Pilot Study On
International Information Exchange
On Dioxins and Related
Compounds
Listing of Laboratories with
Expertise in the Analysis of Dioxins
and Related Compounds
Report Number 168
August 1988
HH^^^
North Atlantic Treaty Organization
Committee on the Challenges of Modern Society
EPA
600
6
90
oie
-------
-------
ACKNOWLEDGEMENTS
This report of the NATO/CCMS Pilot Study on International Information
Exchange on Dioxins and Related Compounds was prepared by the U.S.
Environmental Protection Agency (EPA), Office of Research and
Development, and Versar, Inc., under Contract No. 68-02-4254. Mr. Erich
W. Bretthauer, from the United States Environmental Protection Agency,
was the Study Director for the Exposure and Hazard Assessment Working
Group. The principal authors of this report were Dr. Frederick W. Kutz
of the U.S. EPA Office of Research and Development and Mr. David P.
Bottiroore of Versar. Ms. Wendy Grieder of the U.S. EPA Office of
International Activities contributed to the development of this document.
Versar personnel involved in the preparation of this document
included: Ms. Pat Wood, task manager; Ms. Juliet Crumrine, technical
editor; the Versar secretarial staff, Ms. Kammi Johannsen and Ms. Lynn
Maxfield; and Graphics Department, including Ms. Kathy Bowles and
Mr. Andre Price.
The information contained in this report was collected through the
contributions of tne following lead delegates: Mr. Martin J. Boddington,
Environment Canada, CANADA; Dr. Arne Grove, Kemiteknik, Teknologisk
Institut, DENMARK; Ms. Christa Morawa, Umweltbundesamt, FEDERAL REPUBLIC
OF GERMANY; Dr. Alessandro di Domenico, Istituto Superiore di Sanita,
ITALY; Dr. J. A. van Zorge, Ministerie van Volkshuisvestung, Rumtelijke
Ordening en Milieuoeheer, THE NETHERLANDS; Mrs. Sigrid Louise Bjornstad,
State Pollution Control Authority, NORWAY; Dr. E. A. Cox, HM Inspectorate
of Pollution, UNITED KINGDOM; and Ms. Frances Pollitt of Department of
Health and Social Security, UNITED KINGDOM. We would also like to thank
Werner Beckert, U.S. EPA, and Dr. Sergio Facchetti, Commission of the
European Communities, for their contributions to this listing.
_
o
IffADQUMIERSUBRARY
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
-------
-------
TABLE OF CONTENTS
Page No.
1. INTRODUCTION 1
1.1 Background 1
2. METHOD OK COMPILATION 4
3. DESCRIPTION OF LABORATORIES LISTED 7
3.1 Matrices Analyzed 7
3.2 Quality Assurance Schemes 8
3.2,1 Internal Quality Assurance 9
3.2.2 Externally Moderated Quality Assurance 10
(1) The Troika 11
(2) Contract Laboratory Program (CLP) 12
(3) Community Bureau of Reference (BCR) 13
(4) The WHO Interlaboratory Quality Control
Protocol 13
4. ANALYSIS OF THE LISTING OF LABORATORIES 15
5. THE LISTING OF LABORATORIES WITH EXPERTISE IN THE ANALYSIS
OF DIOXINS AND RELATED COMPOUNDS 22
LIST OF TABLES
Table 1. Number of Laboratories by Geographic Location 17
LIST OF FIGURES
Figure 1. Laboratory Affiliations 18
Figure 2. Laboratory Affiliation in Each Country 19
Figure 3. Quality Assurance Schemes Employed 20
Figure 4. Matrices Analyzed 21
-------
-------
LISTING OF LABORATORIES WITH EXPERTISE
THE ANALYSIS OF DIOXINS AND RELATED COMPOUNDS
1.
INTRODUCTION
This report presents a listing of laboratories with expertise in the
analysis of dioxins and related compounds. The listing was compiled to
facilitate the identification of analytical centers in the participating
North Atlantic Treaty Organization (NATO) nations and their capabilities
for such analyses. Also listed are laboratories located in participating
countries, or as components of international organizations, active as
observers in this project. In addition to the name and location of the
laboratories, the matrices analyzed, principal analysts, and descriptions
of the quality assurance schemes used are included. Finally, a series of
graphical representations that summarize the information in the listing
are presented.
