Symposium on Solid Waste Testing and Quality Assurance
The agenda of the Symposium on RCRA Test Methods and
Quality Assurance, scheduled for July 23-26, 1985 at the Vista
International Hotel (Washington, DC) is as follows*
United States
Environmental Protection Agency
Symposium
on
Solid Waste Testing
and
Quality Assurance
Tuesday, July 23
6sOO - 8*00 p.m. - Registration
Wednesday, July 24 .
\ N
7:00 — 8s30 a.m* - Registration and Continental Breakfast
8s30 - 9s00 ««•« - Opening Session
Opening presentation will be given by Dr.
John B. Skinner, Director, Office of Solid
Waste, U.S. EPA
-8-
-------
9sOO - 9:30 a.m.
9s30 - Noon
9i30 - >Qt30 a.m.
10:30 - 10:45 a.m.
H45 - 12:00 Noon
- Conference Overview
Overview will be presented by David Friedman,
Manager, Methods Program, Office of Solid
Waste, U.S. EPA
- Analysis of Inorganics
Chairperson: Douglas Gillard, Methods Program,
Office of Solid Waste, U.S. EPA
- "Comparative Performances of Inductively
Coupled Plasma (ICP) and Atomic Absorption
Spectroscopy (AAS)"
Speakers: Robert Stevens, Chief, Hazardous
Materials Laboratory, California
Department of Health Service, 2151
Berkeley Way, Berkeley, California
94720
Thomas A. Hinners, Hazardous Waste
Methods Evaluation Branch, U.S.
EPA - EMSL, P.Q. Box 15027, Las
Vegas, Nevada 89114
- Coffee Break
'Comparative Performances of SW—846
Extraction/Digestion Procedures for
Determining Metals in Industrial Wastes*
Speaker: Mirtha Umana, Analytical and
Chemical Sciences, Research
Triangle Institute, Box-12194,
Research Triangle Park, North
Carolina 27709
•Interference Studies in Hydride Generation
Atonic Absorption and Plasma Emission
Spectroraetry"
Speaker: J. Wilson Hershey
Lancaster Laboratories, Inc,
Lancaster, PA 17601
•
•Employment of Alkaline Digestion Procedures
for Determination of Metals in Industrial
Wastes*
Speaker: Joseph Lowry, Chief, Inorganic
Analytical Section, EPA - NEIC,
Box 25227, Denver Federal Center,
Denver, Colorado 80225
-9-
-------
Noon - 1x30 p.m.
1:30 - 5:00 jpr;«.
1:30 - 2x00 p.m.
2:00 - 2x30 p.
2x30 - 3x00 p.m.
Lunch
Methods for Identifying Hazardous Wastes
Chairperson: Todd A. Kimraell, Methods
Program, Office of Solid
Waste (WH-562B), U.S. EPA
•Performance of an Ignitable Solids Methods
in Characterizing Hazardous Wastes*
Speaker: Florence Richardson, Office of
Solid Waste, U.S. EPA (WH-562B),
Washington, DC 20460
•Reactive Sulfidea and Cyanides: Test
Methods and Regulatory Threshold Setting
Models"
Speaker: Paul H. Friedman, Studies and
Methods Branch, Office of Solid
Waste (WH-562B), U.S. EPA,
Washington, DC 20460
•Mobility of Toxic-Compounds in Hazardous
Wastesx Comparison of Three Test Methods
to a Lysimeter Model"
Speaker: C. w. Francis, Soil Scientist,
Building 1505, Oak Ridge National
Laboratory, Box X, Oak Ridge,
Tennessee 37830
3:00- 3x30
3:30 - 4x00 p.m.
4x00 - 5xOO p.m.
- Coffee Break
- "Application of the Toxicity Characteristic
Leaching Procedure (TCLP) to Industrial
Wastesx A Single Laboratory Evaluation"
Speakerx L. R. Williams, U.S. EPA - EMSL,
Box 15027, Las Vegas, Nevada 89114
- Panel Discussion: Overview of the EPA
Program to Define the Characteristics of
Hazardous Wastes.
Participants: Session Speakers
David Friedman, OSW, EPA
C. W. Francis, ORNL
"Oak Ridge, TN
-10-
-------
6:00 - 7:30 p.m.
Thursday, July 25
7:00 - 8:00 a.m.
8:00 - Noon
8:00 - 9:00 a.m.
9:00 - 10:00 a.m.
10:00 - 10sl5 a.m.
10:15 - 10:45 a.m.
- Reception for Symposium Speak*,,
- Continental Breakfast
- Analyzing for Organics
and Attendees
Chairperson:
Sessions:
Paul H. Friedman, Methods
Program, Office of Solid
Waste, U.S. EPA
'Application of (SW-846) Methods to Groundwater
Monitoring Programs: Experiences of Two
Contract Laboratories"
Speakers:
Denis Lin, ETC, 284 Raritan Center
Parkway, CN 3154, Edison, New
Jersey 08818
Mark Carter, Rocky Mountain
Analytical Laboratory, 5530
Marshall Street, Arvada, Colorado
80002
"The Use of (SW-846) Cleanup and Mass Spec-
troscopy Methods to Identify and Quantify
Compounds in Complex Industrial Wastes:
Petroleum Industry Case Histories"
Speakers:
Alice Boomhower, Radian Corporation,
7655 Old Springhouse Road, McLean
VA 22102
John Logsdon, Rocky Mountain Analy-
tical Laboratory, 5530 Marshall
Street, Arvada, Colorado 80002
Coffee Break
•Development of Groundwater Screening
Procedures for Use in Monitoring Programs:
Objectives and Experiment Progress at
Battelle Columbus Laboratories"
-11-
-------
Speaker: S. V. Lucas • _.
