unnea aiaies
Environmental Protection
Agency
Research and Development
tnvironmentai Monitoring
Systems Laboratory
P.O. Box 15027
Las Vegas NV 89114-5027
January i aati
Annual Report
Quality Assurance
Support Laboratory
prepared for the
Office of Emergency
and Remedial Responce
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ANNUAL REPORT
QUALITY ASSURANCE SUPPORT LABORATORY
by
D. M. Schoengold
Quality Assurance Support Laboratory
Environmental Research Center
University of Nevada, Las Vegas
Las Vegas, Nevada 89154
Cooperative Agreement
CR 809-706-01-3
Project Officer
J. G. Pearson
Quality Assurance Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89114
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89114
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NOTICE
Although the research described in this report has been
funded wholly or in part by the U. S. Environmental Protection
Agency through Cooperative Agreement CR 809-706-01-3 to the
University of Nevada, Las Vegas, Nevada, it has not been
subjected to Agency policy review and therefore does not
necessarily reflect the views of the Agency. Mention of trade
names or commercial products does not constitute endorsement or
recommendation for use.
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CONTENTS
Figures iv
Tables v
1. Introduction 1
2. QASL Peer Review 2
3. Staffing 4
4. Laboratory Design and Construction 6
5. instrumentation 7
6. Containment Laboratory 9
7. Performance Evaluation Samples - Inorganic ... 10
8. Performance Evaluation Samples - Organic .... 11
9. Laboratory Evaluation and Protocol
Caucus Trips ..... 13
10. Papers and Presentations . 14
11. Inorganic Protocol Development and Support ... 15
Method detection limit (MDL)
procedure evaluation 15
New inorganic quality control materials . . 16
Municipal sludge 17
Interference check solution ... 18
Protocol chemistry evaluation ....... 18
12. Organic Protocol Development and Support .... 19
13. Inorganic - Preparation of Standard
Reference Materials 20
14. Dioxin Program Support . 21
Preparation of performance evaluation
materials 21
Hyde Park Consent Decree support 22
IFB program support 23
Analysis of EPA-supplied calibration
standards 23
Protocol development 23
15. Support to EMSL-LV Containment Facility .... 25
16. University Related Work 27
Appendix
A. Figures and Tables 28
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FIGURES
Number Page
A-l ICP standard deviation versus sample
concentration 28
A-2 Comparison of actual and measured concentrations
of arsenic across ICP chatter region 29
A-3 Comparison of actual and measured concentrations
of lead across ICP chatter region 30
A-4 Hyde Park soil HP001 total ion chromatogram ... 31
A-5 Hyde Park soil HP002 total ion chromatogram ... 32
A-6 Hyde Park soil HP003 total ion chromatogram ... 33
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TABLES
Number Paqe
A-l Fiscal Year 1984 Inorganic Performance
Evaluation and Preaward Samples 34
A-2 Fiscal Year 1984 Organic Performance
Evaluation Samples . 35
A-3 Results for Fiscal Year 1984 Organic
Performance Evaluation Sample (QB4) 36
A-4 Organic Fiscal Year 1984 QB4 Surrogate
Recovery Results 37
A-5 Matrix Spike Recovery Results for Fiscal Year
1984 Organic QB4 • 38
A-6 CLP On-Site Laboratory Evaluations Conducted ... 39
A-7 CLP Caucuses Attended . 39
A-8 Papers and Presentations • 40
A-9 Municipal Digested Sludge Inorganic Check Sample
Standard Versus Modified Procedure Results ... 41
A-10 ICP Interference Check Solution. Stability
Studies and Final Analyses . 42
A-ll Comparison of Inorganic FY84 QB3 Sample Using
Old and Proposed New Protocols 43
A-12 Analysis of Sized Cuts of Ruston Soil 44
A-l3 Statistical Summary for >75 Micrometer
Ruston Soil 45
A-l4 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample 2)13) ........ 46
A-l5 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample E17) . 47
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A-16 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample Z18) 48
A-17 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample £20) 49
A-18 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample I 25) 50
A-19 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample £26) 52
A-20 Inventory and Recipients of TCDD Performance
Evaluation Samples, (Sample Z31) 54
A-21 Recipients of TCDD Performance Evaluation
Samples 5 5
A-22 Typical Analytical Data for 2,3,7,8-TCDD
Performance Evaluation Samples ......... 57
A-23 Hyde Park Soil Hexachlorobenzene
Homogeneity Data 58
A-24 Hyde Park Soil Target Compound Quantification ... 59
A-25 Recipients of Dioxin Preaward Samples 60
A-26 TCDD Calibration Standards I through V 61
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SECTION 1
INTRODUCTION
The Environmental Research Center of the University of
Nevada has been cooperating with the Environmental Protection
Agency (Environmental Monitoring Systems Laboratory - Las
Vegas) in the operation of a Quality Assurance Support
Laboratory (QASL) in support of the Agency's Hazardous
Substances Program. The specific objectives of the laboratory
are to provide the EMSL-LV with an independent quality
assurance (QA) referee laboratory to support the Superfund
Contract Laboratory Program (CLP) and to provide an expanded
capability to develop/evaluate new analytical protocols for the
hazardous waste program implemented under Superfund legislation.
The University also holds as an objective the development of
both graduate and undergraduate academic programs in analytical
methods and instrumentation.
The program was initiated at the Environmental Research
Center on November 1, 1981 with the initial objectives of
designing, constructing and furnishing the laboratory
(approximately 5400 sq. ft.) in a University-supplied facility.
The laboratory was dedicated on November 15, 1982 and has been
in operation since that date, although certain instruments took
somewhat longer to become fully operational.
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SECTION 2
QASL PEER REVIEW
As part of the cooperative agreement, a peer review of the
laboratory was conducted in May, 198 4 , by a team of three
senior scientists selected by the EPA. The members of the team
were Dr. F. A. Long (Cornell University), Dr. D. J. Northington
(West Coast Analytical Services, Inc.), and Dr. L. Friedman
(Brookhaven National Laboratory). The report of the team was
quite positive. Specific conclusions and recommendations are
listed below:
1. The laboratory serves a very useful function to the
CLP, appears to be a smooth running operation and has a
long term viability.
2. The staff and equipment in the laboratory is
excellent, however, the level of staffing is austere
and could be severely hurt by loss of senior staff
members. Additional laboratory technicians would be very
useful. Also, the hiring of young postdoctoral students
would enhance the capabilities of the QASL.
3. There should be a closer University-laboratory
relationship. The University should have a senior staff
member working in the QASL with independent, outside
funding and access to laboratory equipment. Also,
senior laboratory staff should be appointed to adjunct
professor positions at the University with teaching
or research responsibilities within the University
community.
4. Laboratory responsibilities are too limited and
should be expanded to permit independent study of
protocols beyond the direct support of the CLP.
Development of new protocols should also be a laboratory
responsibility.
As a result of the peer panel recommendations, the
laboratory has added a senior research position to its staff
and is currently recruiting to fill that vacancy. This Ph.D
level, High Resolution Mass Spectrometer (HRMS) qualified
chemist will serve as the principal in investigating protocol
failings or inconsistencies (as reported out of the caucuses
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held by the Agency or noted by other investigators) with the
objective of developing specific enhancements to the methods.
In addition, a junior chemist has already been added; in
this case to provide analytical support to the F. C. Hart
operation (to be discussed in more detail later) at EMSL-LV.
Some of the recommendations dealing with intensified
interactions with University elements are impossible to
implement because of legal restrictions on expenditures of
Superfund money and/or because of insufficient QASL staff to
handle currently assigned tasks and the suggested new ones.
The QASL is continuing, however, in its efforts to enhance
University-laboratory relations through QASL staff involvement
in teaching University courses and in the proposed Master of
Science in Environmental Chemistry program that is currently
undergoing review within the University system.
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SECTION 3
STAFFING
Staffing changes during this past year included the loss
of two senior members and the addition of several new chemists.
Dr. M. Khare, the organic section leader, left to join Rockwell
Analytical and Dr. V. Hodge left the laboratory to rejoin
Scripps Institute of Oceanography in San Diego.
Dr. A. Lange, who replaced Dr. Khare, was formerly manager
of the analytical section of the State Hygiene Laboratory in
Iowa City, Iowa. Dr. Lange has extensive experience in
environmental analyses, chromatography and in Gas
Chr oma t og raphy/Mass Spectroscopy (GC/MS). He also has
extensive experience as an expert witness resulting from his
previous positions in Iowa and elsewhere.
Dr. L. Morgenthaler, who replaced Dr. Hodge, was formerly
with Bausch and Lomb's ARL Division where he headed the ICP
Applications Laboratory. ARL is the manufacturer of the 35000
Inductively Coupled Argon Plasma Emission Spectrometer (ICP)
instrument in the QASL so the special expertise he obtained at
ARL is especially useful. Besides operating experience, he is
knowledgeable in ICP software and instrument design. Dr.