The objective of this listing is to identify laboratories in partici-
pating countries having experience in the analysis of polychlorinated
dibenzo-para-dioxins, dibenzofurans, and related compounds. This listing
was compiled as a contribution toward international information exchange
on the analysis of these important compounds. It should facilitate the
exchange of information among those interested in this phase of dioxin
research and promote the development of improved analytical methods and
standards among the participating nations. The examination of this list-
ing of 108 laboratories in nine nations also illuminates some of the
trends with regard to laboratory affiliation, matrices analyzed, and qual-
ity assurance schemes used. Many of the laboratories listed have partici-
pated in externally moderated interlaboratory quality assurance programs
to validate and compare analytical results.
1.1
Background
This Pilot Study on International Information Exchange on Dioxins and
Related Compounds coordinated an international effort to address issues
associated witn polychlorinated dibenzo-^-dioxins (PCDDs), dibenzofurans
(PCDFs), and related compounds. The 3-year project was conducted under
-------
the auspices of the Committee on the Challenges of Modern Society (CCMS)
of the North Atlantic Treaty Organization. The nations that participated
included Canada, Denmark, Federal Republic of Germany, Italy, Netherlands,
Norway, United Kingdom, and the United States. In addition to the major
information exchange objective, secondary goals included the reduction of
research program duplication and the identification of knowledge voids
during the planning process. As a result, better informed decisions can
be made concerning future research activities and resource allocations.
When the project was initiated in 1985, it was divided into three areas of
study: exposure and hazard assessment, technology assessment, and manage-
ment of accidents.
The Exposure and Hazard Assessment Working Group, chaired by the
United States, was charged with several tasks concerning research and risk
assessment. Numerous information exchange activities were undertaken to
promote interaction and to identify duplicative efforts and knowledge
voids. Some of these activities included the compilation, analysis, and
distribution of information on research projects, regulations and
statutes, and methods of risk and exposure assessment in the participating
nations. In addition, the working group desired to develop an interna-
tional listing of laboratories with expertise in the analysis of dioxins
and related compounds.
The accurate analysis of dioxins in environmental matrices at extreme-
ly low levels of sensitivity is fundamental to many areas of research and
regulation pertaining to these compounds. The development of precise and
repeatable methods for dioxin analysis is required for assessing the risk
of these compounds at very low concentrations. For example, the effec-
tiveness of destruction technologies is measured by the ability of treat-
ment systems to reduce the concentration of these compounds to extremely
low levels. In addition, the success of a remedial action or a human
monitoring effects program depends heavily on the analytical capabilities
available.
-------
Ultimately, the control of these chemicals is directly based on our
ability to analyze them in a variety of environmental matrices. As a re-
sult, the state of the art in dioxin analysis directly impacts many other
forms of research. In recent years, there has been a greater emphasis on
the risks involved with isomers other than 2,3,7,8-tetrachlorodibenzo-£-
dioxin (TCDD), Because of the need to analyze and quantify these com-
pounds at very low concentrations (ppt or ppq) in various environmental
matrices, special analytical methods and equipment have been developed.
Currently, a limited number of laboratories have the capabilities to
analyze these compounds at the detection limits necessary for research and
regulation.
Section 2 presents the methodology used to collect and compile the
information contained in the listing. It also outlines the organizations
contacted for information and the criteria used to determine whether a
lab should be listed.
Section 3 provides a description concerning the laboratories listed
and the information contained in the listing. Specifically, the matrices,
analyzed and the quality assurance schemes used by the laboratories are
presented. Extended discussions on the externally moderated interlabora-
tory quality assurance schemes used by the listed laboratories are also
provided.
Section 4 presents some interpretation of the information contained
in the listing and illuminates some of the trends with regard to labora-
tory affiliation, matrices analyzed, and quality assurance. The Listing
of Laboratories with Expertise in the Analysis of Dioxins and Related
Compounds is presented in Section 5.
-------
2.