Battelle Columbus Laboratories
505 King Street
Columbus, OH 43201
10*45 - 11*30 a.m. - EPA and Industry Panel Discussion: The Need
for Standard Laboratory Procedures and EPA's
•Methods for Evaluating Solid Wastes" (SW-846)
Participants: Session Speakers
Al Verstuyft, Chevron Oil Co.
Ill30 - 1:00 p.m. - Lunch
1:00 - 4:30 p.m. - Sampling Under RCRA
Chairperson: Martin Meyers/ Methods Program/
Office of Solid Waste/ U.S. EPA
Sessions:
1:00 - 1:30 p.m. - "Volatile Organic Sampling Trains for
Hazardous Waste Incinerators: Laboratory
Validation"
Speaker: Thomas Loganr U.S. EPA/ Research
Triangle Park, North Carolina 27711
1:30 - 2:00 p.m. - "Practical Consideration of RCRA Program
Sampling Methods and Techniques at Groundwater
Test Wells"
Speaker: Douglas Richardson/ Geo-Research/
2001 Wisconsin Avenue/ NW/ Suite 200,
Washington/ DC 20007
2x00 - 2:30 p.m. - "Groundwater Sampling and Analysis in the
Enforcement of RCRA Compliance Criteria"
, Speakers Roy Murphy, U.S. EPA (WH-527)
401 M Street/ S.W., Washington,
DC 20460
2:30 - 2s45 p.m. - Coffee Break
2:45 - 3il5 p.m. - "Practical Statistical Considerations in
Designing a Sampling Plan*
Speaker: John Warren, U.S. EPA (PM-223)
401 M Street, SW, Washington/
DC 20460
-12-
-------
3:15 - 3:45 p.ra«
3:45 - 4:15 p.au
4:15 - 4:30 p.m.
- "Design and Implementation "of Sampling Plans
for RCRA Listing and Delisting Programs"
Speaker: John Maney, Vice President, ERGO
205 Alewife Brootc Parkway, Cambridge,
Massachusetts 01238
- "Sampling Techniques for Risk Management: A
Dioxin Case History"
Speaker: Mark Haulenbeek, Raritan Arsenal,
Edison, NJ o8837
- Discussion
7:30 - 9:30 p.m.
"Evaluation of Laboratories Performing
Analyses for the RCRA Program"
Speaker: Alexis Taylor, Technology
Applications, 5201 Leesburg Pike,
Suite aOO, Palls Church, Virginia'
22041
Test Method Support for Enforcement Programs:
Current Applications, Problems, and Experiences
(Panel workshop for BPA and state agency
attendees only)
Chairperson: Michael Barclay, Office of Wast*
Program Enforcement, U.S. BPA
Participants: Ren Jennings, OWPB, EPA
Roy Murphy, GWTP, EPA
Friday, July 26
7:00 - 8:00 a.m.
8:00 - Noon
Continental Breakfast
Quality Assurance Issues
Chairperson: Florence Richardson, Quality
Assurance Officer, Office of
Solid Waste, U.S. BPA
-13-
-------
'xOO - 8:30 a.a*
8t30 - 9:00 a.m.
9:00 - 9:45 a.m.
9:45 - lOsOO
Sessions:
•Documenting the Equivalency of Proposed
Methods to Approved Test Methods for
Evaluating Solid Waste"
Speaker: Llewellyn R. Williams, EPA - EMSL,.
P. O. Box 15027r Las Vegas, Nevada
89114
"Gauging the Information Content of Analytical
Data: Optimizing Quality Control Information"
Speaker: R. Mitchum, Director, QAD/ORD, EPA-
EMSL, Box 15027, Las Vegas, Nevada
89114
•Laboratory Certification Under the Voluntary
Laboratory Certification Program"
Speaker: Peter linger. National Bureau of
Standards, ADMIN A-531, Gaithersbufg,
Maryland 20899
Discussion
Coffee Break
10:00 - 10:30 a.m.
10t30 - Noon
"Controlling and Coping With Unwanted Variance
in Ground Water Monitoring Data: Quality
Control and Statistics"
Speaker: Burnell Vincent, Office of Solid
Waste (WH-565B), U.S. EPA
401 M St., SW
Washington, DC 20460
•Sources and Means of Obtaining Compounds for
the Quality Analysis Materials Bank"
Speaker: Edward Kantor, EPA - EMSL
P. O. Box 15027
Las Vegas, Nevada 89114
Group Discussion: Analytical Structures and
the Regulated Community: What Actions Can
EPA Take to Encourage Commercial Availability
of Analytical Standards
-14-
-------
Cfcaicpcrmr Joiin Vtat«r, W*L. o.»£: tro
2€ 1te»t 8t. Clair StrMt
^ Ohio 4526S
BUL, o.a. era
««l Bolg»r» foxboro/Analabe
J«r»«y Dtr
------- |