Morgenthaler also gained experience in atomic absorption (AA)
spectroscopy when he worked at Perkin Elmer Corporation, the
manufacturer of the two QASL AA instruments.
The senior position in the high resolution group has been
filled by Dr. Y. Tondeur. Dr. Tondeur was formerly with the
Frederick Cancer Research Facility in Frederick, Maryland,
where he worked with a VG Analytical ZAB-2F, the double sector
version of the ZAB-3F instrument to be received during December
1984 in the QASL. He has held postdoctoral posts with Dr. R.
Hass, formerly of National Institute for Environmental Health
Sciences in Research Triangle Park, North Carolina, where he
gained his initial ZAB experience and performed high resolution
dioxin analyses, and with Dr. R. Dougherty at Florida State
University, where he worked on environmental analyses using
negative chemical ionization mass spectrometry.
Two junior chemists have also been added to the QASL. Ms.
H. Biesiada was recently hired to provide support to the F. C.
Hart Associates (FCHA) group who operate the EMSL-LV
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containment facility. Ms. Biesiada expects to receive a
Masters degree in chemistry from Eastern Michigan University by
June, 1985 and has several years of contract analytical
laboratory experience. In,addition to her work on FCHA
samples, she is expected to provide support in other inorganic
tasks and, when necessary, to the organic group. Mr. C. Burton
has joined the QASL as a containment laboratory technician.
Mr. Burton has more than 20 years of experience as a high
school chemistry teacher and nearly as many years of experience
working for H. Walker and Sons (distilleries) in summer
positions.
Current laboratory staffing is as indicated below. Staff
members added this year are underlined.
Dr. D. Schoengold Laboratory Manager
Organic Section
Section Leader
Analytical Chemist
Analytical Chemist
Containment Laboratory
Technician
Inorganic Section
Dr. L. Morgenthaler Section Leader
Mr. C. Jones Analytical Chemist
Ms. H. Biesiada Analytical Chemist
High
Resolution MS Section
Dr.
y.
Tondeur
Section Leader
Student
Laboratory Technicians
MS.
V.
Pickard
Mr.
s.
Kieatiwong
Secretary
Mrs
. C.
Moore
A senior level research chemist with a responsibility for
protocol enhancements and high resolution mass spectrometry
support is being sought. A technician for the high resolution
group will be hired after the instrument is installed and
operating. Also, a quality assurance specialist will be added.
This last individual will provide an external quality assurance
function for the laboratory and will report to the Director of
the Environmental Research Center.
Dr. A. Lange
Mr. B. Klenk
Mr. T. Lieu
Mr. C. Burton
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SECTION 4
LABORATORY DESIGN AND CONSTRUCTION
Several changes in the laboratory physical plant were
initiated and/or completed this past year. Major changes in
progress include the addition of over 900 square feet of
laboratory and office space and modifications to the overall
laboratory air handling system.
Two work areas in the Natural History Museum have been
converted to QASL usage. A 600 square foot area is being
remodeled for use as a high resolution mass spectrometry
laboratory, consisting of instrumental space, bench space for
final sample workup and office space for two senior scientists
and a technician. In addition, a room with an area of about
300 square feet has been modified by addition of extensive
shelving to serve as a storage room. This facility will serve
to provide more storage space and more efficient access and
accounting of laboratory supply items.
It was noted that during summer months, working in the
containment facility at the hood faces, while in full
protective clothing, was almost impossible because of the hot
outside air being circulated across the operator by the hood
makeup fans. Evaporative chillers were installed in the
auxiliary air system to pretreat the makeup air and eliminate
this problem.
Pressure drop gauges were installed across the High
Efficiency Particulate Air (HEPA) filter systems so their
efficiency could be monitored on an ongoing basis. HEPA
filters are expensive, their replacement is difficult and time
consuming, and the used filters must be disposed of properly.
It is important, therefore, to only replace the filters when it
is absolutely necessary.
When the laboratory was constructed, it was assumed that
heat from the instruments would be sufficient to heat the
entire laboratory. The distribution of heat has not been
satisfactory and certain areas have been extremely cold during
the winter months, adversely affecting specific laboratory
procedures. Modifications to the air handling system to
provide heat to these lab areas is in progress.
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SECTION 5
INSTRUMENTATION
The major instrument that was ordered during this past
year was a VG Analytical, ZAB-3F, Triple-Sector ,
High-Resolution, Mass Spectrometer. This instrument will
provide routine one part per trillion (ppt)
tetrac h 1 or od ibenzo-p-dioxin (TCDD) sensitivity at high
resolution, rapid and specific identification of TCDD in the
mass spectrometry/mass spectrometry (MS/MS) mode and, in
general, greatly increase the ability of the QASL to support
the CLP and the National Dioxin Program. The QASL instrument
will be the third installation of an instrument of this type in
the United States, sixth in the world, and the only one in an
environmental laboratory. Delivery is expected about December
15, 1984. Laboratory modifications necessary to accommodate
the installation of this system will also be accomplished by
that date.
The full list of major analytical instrumentation in the
QASL is given below. Instruments or components which were
either ordered or received during this past year are
underlined:
High resolution gas chromatograph-hiqh resolution triple
sector mass spectrometer (VG ZAB-3F)
Gas chromatograph-mass spectrometer (Finnigan 4510)
Gas chromatograph-mass spectrometer (Finnigan OWA-30B)
Gas chromatograph/high performance liquid chromatograph
(Varian Vista 54/6000)
Gas chromatograph equipped with BASIC programming option
and cartridge tape backup (Hewlett Packard 5880)
Automated gel permeation chromatograph (under construction
in the QASL using ISCO detector, autosampler and fraction
collector and a Tracor pump)
Refrigerated Centrifuge (IEC model 2345) (not yet
received)
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Ion chromatograph (uses pump and data system from Varian
HPLC with Biorad CM-8 high performance conductivity
monitor, (under construction))
Inductively coupled argon plasma emission spectrometer
(Bausch & Lomb ARL 35000) equipped with Control Equipment
model AMI-10 3 automatic multiflow injector, Tylan
automated mass flow controllers and Cole Palmer
multichannel peristaltic pump
Atomic absorption spectrophotometer with HGA graphite
furnace (Perkin Elmer 5000)
Atomic absorption spectrophotometer (flame) (Perkin
Elmer 5000)
UV-visible spectrophotometer (Beckman DU 8)
IR spectrophotometer (Beckman 4250)
Gradient elution controller/data acquisition system (ISCO
model 2303) (not yet received)
Autoanalyzers (2) (Technicon II)
Major problems with the two Finnigan mass spectrometers
have had a severe impact on the output and performance of the
organic section. From mid-May, 1984, the QASL has kept
detailed records on instrument downtime and on the response of
Finnigan's maintenance personnel to these problems. The OWA
has been down 6 times (52 days total) during this period; i.e.,
29% downtime. This amounts to 8.7 days per maintenance problem.
In addition, the tape drive was inoperative for 40 of the 177
days (23%) between mid-May and the date of this report. The
most recent OWA problem took 17 days to repair. The Finnigan
4510 has a marginally better service record. It has been down
four times, a total of 33 days (8.2 days per service call) for
19% of the time.
The downtimes reported above indicate when the instruments
were totally non-functional. They do not include the times
when they were not working well but were usable or when data
system problems such as continual operating system errors or a
failure of one of the two disk drives made operation
inefficient.
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SECTION 6
CONTAINMENT LABORATORY
The containment facility is in routine use in support of
the dioxin program. A technician has been hired with a primary
responsibility of performing those procedures restricted to
that facility and to maintain it in a highly operational state.
The addition of this technician has greatly enhanced the
utility of this part of the QASL since, previously, it had been
necessary to divert one of the chemists from other work when
containment laboratory work was necessary. The actual work
performed in the containment facility will be discussed in the
section on dioxin program support.
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SECTION 7
PERFORMANCE EVALUATION SAMPLES - INORGANIC
The routine and preaward inorganic performance evaluation
(PE) samples that were analyzed by the QASL in FY84 are
summarized in Table A-l. Four routine PE, one preaward, one
Special Analytical Services (SAS) contract and two EMSL-Cin
water program evaluation samples were analyzed. In general,
results were very good. Analytical/protocol related problems
have been reported to EPA along with the final data packages.
The QASL has also reported on several problematic areas in the
current inorganic IFB protocol (WA84 J091/J092). Some of them,
relating to general procedures, will be discussed later in this
report.