METHOD OF COMPILATION
At the time at which the Committee on the Challenges of Modern Society
adopted this project on International Information Exchange on Dioxins,
each NATO-member nation interested in participating appointed a lead dele-
gate to coordinate and administer the project for their country. The
following NATO-member nations appointed lead delegates: Canada, Denmark,
Federal Republic of Germany, Italy, Netherlands, Norway, United Kingdom,
and the United States. Observing organizations were the Commission of
European Communities (CEC), the Organization for Economic and Cooperative
Development (OECD), the United Nations Environmental Programme, and the
World Health Organization (WHO). In some countries, representatives of
industrial trade organizations and non-governmental environmental public
interest groups were invited to contribute as observers. For example, the
Chemical Manufacturers Association represented the chemical industry from
the United States, the Verband der Chemischen Industrie represented the
chemical industry from the Federal Republic of Germany, and the Environ-
mental Defense Fund represented the American public interest environmental
groups. In addition, the governments of Austria and Sweden, although not
members of NATO, requested to be kept informed of the progress of the
project.
To compile this inventory, requests were sent to the lead delegates
of participating nations and to representatives of observer organizations.
These requests asked for information on analytical centers with expertise
in dioxin analysis within their organizational or political areas of rep-
resentation. Information requested included: (1) name and address of the
laboratory, (2) name of the principal analysts, (3) matrices analyzed, and
(4) a brief summary of the quality assurance schemes in use at each labo-
ratory. Recommended criteria for inclusion on the list were (!) actual
experience with the analyses for dioxins, furans, and related compounds;
(2) procedures utilizing combined high resolution gas chromatography-mass
spectrometry; and (3) demonstrated ability to perform analyses at the
parts-per-trillion sensitivity level on environmental matrices.
-------
Several of the laboratories listed have participated in studies
sponsored by international organizations. The CEC Joint Research Centre,
Ispra Establishment, has been the moderating laboratory for CEC sponsored
studies and identified numerous laboratories included in this listing.
The laboratories affiliated with the World Health Organization (WHO)
study on levels of dioxins and related compounds in human milk were
compiled from the report of their most recent meeting in February 1988.
The report, "Summary of Consultation on Results on Analytical Field
Studies on Levels of PCBs, PCDDs, and PCDFs in Human Milk," contained a
listing of the participating laboratories and a description of the inter-
laboratory quality assurance program used to provide consistent analytical
results.
Laboratories in the United States were identified through several
mechanisms. In addition to EPA's Contract Laboratory Program (CLP), the
EPA has several laboratories that provide dioxin analyses. As part of the
EPA's National Dioxin Study which was completed in 1986, the analytical
methods development and quality assurance aspects of the project were
provided by the Troika. The Troika consisted of three EPA laboratories
and two supporting university laboratories and their function was to
provide immediate and valid analysis for the National Dioxin Study and to
serve as the nucleus for the development of the Contract Laboratory
Program after private laboratories demonstrated their analytical capabili-
ties. Information on the Troika laboratories and quality assurance was
collected from "Analytical Procedures and Quality Assurance Plan for the
Analysis of 2,3,7,8-TCDD in Tier 3-7 Samples of the U.S. EPA National
Dioxin Study."
In the United States, in addition to listing laboratories involved in
government programs, a survey of members of the American Council of Inde-
pendent Laboratories was made. Laboratories that were members of this
council and had combined gas chromatography-mass spectrometry capabilities
as reported to the Council's headquarters in Washington, D.C., were con-
tacted by telephone and asked if their capabilities matched the inclusion
-------
criteria. This process added several laboratories to the list and con-
firmed the analytical capabilities of several laboratories already listed.
-------
3.0
DESCRIPTION OF LABORATORIES LISTED
The listing contained herein presents the name and address of labora-
tories and the identification of principal analysts. In addition, the
matrices analyzed and quality assurance schemes employed are also included
as part of the listing. This information has been included as an integral
part of the listing, which serves to indicate the type of analyses per-
formed, and to promote interaction among labs in the participating
nations. Increased awareness of the type of analyses being conducted,
especially when dealing with difficult matrices, can result in greater
cooperation among labs in the forms of sample exchanges and other activi-
ties in order to develop improved methods.