The QASL has encountered problems in the determination of
silver and antimony in soil samples for every sample analyzed
this year. The problems occur only for soil samples; data from
the aqueous samples have been uniformly excellent. Results for
silver are erratic and spike recoveries for this element tend
to be low. This problem can be eliminated by making changes in
the protocol chemistry. The current version of the protocol
requires that the final solution be 2-5% HCl. At this
concentration, the predominant form of silver is AgCl2. This
may be colloidal or it may plate out on the walls of the
container. In either case, the ICP results for silver will be
erratic _and unpredictable. The principal form of Ag+ will not
be AgCl2 until the HCl concentration is about 8-10%. In other
words, the HCl destabilizes the solution for silver.
The poor recoveries for antimony are due to hydrolysis of
the solubilized antimony to an insoluble oxide or oxychloride
and a resulting loss during filtration. Successful procedures
for disolution of antimony involve addition of tartaric, citric
or lactic acids to complex the antimony and prevent its
hydrolysis.
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SECTION 8
PERFORMANCE EVALUATION SAMPLES - ORGANIC
The analytical results for the organic performance
evaluation samples that were run by the QASL during FY84 are
summarized in Table A-2. For two of the samples (FY84,QB1 and
QB3), the QASL achieved the highest analytical scores of any of
the reporting laboratories. In addition, the results on FY83,
QB4 and the WP012 Cincinnati water pollution samples were
excellent. For one sample (FY84, QB2), however, the laboratory
score was quite low. The temperature in the laboratory was
very low when the workup was being performed for this sample
and poor recoveries were attributed to this factor. The
heating system has since been redesigned to eliminate low
laboratory temperatures as a factor in the analyses.
The poor analytical results for FY84 QB4 are difficult to
explain. The results for the analyses of FY84 QB3 and WP012,
which were run before FY84 QB4, were excellent (Table A-2).
However, the analysis of FY84 QB4, which was run using the same
extraction and analytical conditions as the previous samples,
gave results for six analytes which were lower (10 to 20%) than
the acceptance range.
There were problems with the QA for this sample (Tables
A-4 and A-5) and the data package for it should not have been
released from the QASL. Measures to increase the level of
ongoing routine monitoring of the protocol QA to ensure that
analytical reports from the QASL are essentially perfect have
been implemented.
The relatively low level of reliability being experienced
with the Finnigan mass spectrometers has significantly
contributed to the laboratory's analytical problems. As
previously indicated, the downtime on the OWA was approximately
29 percent and the downtime on the 4510 was about 19 percent.
If these periods of downtime occur when a performance
evaluation sample is being analyzed, anticipated schedules are
ruined, sample holding times are exceeded and there is a
personal pressure to rush the sample through when the
instruments finally do achieve operational status. Although it
is clearly stated that the philosophy and priority of both the
EPA and the QASL is that analyses must be done in accordance
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with CLP requirements and it is more important to be correct
and follow the protocol than be on-time, the pressure to be
prompt with the sample analytical results still exists when
work is delayed due to inoperative instrumentation.
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SECTION 9
LABORATORY EVALUATION AND PROTOCOL CAUCUS TRIPS
Two organic section chemists - Dr. A. Lange and Mr. T.
Lieu - participated in CLP on-site laboratory evaluations this
year (Table A-6) . The trip to Acurex was the first evaluation
trip for Mr. Lieu. His addition to the CLP audit team enables
the QASL to be more flexible in providing support to the CLP.
Dr. L. Morgenthaler also participated in a CLP on-site
laboratory evaluation (Table A-6), in this case as the
inorganic chemistry expert on the team.
Dr. Lange participated in the April, 1984 organic caucus
in Washington, D.C. (Table A-7). The main subject of this
caucus was the new Concensus Organic Protocol. Dr.
Morgenthaler participated in three inorganic review caucuses
(Table A-7). Topics of discussion were the new inorganic
protocol, the proposed new High Hazard Inorganic Protocol and
the role of F. C. Hart Associates, Inc. in the inorganic
program. During the June meeting in Houston, Texas, an ICP
users session was held. Dr. Morgenthaler presented a paper
titled, "Performance Factors for Sequential ICP's." In this
paper, software anomalies which can cause analytical
inaccuracies in trace level (near detection limit) analyses
using sequential type ICPs were discussed. The data presented
in the paper will be discussed in more detail later.
During the 1984 Contract Laboratory Program meeting in Las
Vegas, Dr. D. Schoengold discussed the QASL protocol for
preparation and verification of dioxin performance evaluation
samples. At this meeting, both Dr. Lange and Dr. Morgenthaler
participated in analytical caucus meetings. Since full EPA
regional participation was not achieved at the Las Vegas caucus
meetings, no major protocol decisions were made. As there was
an excellent attendance of the contract laboratories, however,
they did provide an excellent medium for exchanging ideas and
discussing problems between contract laboratories and EPA
personnel.
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SECTION 10
PAPERS AND PRESENTATIONS
Dr. D. Schoengold presented a paper titled, "Quality
Assurance in the Superfund Program" at a Specialty Conference
of the Air Pollution Control Association on Quality Assurance
in Air Pollution Measurements in Boulder, Colorado in October,
1984. The paper presented aspects of the CLP program which
could be used as a model for air pollution measurements and
analyses.
Drs. Lange and Morgenthaler have a paper accepted for
publication in Analytical Chemistry on a new procedure for
protecting active metals such as aluminum from reaction with
acidic or basic solvents. The paper presents an original
method of depositing a protective plastic film on the metal
surface that is both strong and flexible.
Three additional papers by laboratory staff have been
accepted for presentation at the 1985 Pittsburgh Conference in
New Orleans. Titles, authors, and short descriptions are
included in Table A-8.
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SECTION 11
INORGANIC PROTOCOL DEVELOPMENT AND SUPPORT
In addition to active participation in protocol reviews
and caucuses as already described, the QASL provided technical
support to the development and improvement of the inorganic
protocol.
Most of the technical work done on protocol
was implemented in the recently published ino
procedure (IFB WA84 J091/J092). This work involved
functional areas:
METHOD DETECTION LIMIT (MDL) PROCEDURE EVALUATION
Previous versions of the inorganic protocol used the
International Union of Pure and Applied Chemistry (IUPAC)
method to determine a detection limit. This method is based on
the noise level in a signal from a blank sample. The problem
with the IUPAC method is that it ignores matrix effects due to
the sample.
The MDL method would appear to provide a superior measure
of detection limits because it uses a mixture of analytes and
thus takes into account matrix effects. However, because of
Dr. Morgenthaler1s special expertise in ICP software and his
work experience with ICP manufacturers, the QASL determined
that the MDL procedure can give an inaccurate measure of the
detection limit for sequential ICPs. All sequential ICPs have
a signal region where the signal is somewhat undefined which is
not caused by the ICP itself but rather by an anomaly in the
data system. Two algorithms are used by the data system to
determine signal intensity. One algorithm is used when the ICP
output signal is below a predefined function of the background
signal level and the other algorithm is used when the output
signal is above the predefined signal level. The concentration
for an element at which this algorithm crossover occurs depends
upon the intensity of the signal line chosen and the
sensitivity for that element. It also occurs for each of the
elements. The effect on the instrumental output if the signal
is in this area is a large amount of chatter and an increase in
the standard deviation for a series of repetitive measurements
from a single sample.
development
rgani c IFB
three major
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The effect of this phenomena is shown graphically in
Figure A-l. The concentrations for arsenic and lead were
chosen so the signals would be in the chatter region and the
cadmium was chosen as a control element because it was known
that the chatter would not occur in this same concentration
range. It can be clearly seen that the chatter in the signals
for arsenic and lead is three to five higher in the critical
signal area than outside this area for both of these elements
or for the cadmium control data within the critical area.
For several of the required inorganic analytes, the
solution concentrations required to perform the MDL procedure
fall very close to or within a critical chatter region for that
element. This will cause the detection limit, as determined by
this procedure, to be inaccurate because of the large
uncertainty in the signal.
There is, however, another more subtle problem. The
computer must use an algorithm to calculate maximum peak
intensity and it uses different equations above and below the
chatter region. This means that there will be two different
analytical calibration curves, one for concentrations below the
chatter region and the other for concentrations above the
chatter region. These curves have slightly different slopes
(Figures A-2 and A-3). For arsenic, the slope below the
chatter region is 10% greater than that above the chatter
region. If the instrument is calibrated using solutions
suitable for the one region and the analyte concentration is in
the other region, the result will be inaccurate.
The calibration curve problem just described leads to
still a third difficulty. In the small chatter region, the
data system will jump from one calibration curve to the other
depending upon very slight signal differences. In other words,
the data in this region are unreliable.
The problems described above are common to all sequential
ICPs, are unavoidable, are unknown to most analysts, and can
create severe problems to the MDL procedure if the detection
limit falls within the chatter region. This problem did occur
in the determination of several QASL detection limits. The
problem can be avoided by using slightly different solution
concentrations but this would require a change in the protocol.
The MDL procedure is the method currently implemented by the
Agency.