3.1
Matrices Analyzed
When the requests for information on laboratories with dioxin analysis
capabilties were made, one of the data elements requested was the matrices
analyzed. Because of the variety of environmental matrices analyzed and
the varying detail of the available information reported on each analyti-
cal center, a summary grouping of matrices was developed. For example,
surface waters, ground waters, and drinking waters were grouped together
and presented in the listing as water. Other groupings, for which simi-
larities were not as immediately obvious, were combined for the listing
based on chemical/physical properties such as hazardous waste and chemi-
cals. In contrast, to many environmental samples where the matrices are
generally different from the constituents of concern, hazardous wastes and
chemicals may contain constituents very similar in structure and concen-
tration. As a result, many of the extraction and cleanup steps may be
similar.
In general, the matrix groupings were summarized for this listing with
respect to the type and concentrations of potentially interferring con-
stituents, the extraction and cleanup methods required, and the overall
difficulty in analyzing these matrices. We recognize the potential dif-
ferences in these matrices, and that, in some cases, they may require
entirely different extraction or cleanup methods and/or may result in
-------
varying detection limits achievable because of interferences from other
constituents. If you have any questions related to a particular labora-
tory and the types of analyses carried out, we encourage you to contact
that laboratory directly.
The groupings are generally as follows:
Water
Soil
Hazardous Waste/Chemicals
Combustion sources
Tissue
Food
Vegetation
drinking water, surface water, ground
water, etc.
soils, sediments, sludges
industrial effluents, solid waste,
chemical products, oil, pesticides
incinerator emissions, fly ash, air,
stack gas, automobile emissions
animal and human tissue, blood, milk
food from animal sources
vegetation, food from plant sources
3.2
Quality Assurance Schemes
At the time that this compilation was initiated, the lead delegates
from each country were requested to determine and describe quality assur-
ance schemes employed at each analytical center. The quality assurance
schemes employed at the labs listed vary considerably. All labs provide
elements of internal quality assurance; in addition, some reported partic-
ipation in externally moderated programs. Internal quality assurance
denotes that the analytical center uses procedures within the control of
the individual laboratory. This is the usual case in research studies
that are oriented toward analytical methods development. Externally
moderated quality assurance denotes that the laboratory participates in a
program under the technical direction of an independent organization
outside the laboratory's direct control. This type of program is usually
employed when a large number of samples are analyzed, as in organized
exposure monitoring studies. It is usually resource intensive, with some
type of technical assistance available from the moderating laboratory.
In general, the interaction among labs in externally moderated quality
assurance programs has improved the state of the art of dioxin analyses by
validating methods and analytical results through interlaboratory sample
exchanges. As a result, all labs, including those that use internally
-------
developed quality assurance schemes, benefit from these activities. Many
labs follow the quality assurance procedures developed from these exter-
nally moderated programs, including the frequency of instrument calibra-
tion, matrix spike analyses, and method blanks.
Both types of quality assurance programs are statistically based, and
their goals are to provide data on the variability, accuracy, and preci-
sion of the analytical methodology. There are no value judgments placed
by listing the internal/external quality assurance guidelines in terms of
the accuracy of the analyses performed. In many cases, the internal qual-
ity assurance standards are as rigorous as those followed by the external-
ly moderated laboratories. We have chosen to include this information to
supplement the information exchange aspects of the project because the
laboratories participating in externally moderated quality assurance pro-
grams are already utilizing information exchange to their benefit. Below
are some descriptions of the types of quality assurance {both internal and
external) being used by the laboratories.
3.2.1 Interral Quality Assurance
Laboratories reporting internal quality assurance schemes use proce-
dures controlled within the management structure of the laboratory.
Internal procedures comprise a discrete series of operations that vary
from simple to complex and generally cover the entire analytical proce-
dure. Operations include, but are not limited to, calibration of scales
and measuring equipment, confirmation of the decontamination of glassware
and other equipment, and more complex procedures such as recovery calcula-
tions and instrument calibration. The underlying objective is the deter-
mination of the accuracy, precision, and overall variability of the proce-
dure. Samples are analyzed in specific sets with both positive and nega-
tive controls associated with each analytical series.
The exact procedures employed at each laboratory vary, but records are
kept to document procedures. The proper evaluation of a laboratory always
includes a review of the internal quality assurance data base.
-------
3.2.2 Externally Moderated Quality Assurance
In the effort to develop accurate and reproducible analytical methods
for dioxin analysis, several externally moderated quality assurance pro-
grams have been established. In general, the interaction among labs in
the form of round-robin sample exchanges, blind QA samples, and coopera-
tive development of methods, has improved the state of the art of dioxin
analysis. Additionally, such externally moderated programs are structured
to promote the development and use of precise analytical methods including
instrument calibration procedures and multiple laboratory confirmation
procedures to produce consistency among laboratories.