NEW INORGANIC QUALITY CONTROL MATERIALS
Two new materials were under consideration as new
quality control materials to be used in the new protocol. a
digested municipal sludge as a laboratory control solution and
a new ICP interference check solution were proposed. The QASL
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evaluated both of these materials.
Municipal Sludge
The EMSL-Cincinnati municipal sludge sample was proposed
as a laboratory control sample to verify the ability of a
laboratory to obtain correct answers with a 'real-world* sample.
The QASL was tasked to investigate this material since there
were several questions at the inorganic caucus meeting as to
reproducibility of results from this sample.
Initial QASL results verified that reproducibility was
poor with 90% confidence limits ranging from 4% to 67% of the
mean value (Table A-9). Upon running the samples which were
contained in borosilicate volumetric flasks, it was noted that
gas bubbles were forming on and in the teflon sampling
capillary of the ICP. An initial assumption was that this
represented some residual hydrogen peroxide or excess oxygen
dissolved in the liquid which could be removed by shaking.
This proved to be not the case, however, since bubble formation
remained after the flasks were shaken for fifteen minutes.
When one of the samples was transformed to a clean, linear
polyethylene bottle, there was an immediate evolution of gas.
When the sample in the polyethylene bottle was run on the ICP,
no bubble formation was observed, signal levels increased and
precision improved. Results for samples contained in plastic
bottles showed a highly significant improvement and yielded 95%
confidence limits with individual results ranging from 1% to 3%
of the mean instead of the 4% to 67% observed with glass
bottles (Table A-9).
Examination of the ultraviolet spectrum of the sample
contained in glass bottles suggested that the bubbles are a
result of decomposition of a peroxide compound. Since this
phenomona might occur for other samples containing appreciable
organic material, it was recommended that for any protocol that
involves use of hydrogen peroxide, the digestate should be
transferred to a polyethylene bottle and shaken before analysis
by flame AA or ICP.
The analytical results for the municipal sludge using the
modified procedure were in general agreement with the
Cincinnati results and the range of results within the 95%
confidence limit was much tighter than the Cincinnati reported
95% confidence limit range. The QASL recommendation was that
this material would make an excellent laboratory control sample.
The material has not, however, been introduced for use in the
inorganic protocol as of this time.
17
-------
Interference Check Solution
The ICP interference check solution is used to determine
if the spectral lines from the high levels of iron, aluminum,
calcium and magnesium, which are naturally abundant in soils,
interfere with the trace level determinations of the protocol
required elements. The QASL was tasked to prepare and analyze
the ICP interference check solution, and bottle appropriate
aliquotes and ship them to inorganic CLP laboratories. The
QASL prepared two hundred 50 ml bottles of ICP check solution
concentrate which is sufficient to prepare 100 liters of
diluted check solution. Because it is critical that the levels
of the trace analytes be precisely known, multiple analyses of
the ICP interference check solution over a period of several
weeks were performed (Table A-10). Solution stability was
checked by storing bottles for several weeks at temperatures
between 4°C and 5 2°C. The analyte concentrations appeared to
be unaffected by storage temperature or time over the range
tested. Forty units were transferred to the EPA in October,
1984, in support of the inorganic preaward IFB WA8 4 J091/J092.
One hundred and sixty units remain in inventory and no units of
interference check solution have been shipped to contract
laboratories.
PROTOCOL CHEMISTRY EVALUATION
Ultimately, the test of any new protocol must be whether
it can provide accurate and reproducible results. In the CLP,
testing includes evaluations of the protocol and required
deliverables and an analysis of samples using both the current
and proposed new protocols to ensure that the new protocol has
no bias. The QASL participated in both of these steps with the
new inorganic protocol and the FY84 QB3 performance evaluation
sample was analyzed using both protocol versions. An excellent
score (97%) was obtained using the old version of the protocol
and essentially no difference was noted in the results obtained
using the new protocol (Table A-ll) However, the laboratory
did have some problems with the technical and organizational
content of the protocol. The main issues occurred in the
section on sample spiking. Instructions for sample
quantification for a spiked sample analyzed by furnace
AA were logically circular and, thus, impossible to achieve.
Also, spiking levels were often inappropriate; for example,
there is one requirement that a sample must be spiked at two
times the CRDL, regardless of the analyte level in the sample.
If the analyte level is high, the signal for this level of
spiking will be lost in the noise. In general, the portion of
the protocol relating to spiking was in need of change and
several revisions were suggested.
18
-------
SECTION 12
ORGANIC PROTOCOL DEVELOPMENT AND SUPPORT
A new version of the organic protocol was also implemented
during this past year. This version is organized in a much
more logical and consistent manner than previous versions. The
QASL supplied written comments on several versions of the
protocol before its final acceptance. In addition, as
mentioned above, Dr. Lange participated in an organic caucus
meeting in Washington, D.C. in April, 1984 where this protocol
was the major topic of discussion. The QASL also analyzed a
sample (FY84, QB3) under both the previous and a proposed new
version of the concensus organic protocol to demonstrate that
comparable results could be obtained. Initial examination of
the data showed good agreement between the two analyses.
However, it has been impossible to generate the final report on
this sample because the data tape from SAS 1033 HQ cannot be
read by the Finnigan tape drive, even though it was verified as
readable when it was created.
19
-------
SECTION 13
INORGANIC - PREPARATION OF STANDARD REFERENCE MATERIALS
As part of the effort to evaluate the pollutant levels
near the Ruston, Washington smelter site, the QASL was
requested to prepare an area specific reference material.
Twenty three kilograms of Ruston soil was received in the QASL.
After initial drying and rough sizing through large mesh
screens, the material was divided into three cuts (>180
micrometers, >75 and <180 micrometers, and <75 micrometers).
Each sized cut was digested using the standard nitric
acid-peroxide procedure and analyzed in triplicate by ICP
(Table A-12). There were significant differences in the
results for the different sized cuts with the cuts containing
smaller particles tending to have a higher concentration of
analytes. This is probably due to improved digestion
efficiency for the smaller particles.
Because the inclusion of the fines (<75 micrometers) could
lead to physical stratification of the standards, loss of
material in moving air and filtration difficulties, the final
reference material contains none of the <75 micrometer fines.
The two larger cuts were combined and riffeled five times to
generate nine kilograms of the final product. Six randomly
chosen samples were digested by the standard
nitric acid-peroxide procedure and analyzed twice by ICP. The
analytical repeatability for the elements determined based on
duplicate analyses of six digestates, generally ranged from
four to six percent (Table A-13). Thirty units (10 gram
aliquotes) were transferred to EPA in July, 1984 for use as the
FY84, QB3 inorganic quarterly blind sample. None of the
material has yet been used as a Ruston area, standard material.
20
-------
SECTION 14
DIOXIN PROGRAM SUPPORT
A major effort has been expended by the organic section
this past year in support of the dioxin program, primarily in
the areas of protocol development, IFB support, preparation,
analysis and shipment of performance evaluation (PE) samples,
analysis of EPA-supplied analytical standards, and support of
the Hyde Park, New York consent decree. Each of these areas is
discussed below.
PREPARATION OF PERFORMANCE EVALUATION MATERIALS
In terms of time invested, preparation and analysis of
performance evaluation samples has been the largest QASL dioxin
related effort. The TCDD protocol requires that contract
laboratories analyze one performance evaluation sample per
batch (20) of samples analyzed. The QASL has prepared about 35
kilograms of materials for this program comprising seven
different batches of PE materials ranging in concentration from
approximately 10 ppt to 10 ppb (Tables A-14 - A-21). Thirteen
additional batches have been prepared but not yet analyzed.
The materials were prepared in 500-gram lots by mixing one
liter of solvent containing known levels of 2,3,7,8-TCDD and
nominal levels of interferences with the support phase and
taking it to dryness in a rotary evaporator. When nine lots at
the same concentration level had been prepared, they were mixed
and homogenized in a V-blender and then packaged into amber
glass vials, 20 grams of PE material to each vial. Homogeneity
was verified by analysis of randomly selected vials. Data for
typical sample sets are shown in Table A-22. Homogeneity is
tested by determining if any of the values for a set are
outliers. If there are no outliers, the set is assumed to be
homogeneous. If there are outliers, the set is reanalyzed to
determine if the outlier was an experimental fluke or is a true
outlier. If the second analysis confirms the presence of the
outlier, the batch is rejected and the material is reblended.
To date, no sets have failed this test for homogeneity.
The QASL has shipped 859 units of performance evaluation
samples (Tables A-14 - A-21). Most of the shipments have been
to EPA regional laboratories although some samples have also
been shipped to contractors, university laboratories or groups
21
-------
monitoring waste site cleanup efforts. The number of vials per
shipment ranged between one and one hundred vials.
HYDE PARK CONSENT DECREE SUPPORT
The QASL was also requested to provide support as
technical input to the Hyde Park, New York consent decree.
Three independent laboratories had previously been involved in
monitoring the cleanup of this waste site, however, each of
them used a different protocol to analyze for 2,3,7,8-TCDD.
The QASL was requested to manage a method comparability study.
The first step in the program was the preparation of three
characterized, homogeneous, site-specific, reference materials.
The procedure for sample preparation was verified first using a
sample of Las Vegas soil and then using a sample of dioxin-free
Hyde Park soil. The material was difficult to work with
because it contained a large amount of foreign matter, was
moist and clayey, and also contained many lumps which were
difficult to pulverize. However, drying, extensive crushing,
final grinding in a blender, sieving through window screen and
homogenization in a V-blender, produced a fine soil that
appeared physically homogeneous.
Three 10-kilogram samples (HP001, background; HP002, fence
at Vector D; HP003, 18 feet from fence at Vector H) were
received from the waste site and the procedure previously
described was used to prepare a quantity of reference material.
Thirty-nine extractions (13 extractions of each of the samples)
and analysis for hexachlorobenzene were performed to verify
homogeneity. Each extract was analyzed several times and more
than 150 GC runs (including calibration, retention time, etc.
runs) were necessary to verify homogeneity (Table A-23). The
homogeneous samples were then analyzed for six target compounds
(Table A-24). Sample HP002 (fence at Vector D) had the highest
level of these six compounds. Analyses for 2,3,7,8-TCDD were
then performed using the EPA IFB protocol. Two of the samples
(HP0 01 and HP003 ) contained no TCDD at the 1 ppb detection
limit (Figures A-4 and A-6). The third (HP002) had a strong
chemical odor, had extensive GC/MS interferences in the
extracts, and could not be cleaned up sufficiently using any of
the standard protocol steps to achieve a TCDD detection limit
less than 30 - 40 ppb (Figure A-5). At this level, no TCDD was
detected. High resolution mass spectrometry, with its better
detection limit and greater insensitivity to interferences, is
the obvious next step to determine the TCDD levels in this
sample. Samples have been submitted to the EPA for high
resolution analysis but as yet no results have been reported.
It is anticipated that the QASL will attempt to analyze these
samples once the ZAB-3F is installed.
It was anticipated that the next step in the Hyde Park
22
-------
study would be to submit samples to the laboratories specified
in the consent decree for analysis by their individual
procedures as well as to a fourth laboratory which would use
all three methods. To date no request from EPA to continue
with this part of the project has been received.
IFB PROGRAM SUPPORT
This past year, the TCDD analytical program was converted
from a Special Analytical Services (SAS) contractual program to
the more conventional IFB contract program (IFB WA84-A002).
The QASL has provided support in two areas. The preaward
proficiency samples used for this contract consisted of four
samples (one TCDD spiked sample, a blank, an interferent spiked
blank and a duplicate TCDD spiked sample) prepared in the QASL
and one high level TCDD sample. Because of the laboratory's
expertise in shipping high hazard samples in accordance with
DOT regulations, the QASL packaged and shipped the sample sets
used for the IFB to the 20 laboratories that responded to the
Invitation for Bid (Table A-25).
The QASL routinely provides referee analyses of all
preaward samples. Even though the laboratory had prepared four
of the five samples and knew the levels, it still analyzed the
samples on the same basis as a contract laboratory to provide
additional data for setting performance windows. The results
of the referee analyses were in good agreement with the initial
analyses.
ANALYSIS OF EPA-SUPPLIED CALIBRATION STANDARDS
The TCDD protocol is structured so that contract
laboratories need supply or prepare none of the calibration or
reference materials required in the protocol. The agency
through contracts or cooperative agreements supplies all
standards. The QASL prepares, as previously described, the
performance evaluation sample, and Northrup Services Inc.,
which operates the EPA Quality Assurance Materials Bank,
supplies the rest of the standards. In its role as a referee
laboratory, the QASL analyzed all the calibration and spiking
solutions prepared by Northrup to verify that the levels are as
specified in the protocol. Typical results for several
Northrup sample sets of five TCDD calibration solutions are
shown in Table A-26.
PROTOCOL DEVELOPMENT
The initial dioxin IFB was issued in December, 1983.
Prior to this date, the QASL provided extensive written
comments and dry run analyses to evaluate the new protocol.
Over the course of the year, the protocol has remained
essentially unchanged.
23
-------
There is, however, a new round of protocol changes and
improvements anticipated, and a proposed new version of the
TCDD protocol has been circulated for comment. The QASL has
reviewed this protocol and has furnished written comments to
EPA. A dioxin caucus meeting is planned for Seattle,
Washington during November, 1984. Laboratory personnel will
participate in the caucus meeting.
24
-------
SECTION 15
SUPPORT TO EMSL-LV CONTAINMENT FACILITY
The F. C. Hart Associates,
to operate the containment
responsibility of this group is
hazardous samples and then sh
laboratories for analysis.
Inc. (FCHA) has been contracted
facility at EMSL-LV. The
to prepare sample extracts from
ip the extracts to contract
Because FCHA has no analytical instrumentation to perform
the QC analyses specified in their extraction protocol, the
QASL has been tasked to do the analytical work. Specific work
to be performed includes analyses for inorganics by ICP and
atomic absorption and analyses for extractable and volatile
organics by either GC or GC/MS. Because the FCHA work load
could not be handled with existing laboratory staff, a chemist
was hired to support this project.
To date, two sets of FCHA performance evaluation samples
have been analyzed, protocols have been written to cover the
required chemical procedures and forms have been designed for
reporting data and results. The analytical protocols and the
proposed forms have been submitted to FCHA for their approval.
The first set of PE samples was analyzed with excellent
results using a modified version of the official FCHA protocol
where the samples for ICP analysis were diluted to lower the
high solids and salt content to acceptable levels. The second
set was analyzed using the protocol explicitly and major
problems were encountered in the ICP analysis. A high solids
content in the samples coupled with the fact that the ICP in
the QASL is a sequential type instrument (the protocol was
written for a simultaneous type instrument) contributed to the
analytical problems. The small orifices in the nebulizer
clogged, a nebulizer was ruined and the instrument was
non-operational for several days. In fact, the protocol
specifically states that problems will be encountered if it is
attempted using a sequential instrument.
Two technological adjustments to this problem are possible.
The QASL has demonstrated that by modifying the protocol
through dilution of the sample, the samples can be run with
existing instrumentation in the laboratory without undue loss
of sensitivity. In the short run, after discussion with and
25
-------
approval by FCHA, this modification will probably be
implemented to eliminate the problem. A more exciting
alternative is being considered, however. Dr. Morgenthaler has
designed a modified ICP nebulizer which should permit high
solids samples to be run with no clogging of the orifices.
This new nebulizer also appears to provide considerably higher
instrument sensitivity with normal low-solids samples. The new
nebilizer employs a jet with a very small orifice to generate a
high velocity sample stream. Impact of the stream on a
suitable surface generates a fine mist that is introduced into
the ICP. Because the sample passes through the jet under
pressure, the orifice is inherently non-clogging. The jets
used are drilled sapphire watch jewels which only cost about
ten dollars each. Should they clog, the replacement cost will
be much less than the several hundred dollar cost of a standard
ICP nebulizer. The ICP has also been equipped with an
automatic multiflow injector so it can be used as a continuous
analyzer autosampler. The combination of these two
instrumental modifications should enable samples with several
percent solids content to be run routinely. This will greatly
enhance the ability of the laboratory to run difficult samples
on a routine basis.
26
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SECTION 16
UNIVERSITY RELATED WORK
In addition to its role in support of the Superfund CLP,
the QASL provides support to UNLV academic and research
programs. Mr. C. S. Crownover, a graduate student in
Anthropology, did his laboratory work in the QASL. The project
involved relating the levels of 18 inorganic elements in the
human skeletal system to stress indicating Harris lines in the
long bones.
Other work done for the University included analysis of a
number of rat urine samples and analysis of PCB samples.
Drs. Schoengold and Morgenthaler co-taught an evening
course on trace chemical analysis during the fall semester of
the 1983-84 academic year. Twelve students, including several
EPA and EPA-contractor employees, took the course and the
reaction was very positive. The course will be offered again
next year.
The University is in the process of setting up a Master of
Environmental Chemistry program. This will be a cooperative
effort of the QASL and the chemistry department. Initial local
approval for the program has been received and a detailed
program plan has been submitted to the Board of Regents for
final approval.
27
-------
0.060 ~
0.050
Arsenic
Cadmium
Lead
0.040
0.030 _
0.020
0.010
0.2
0.4
0.6
0.8
Concentration (yg/ml)
Figure A-l. ICP standard deviation versus sample
concentration.
28
-------
1.0 -
ro
10
60
71
c
o
•H
,8 -
.6 -
nj
u
4J
c
0)
u
•c
8 .4
*a
a>
Vj
3
U)
«
-------
OJ
o
60
ZL
c
o
m
ij
¦U
c
a)
u
c
o
o
-o
-------
RIC
0V21/84 I4i26:M
SMflE: HYDE PARK- MP-001 (Background soil)
OATA: 84BNA0072
SCANS 1 TO 2000
2146300.