In the NATO member nations participating in this project, four formal
externally moderated QA programs were identified: (1) the Troika, (2) the
Contract Laboratory Program (CLP), (3) the Community Bureau of Reference
(BCR), and (4) the WHO Interlaboratory Quality Control Protocol. Each of
these programs are described below. In addition, some comparative labora-
tory measurements and sample exchanges have been used in the Federal
Republic of Germany and the United States as a means to provide data with
greater consistency and validity. Working groups were established by the
Association of German Engineers and the Federal Environmental Agency for
analysis of emissions of PCDD/PCDF from waste incineration facilities in
the Federal Republic of Germany.
A Lake Ontario TCDD bioaccumulation study conducted by the U.S. EPA,
New York State Department of Health, and Occidental Chemical Corporation,
utilized interlaboratry comparisons using well documented analytical
protocols. Although it was not developed as a formal externally moderated
quality assurance program, the study utilized the analytical expertise of
the EPA-Duluth, the New York State Department of Health, and the Ontario
(Canada) Ministry of the Environment Laboratories, in round-robin compari-
sons to confirm analytical results for the use in bioaccumulation studies
of TCDD in fish and sediment from the Hyde Park landfill to Lake Ontario.
Included below are descriptions of the four formal externally moder-
ated quality assurance schemes.
10
-------
(1) The Troika
The Troika program was initiated in 1983 to provide a consistent
standard for dioxin analysis in the United States. The quantification of
2,3,7,8-TCDD and related compounds was performed by a limited number of
labs in the U.S. In order to satisfy the demand for sensitive analyses
at the parts-per-trillion level of detection, the United States Environ-
mental Protection Agency (EPA) delineated special measures to validate
the accuracy of analytical procedures for 2,3,7,8-TCDD to be used in the
conduct of analysis for the National Dioxin Study. Because the analytical
portion of the National Dioxin Study was completed, the Troika program
was terminated at the end of 1986.
The four basic principles of the program were: (!) studies to vali-
date methods; (2) "blind" QA samples; (3) multiple laboratory participa-
tion; and (4) defining analytical criteria for confirmation of 2,3,7,8-
TCDD. The Troika consisted of the Environmental Research Laboratory-
Duluth (ERL-D), the Environmental Monitoring Systems Laboratory-Research
Triangle Park (EMSL-RTP), and the Environmental Chemistry Laboratory-Bay
St. Louis (ECL). Also working with the Troika under cooperative agree-
ments were Dr. Mike Gross of the University of Nebraska, Lincoln, and
Dr. Thomas Tiernan of Wright State University.
The Troika program was structured to facilitate the exchange of QA
samples, test samples, and analytical results. The validation capabili-
ties inherent in these sample exchanges and "blind" QA samples, along with
detailed sample preparation and analytical methods, provided the means
for the generation of scientifically sound data. The interaction among
labs not only verified the accuracy of analysis, but also enabled the labs
to develop new methods or make modifications required to analyze trouble-
some samples. Overall, the Troika program established reference standards
for analytical procedures to provide accurate and reproducible methods,
enhanced credibility, and validity for the data from participating labs.
11
-------
(2) Contract Laboratory Program (CLP)
The Contract Laboratory Program (CLP) was established by the U.S.
Environmental Protection Agency (EPA) to provide analytical services in
support of EPA's Superfund program for remediating hazardous waste sites.
Because of the concern for dioxins in such contaminated sites and the need
for accurate analytical data for these compounds, the Agency established
detailed quality assurance criteria and validation procedures for a net-
work of commercial analytical laboratories with capabilities for dioxin
analysis. The CLP provides the Agency with consistent and accurate
analytical services and is closely controlled by the use of specific
methods, procedures, and reporting requirements.
The QA/QC program associated with dioxin analysis conducted under the
CLP includes:
Detailed requirements for initial and periodic calibration and
instrument performance checks, and specified actions that must be
taken when the specified criteria are not met;
Specifics on frequency of and criteria for method blank and
matrix spike analyses;
Field blanks with every batch of samples;
A blind performance evaluation sample with every batch of samples
- the acceptability of the analytical results depends on the
performance evaluation sample results.