RIC
Scan #
2000
Figure A-A. Hyde Park soil HP001 total ion chroTTiatogram.
-------
RIC DATA: 846NA0076 SCANS I TO 2000
0V21'84 17« 22:00
SAflPLE; HYOE PARK - HP-002 (Fence at Vector D)
RIC.
Scan #
1500
500
Figure A-5. Hyde Park soil HP002 total ion chromatogram.
-------
RIC
0V2I/84 15i52:P«
SAWLE: HVOE PAflK-+ff-fl03
OATAi 04BNM074
(18 feet from fence at Vector H)
SCANS 1 TO 2M0
2060200.
n^i j
, ir.i Jh. -A
Scan it see ieee isee
Figure A-6. Hyde Park soil HP003 total ion chromatogram.
2000
-------
TABLE A-l. FISCAL YEAR 1984 INORGANIC PERFORMANCE EVALUATION
AND PREAWARD SAMPLES
Sample Case Score Ranking Notes
QB1
QB2
QB3
SAS1033H2
2199
67/75(89%) 5/12
2324,2325 64/72(88.9%) 2/12
2547 70/72(97%) 2/15
Identification and quanti-
fication perfect. 3 dupli-
cates outside window.
One matrix spike outside
window
Same sanple as QB3 using
new protocol. Excellent
agreement with QB3.
QB4
3062,3063 64/72(88.9%) 5/13
Two elements outside window.
Technical problems due to
high Pe and A1 levels in ICP
check solution caused QA
errors for these elements.
WP012
No inorganic errors.
Preaward WA84 J091/092 241/250 3/33
(96.4%)
WP013
No audit results available
yet.
34
-------
TABLE A-2. FISCAL YEAR 1984 ORGANIC PERFORMANCE EVALUATION
SAMPLES
Sairple
Case Score
Rariking Notes
FY83 QB4 1954
QB1 2179
QB2 2323
QB3
WP012
QB4
WP013
2543
36/40(90%)
40/40(100%)
90.71/120
(76%)
103.28/105
(98.4%)
23/25
3061 92/180(77%) 11/27
Missed 1 ccrrpourri
Highest scoring lab
Low lab tenperature
contributed to poor
extraction recoveries
1/32 Highest scoring lab
Missed 1 of 2 DDD
values. No other
errors
See Section 8
No audit results
available yet
35
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TABLE A-3. RESULTS FOR FISCAL YEAR
1984 ORGANIC PERFORMANCE
EVALUATION SAMPLE (QB4)
Ccnpcund QASL Itesults Confidence limits (EPA) Error
2-methylphenol
231
**
123-277
4-methylphenol
90.5
28-116
2-nitrophenol
66
*
78-153
-15%
2,4-dichlorophenol
140.5
108-232
p-chloro-m-cresol
42
*
56-231
-25%
2,4,6-trichlorophenol
82
*
93-214
-12%
bis(2-chloroethyl)ether
223.5
149-258
1,3-dichlorobenzene
43.5
34-65
bis(chloroisopropyl)ether 179
120-221
n-nitrodipropylamine
197.5
136-261
isophorone
47
42-83
1,2,4-trichlorobenzene
42.5
41-81
2,6-dinitrotoluene
79.5
*
90-188
-12%
fluorene
34
32-65
hexachlorobenzene
71.5
40-123
phenanthrene
87.5
72-133
chloroform
149.5
138-208
1,2-dichloroethane
90.5
87-132
1,1,1-trichloroethane
41.5
38-62
carbon tetrachloride
24
*
25-37
-4%
branodi chlor anet hane
24.5
*
30-43
-18%
trichloroethane
34
34-49
dibrcmochl or anet hane
44.5
44-60
brcnoform
38.5
38-59
tetrachloroethane
15.5
15-25
heptachloroepoxide
448
~
182-443
+1%
dieldrin
258
162-423
4,4'-DDD
183
111-359
chlordane
1555
805-1697
* Outside 95% confidence limits.
** Data in vg/l.
36
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TABLE A-4. ORGANIC FISCAL YEAR 1984 QB4 SURROGATE fcXXVERY RESULTS
Sarple
(recovery
windows)
Toluene-d5
(86-119)
1,2-dichloro-
ethane-d4
(77-120)
nitro-
benzene-d5
(41-120)
2-fluoro
biphettyl
(44-119)
terphenyl-
dl4
(33-128)
phenol-
d5
(15-96)
2-fluoro-
phenol
(23-107)
2,4,6-tribrano-
phenol
(20-105)
Lato Blank
116**
95
Field Blank
110
98
42
48
73
26
38
89
Sanple
107
95
74
60
100
50
27
70
Dupl. Sanple
103
92
84
68
84
84
98
120 *
Spike Saiple
111
100
74
98
124
72
92
82
Dupl. Spike
Sanple
115
100
84
68
84
84
98
120 *
* Beyond contract limits.
** Data in percent (%).
-------
TABLE A-5. MATRIX SPIKE RECOVERY RESULTS FOR FISCAL YEAR 1984
ORGANIC QB4
QC limits
% Recovery % Recovery (advisory
Compound Sample duplicate only)
1,1-dichloroethene
106
108
61-145
trichloroethene
88
88
71-120
chlorobenzene
100
120
75-130
toluene
108
120
76-125
benzene
82
84
76-127
1,2 , 4-trichlorobenzene
92
114*
39-98
acenaphthene
92
108
46-118
2,4-dinitrotoluene
98*
112*
24-96
Di-n-butylphthalate
86
76
11-117
pyrene
114
114
26-127
N-nitroso-di-n-propyamine
124*
104
41-116
1, 4-dichlorobenzene
100*
112*
36-97
pentachlorophenol
83
117*
9-103
phenol
51
73
12-89
2-chlorophenol
0*
59
27-123
4-chloro-3-methylphenol
10*
30
23-97
4-nitrophenol
40
62
10-80
* outside advisory limits
38
-------
TABLE A-6.
CLP ON-SITE LABORATORY
EVALUATIONS CONDUCTED
Laboratory
Date (days)
Individual
Purpose
JTC Environmental
Consultants
January, 1984 (1)
L. Morgenthaler
Inorganic
Acurex
August, 1984 (1)
T. Lieu
Organic (observer)
Envirodyne
May, 1984 (1)
A. Lange
Organic
Envi rodyne
May, 1984 (1)
A. Lange
Di o* i n
Rocky Mountain Analytical
May, 1984 (1)
A. Lange
Organic
Rocky Mountain Analytical
May, 1984 (1)
A. Lange
Dioxin
TABLE A-7. CLP CAUSUSES ATTENDED
Location
Date (days)
Individual
Purpose
Washington, D.C. January (3)
Houston, Texas June (3)
Denver, Colorado July (1)
Washington, D.C. April (3)
L. Morgenthaler
L. Morgenthaler
L. Morgenthaler
A. Lange
Proposed new inorganic protocol.
Introduction to F. C. Hart.
Proposed new inorganic protocol,
ICP Seminar (presented a paper),
High hazards protocol.
Concensus organic protocol
-------
TABLE A-8. PAPERS AND PRESENTATIONS
Title
Author
Journal/location
Performance Factors for
Sequential ICP's
Quality Assurance in the
Superfund CLP
Corrosion Resistant Coating for
Laboratory Equijment
Design of a Jet Inpact Nebulizer
for a Sequential ICP Spectrometer
Performance of a Jet Inpact
Nebulizer for ICP Analyses of
High Solids Sanples
Detection of Selected Polynuclear
Arcmatics in Water at the Sub
Part Per Billion Level
L. Morgenthaler
D. Schoengold
L. Margenthaler,
A. Lange
L. Morgenthaler,
C. Jones
L. Morgenthaler,
C. Jones
A. Lange,
T. Lieu
Inorganic caucus;
Houston, Texas;
July
Q. A. in Air Pollution
Measurements Meeting
Analytical Chenistry
(accepted for
publication)
Pittsburgh Conference
on Analytical Chanistry
(to be presented
March, 1985)
Pittsburgh Conference
on Analytical Chanistry
(to be presented
March, 1985)
Pittsburgh Conference
on Analytical Chemistry
(to be presented
March, 1985)
40
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TABLE Ar-9. MUNICIPAL DIGESTED 3.UDGE INORGANIC CHECK SAMPLE
SBVNDARD VERSUS MODIFIED PROCEDURE RESULTS
Elenent Cincinnati Results (mg/kg) UNLV Unmodified (iqg/kg) UNLV Modified (nig/kg)
X 95% Confidence X 90% Confidence X 90% Confidence 95% Confidence
range range range range
Aluidnian
4560
2010-7110
3760
3481-4039
4031
3954-4108
3933-4129
Beryllium
0.28
0-2.99
0.77
0.64-0.90
0.78
0.75-0.81
0.75-0.81
Chromium
193
150-246
15.6
5.6-25.6
168
167-169
166-170
Copper
1080
882-1280
968
912-1024
1028
1013-1043
1009-1047
Iron
16500
11200-21700
14438
13830-15046
15333
15146-15520
15096-15570
Manganese
202
182-223
184
175-193
197
195-199
195-199
Nickel
194
164-235
150
141-159
164
162-166
161-167
Lead
526
372-680
400
399-441
463
447-478
445-481
Vanadium
13.0
1.7-24.4
8.3
6.3-10.3
9.7
9.27-10.13
9.15-10.25
Zinc
1320
1190-1450
1004
910-1098
1122
1105-1139
1101-1143
Cadmium
19.1
10.5-27.8
16.5
15.3-17.7
18.4
18.1-18.7
18.0-18.8
Silver
80.6
0-203
60.0
56.6-63.4
67.6
66.4—68.8
66.1-69.1
-------
TABLE A-10. ICP INTERFERENCE CHECK SOLUTION
STABILITY STUDIES AND FINAL ANALYSES
Element Analyses Analyses
(7/15/84) (11/20/84)
ivq/1) (ug/1)
Mean
(n=5 7)
R.S.D.(%)
Initial
Fi nal
Barium
464
1.9
478
492
Beryllium
412
2.0
388
406
Cadmium
840
2.2
* * *
* **
Chromium
705
2.0
688
715
Cobalt
549
3.2
554
560
Copper
553
2.8
555
580
Manganese
617
1.8
613
631
Nickel
890
3.3
896
914
Vanadium
508
3.2
525
531
Zinc
874*
2.7
937
965
Aluminum**
448
1.0
456
463
Calcium**
445
1.3
450
455
Iron**
422
2.4
411
423
Manganese**
425
1.2
427
423
* The data for zinc shows a bimodal distribution. Based on 45
of 57 samples.
** Data in mg/1.
*** Not analyzed by ICP in this protocol.
42
-------
TABLE A-11. COMPARISON OF INORGANIC FY84 QB3 SAMPLE
USING OLD AND PROPOSED NEW PROTOCOLS
Liquid
Sample
Solid
Sample
Element
Old
New
Old
New
(ug/1)
(mg/kg)
Aluminum
919
910
4,280
3,550
Antimony
<5
<5
<0.25
<0.25
Arsenic
18
18
4.2
4.7
Barium
<10
<10
55.9
54. 2
Beryllium
16
16
0.401
0.37
Cadmium
3
2
0.3
0.2
Calcium
90,265
88,000
36,700
36,700
Chromium
56
59
8.34
7.33
Cobalt
<30
<30
10.8
11.7
Iron
269
266
5,000
4,300
Lead
<3
<3
9.0
9.0
Magnesium
25,300
25,300
12,000
12,000
Manganese
63
61
113
113
Mercury
0.8
0.8
<0.08
<0.08
Nickel
100
100
5.04
4.30
Potassium
5,100
4,800
not required
866
Selenium
10
7
<0.1
<0.1
Silver
<125
<25
<1.25
<1.25
Sodium
107,000
104,000
not required
196
Thallium
<2
<2
<0.1
<0.1
Tin
<10
<10
<0.5
<0.5
Vanadium
<20
<20
11.0
10.3
Zinc
110
124
22.0
22.1
43
-------
TABLE A-12. ANALYSIS CF SIZED CUTS CF RJSTON 90IL
Concentrations (mq/kq)
<180 and
>180 ym >75 ym Ratio of <75 um Ratio of
Element (cut 1) (cut 2) (cut 2:1) (cut 3) (cut 3:2)
silver
3
7
2.3
8.5
1.2
aluminum
10200
13250
1.3
16400
1.2
arsenic
210
345
1.6
550
1.6
beryllium
0.
15
0.25
1.7
0.3
1.2
barium
145
205
1.4
280
1.4
calcium
2250
3750
1.7
4300
1.1
cadmium
8
12
1.5
15.5
1.3
cobalt
7
8.5
1.2
10.
1.2
chromium
22
25.5
1.2
32.5
1.3
copper
750
1450
1.9
1850
1.3
iron
11500
11250
0.98
14750
1.3
magnesium
2950
2750
0.9
2950
1.1
manganese
490
600
1.3
600
1.0
sodium
75
95
1.3
100
1.1
nickel
21.
5
27
1.3
34.5
1.3
lead
400
750
1.9
900
1.2
sulfur
360
550
2.4
950
1.1
antimony
38
65
1.7
120
1.8
selenium
37
46
1.2
60
1.3
tin
6
9
1.5
15
1.7
thallium
15.
5
27
1.7
37.5
1.4
titanium
330
340
1.03
420
1.2
zinc
190
335
1.8
445
1.3
44
-------
TABLE ft-13. STATISTICAL SJfWARY FOR >75 MICROMETER RJSTON SOIL
Element
ppm in Soil
Standard Deviation
90% Confidence Limits
RSD !
Silver
3.05
0.27
2.46-3.65
8.9
Aluminum
11400.0
450.0
10421-12379
3.9
Arsenic
232.0
10.96
208-256
4.7
Beryllium
0.204
0.01
0.182-0.226
4.9
Barium
143.29
5.76
131-156
4.0
Calcium
2917.5
88.85
2724-3111
3.0
Cadmium
7.82
0.59
6.54-9.10
7.5
Cobalt
8.27
0.45
7.29-9.24
5.4
Chromium
17.9
1.02
15.6-20.1
5.7
Copper
939.0
47.11
836.7-1041
5.0
Iron
11250.0
512.6
10134-12366
4.6
Magnesium
3005.8
123.5
2737-3274
4.1
Manganese
501.71
26.52
443-558
5.3
Sodium
94.12
15.71
59.9-128
16.7
*
89.7
4.73
79.4-100
5.3
Nickel
26.54
0.86
24.8-28.4
3.2
Lead
592.5
199.9
157-1028
33.7
**
511.5
28.07
450-573
5.5
Sulfur
434.0
16.79
401-475
3.9
Titanium
358.1
22.39
309-407
6.3
Vanadium
21.9
0.99
19.8-24.1
4.5
Zinc
240.3
8.38
222-259
3.5
* Sodium without ckta for sample 1
** Lead without data for sanple 4
45
-------
TABLE A-14. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Sample £ 13
Shipment Cumulative
Sequence Recipient Date Sent No. Sent No. Sent
2.
4.
5.
6.
8.
R. James
Southern Research 1/16/84
Institute
M. Kuehl
EPA Region 5 8/10/84
M. Kuehl
EPA Region 5 9/19/84
B. F. Dudenbostel
New Jersey Department
Environmental Protection 9/25/84
R. Wiggenden
Argonne National
Laboratory 10/4/84
T. Handel
Centec 10/4/84
M. Kuehl
EPA Region 5 10/4/84
G. Hacker
Versar, Inc. 10/11/84
12
10
10
12
22
27
37
39
41
49
54
46
-------
TABLE A-15. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Shipment
Sequence
Sample 117
Cumulat ive
Recipient Date Sent No. Sent No. Sent
1.
2.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
R. Kleopfer
EPA Region 7
M. Hiatt
EPA Region 9
W. Coakley
EPA Region 2
R. Kleopfer
EPA Region 7
R. Kleopfer
EPA Region 7
R. Kleopfer
EPA Region 7
J. Donnelly
LEMSCO
J. Woods
EPA Region 7
P. Krantz
EPA Region 3
W. Coakley
EPA Region 2
M. Bradford
EPA Region 9
J. Hoe
EPA Region 9
P. Krantz
EPA Region 3
11/14/83
11/15/83
11/17/83
11/18/83
12/7/83
1/4/84
2/7/84
3/16/84
5/2/84
6/4/84
6/5/84
6/19/84
6/22/84
50
12
50
20
24
30
50
51
63
113
118
138
144
168
173
203
205
207
209
47
-------
TABLE A-16. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Sample I 18
Shipment
Sequence
Recipient
Date Sent No. Sent
Cumula t ive
No. Sent
1.
4.
5.
6.
8.
9.
10.
11.
12.
P. Krantz
EPA Region 3 7/23/84
S. Richardson
Ecology and Environment
EPA Region 8 FIT Team 7/26/84
P. Krantz
EPA Region 3 7/26/84
C. Hooper
EPA Region 4 8/22/84
R. Wiggenden
Argonne National
Laboratory 9/19/84
B.F. Dudenbostel
New Jersey Department of
Environmental Protection 9/25/84
R. Wiggenden
Argonne National
Laboratory 10/4/84
T. Handel
Centec
Ruston, VA 10/4/84
R. Thompson 10/9/84
NSI
J. Moe
EPA Region 9 10/9/84
W. Coakley
EPA Region 2 10/12/84
R. Harris
American Analytical 10/26/84
4
20
30
12
15
20
25
31
35
55
56
86
87
48
-------
TABLE A-17. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Sample I 20
Shipment
Sequence
Recipient
Date Sent No. Sent
Cumulative
No. Sent
M. Kuehl
EPA Region 5
10/4/84
2.
G. Hacker
Versar, Inc.
10/11/84
13
49
-------
TABLE A-18. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Sample I 25
Shipment Cumulative
Sequence Recipient Date Sent No. Sent No. Sent
1.
2.
4.
6.
7.
9.
10.
11.
12.
R. Kleopfer
EPA Region 7 11/18/83
J. Donnelly
LEMSCO 2/7/84
R. Kleopfer
EPA Region 7 2/10/84
J. Woods
EPA Region 7 3/26/84
P. Krantz
EPA Region 3 5/2/84
W. Coakley
EPA Region 2 6/4/84
P. Krantz
EPA Region 3 6/22/84
P. Krantz
EPA Region 3 7/23/84
C. Hooper
EPA Region 4 8/22/84
S. Richardson
Ecology and Environment
EPA Region 8, FIT Team 8/30/84
J. Donnelly
LEMSCO 9/20/84
B.F. Dudenbostel
New Jersey Department of
Environmental Protection 9/25/84
50
50
24
20
50
56
106
130
135
153
160
163
168
170
172
177
50
-------
TABLE A-18. (Cont.)
Sample I 25
Shipment Cumulative
Sequence Recipient Date Sent No. Sent No. Sent
13.
14.
15.
16.
17.
B. Emme1
Radian Corporation
Utah
R. Wiggenden
Argonne National
Laboratory
T. Handel
Centec
J. Moe
EPA Region 9
J. Chaney
North Coast Lab
9/27/84
10/4/84
10/4/84
10/9/84
10/12/84
180
181
183
184
185
51
-------
TABLE A-19. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Shipment
Sequence
Rec ipient
Sample £ 26
Date Sent No. Sent
Cumulat ive
No. Sent
1.
3.
4.
5.
6.
7.
8.
9.
10.
11.
R. Kleopfer
EPA Region 7
R. Kleopfer
EPA Region 7
J. Donnelly
LEMSCO
R. Kleopfer
EPA Region 7
J. Woods
EPA Region 7
P. Krantz
EPA Region 3
W. Coakley
EPA Region 2
P. Krantz
EPA Region 3
P. Krantz
EPA Region 3
C. Hooper
EPA Region 4
R. Wiggenden
Argonne National
Laboratory
11/18/83
1/4/84
2/7/84
2/10/84
3/16/84
5/2/84
6/4/84
6/22/84
7/23/84
8/22/84
10/4/84
50
19
50
24
20
50
69
75
125
149
154
174
179
184
187
190
52
-------
TABLE A-19. (Cont)
Sample I 26
12. T. Handel
Centec 10/4/84
13. W. Coakley
EPA Region 2 10/12/84
53
-------
TABLE A-20. INVENTORY AND RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Sample I 31
Shipment Cumulative
Sequence Recipient Date Sent No. Sent No. Sent
1.
G. Hacker
Versar, Inc.
10/11/84
100
100
54
-------
TABLE A-21. RECIPIENTS OF TCDD PERFORMANCE EVALUATION SAMPLES
Shipment
Sequence
Recipient
Number sent
1.
R. James
Southern Research Institute
12
2.
3.
M. Kuehl
EPA Region 5
B.F. Dudenbostel
New Jersey Department of
Environmental Protection
31
20
4.
5.
R. Wiggenden
Argonne National Laboratory 17
T. Handel
Centec 10
6.
7.
8.
9.
10.
G. Hacker
Versar, Inc.
R. Kleopfer
EPA Region 7
M. Hiatt
EPA Region 9
W. Coakley
EPA Region 2
J. Donnelly
LEMSCO
110
3 44
132
20
11.
J. Woods
EPA Region 7
72
55
-------
TABLE A-21 (Cont)
Shipment
Sequence
Rec ipient
Number sent
12.
13.
14.
15.
P. Krantz
EPA Region 3
M. Bradford
EPA Region 9
J. Moe
EPA Region 9
S. Richardson
Ecology and Environment
EPA REGION 8 FIT Team
47
2
16.
17.
C. Hooper
EPA Region 4
R. Thompson
NSI
20
18.
19,
R. Harris
American Analytical
B. Emme1
Radian Corporation
Utah
56
-------
TABLE A-22. TYPICAL ANALYTICAL DATA FOR 2,3,7,8- TCDD
PERFORMANCE EVALUATION SAMPLES
Run TCDD TCDD
Concentrat ion(ppb) Concentration(ppb)
1. 7.34 4.39
2. 9.07 4.55
3. 8.20 4.35
4. 8.62 4.43
5. 7.73 4.13
6. 4.23
7. 3.79
Mean 8.19 4.27
Standard Deviation 0.69 0.27
57
-------
TABLE A-23. HYDE PARK SOIL HEXACHLOROBENZENE HOMOGENEITY DATA
Sample # HP002
Replicate Replicate Replicate
Sample Run Run Run
Extraction 12 3
(area) (area) (area)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
2374
2756
3063
5148
3548
3529
3652
3344
4465
2293
3011
3294
3016
3030
2686
2544
3202
2956
2929
2758
3459
3526
2841
2908
3846
3241
2946
3097
3252
3426
3061
3266
3248
3331
3481
3207
2972
3889
3483
SUMMARY OF ALL SAMPLE AREAS
Sample
Mean Area
2SD
HP001
HP002
HP003
39
39
39
1777
3242
909
8.08
15.7
15.8
58
-------
TABLE A-24. HYDE PARK SOIL TARGET COMPOUND QUANTIFICATION
Chlorotoluene 2,4,5-trichlo- hexachloro chloro
Sample 0 MP phenol benzene benzene
HP001
ND
ND
ND( 2)
192
63
ND(3)
HP001D (1)
ND
ND
ND
180
57
ND
HP002
100
296
153
492
49,000
ND
HP002D
186
274
165
417
48,500
ND
HP003
ND
55
ND
147
282
ND
HP003D
ND
35
ND
125
266
ND
Results are in ppb
(1) D = duplicate sample
(2) < 10 ppb is detection limit for chlorotoluene
(3) < 0.5 ppb is detection limit for chlorobenzene
59
-------
TABLE A-25. RECIPIENTS CF DICKIN PREAWARD SAMPLES
Laboratory
Location
American Analytical and Technical Service
Cushing, OK
Analytical Technologies
Itetional City, CA
Biospherics
Rockville, J*E
California Analytical laboratories
W. Sacramento, CA
EAL Corporation
Richmond, CA
Envirodyne Engineers
St. Louis, MO
Environmental Research Group, Inc.
Ann Arbor, MI
ETC Corporation
Edison, NJ
Geochem Research Institute
Houston, IX
Gulf South Research Institute
Baton Rouge, LA
Hazleton Laboratories America
Madison, WI
Laucks Testing Laboratories
Seattle, WA
Mead Conpuchem
Research Triangle
Park, NC
National Analytical Laboratories
Tulsa, OK
O'Brien & Gere Engineers
Syracuse, NY
Rocky Mountain Analytical laboratories
Arvada, CO
S-Cubed
San Diego, CA
Southwest Laboratories of Oklahoma
Tulsa, OK
U. S. Testing Company
Hoboken, NJ
Versar, Inc.
Springfield, VA
60
-------
TABLE A-26. TCDD CALIBRATION STANDARDS I THROUGH V
(Internal Standard Method)
Lot No.
Description
2,3,7,8-TCDD
Concentration (ng/yl)
QASL Protocol
37C1-TCDD
Concentrati^Jn^h^
QASLProtocol
C-077 Cali. I. 0.209
C-078 Cali. II 0.971
C-079 Cali. Ill 4.93
C-080 Cali. IV 19.3
C-081 Cali. V 35.4
0.2 0.0605 0.06
1.0 0.112 0.12
5.0 0.190 0.20
20.0
40.0
-------
TABLE A-26 (Cont.) TCDD CALIBRATION STANDARDS I THROUGH V
(External Standard Method)
13C-TCDD 2,3,7,8-TCDD 37C1-TCDD
Concentration (ng/iil) Concentration (ng/lil) Concentration (ng/tjl)
Lot No. QASL Protocol QASL Protocol QASL Protocol
C-077 1.06 1.0 0.224 0.2 0.066 0.06
C-078 1.08 1.0 1.17 1.0 0.130 0.12
C-079 1.06 1.0 5.40 5.0 0.18 0.20
C-080 1.06 1.0 21.9 20.0
C-081 1.06 1.0 35.20 40.0
------- |