In addition, the EPA performs complete and detailed data audits of
approximately 20 percent of the results submitted by the contract labora-
tories. A large and increasing data base is maintained by the EPA, which
facilitates establishing realistic requirements for QA/QC and for preci-
sion and accuracy. The EPA also maintains a standards repository for use
by the laboratories participating in the CLP.
These QA/QC measures are complemented by periodic onsite laboratory
evaluations conducted by EPA teams of qualified scientists.
12
-------
(3) Community Bureau of Reference (BCR)
The Commission of European Communities (CEC) formed a group to improve
the analytical methodologies for the determination of chlorinated dibenzo-
dioxins and furars. Specifically, the various isomers in addition to
2,3,7,8-TCDD have been chosen as the subjects of the study. The analysis
of dioxins is being studied in a series of collaborative exercises to
improve and standardize the analytical methods used. The participants
have evaluated several analytical steps for the study including sample
preparation, extraction, clean-up, GC-injection and separation, and MS-
quantification and identification.
Identification and quantification at parts-per-trillion levels have
been studied using solutions of pure dioxin-congeners that are labelled
with C13 isotopes. By using statistical techniques for collaborative
tests and examining the experimental conditions, the sources of error in
the various steps of the entire analytical procedure can be determined.
As a result, the entire methodology can be improved, and through such
collaborative efforts the sources of error can be minimized. After having
improved their methodology, the participants disseminate their information
in the form of certified materials.
This Community Bureau of Reference (BCR) program is being conducted
with numerous analytical laboratories in several CEC-member nations. The
overall program is being moderated through the CEC Joint Research Centre,
Ispra. Of the 22 analytical centers participating in the BCR in addition
to the Ispra establishment, 17 are located in NATO nations which partici-
pated in the CCMS project. (Four are located in France and one is in
Belgium). These analytical centers have also been included in this
listing.
(4) The WHO Interlaboratorv Quality Control Protocol
In order to provide consistent analytical results for a World Health
Organization (WHO) study on dioxins in human milk, a group of 18 labora-
tories participated in an interlaboratory quality assurance program. This
study was initiated in 1985 to produce more data on the levels of, and
13
-------
routes of exposure to, dioxins and related compounds in various countries
and geographic areas. Samples of milk were collected according to a well
defined scheme and analyses for PCDDs, PCDFs, and PCBs were completed at
18 selected laboratories, 16 of which participated in the CCMS Pilot
Study (and 5 of these also participated in the BCR).
The interlaboratory analytical quality assurance program was imple-
mented to ensure the validity and comparability of the analytical results
in order to produce reliable data for subsequent risk assessments. The
analytical protocol was developed and moderated by Or. Rappe of the
University of Umea, Sweden. Two separate pools of human milk were dis-
tributed from the moderating laboratory along with the C-labelled
standards to the participating laboratories. Analyses for PCDDs and PCDFs
were received from 12 labs and PCB results from six labs. In general,
high resolution GC/MS was used for PCDD/PCDF analysis while PCB analysis
was performed using gas chromatography equipped with EC detection or a
similar technique.
Additional interlaboratory studies are planned to take place as an
ongoing process with additional laboratories tentatively invited to
participate.
14
-------
4.
ANALYSIS OF THE LISTING OF LABORATORIES
The following tables and figures illustrate the information contained
in the listing. These graphical representations are intended to illumi-
nate some of the more notable trends pertaining to the laboratory affilia-
tion, type of analysis performed, and the quality assurance schemes used.
Table 1 presents, the number of laboratories in each of the nations that
participated in this project. There are 108 laboratories listed from
9 nations. Figure 1 presents the breakdown of laboratory affiliation
(government, university, or commercial) for all the labs listed. Of the
108 laboratories listed, 40 percent are commercial labs, 37 percent are
affiliated with government agencies, and 23 percent are university
laboratories.
Figure 2 displays the affiliation of the laboratories in each nation.
In Canada, Italy, and the United Kingdom, the majority of the labs are
affiliated with government agencies while in the United States and the
Federal Republic of Germany, more labs are commercially operated than in
the government agencies. It should be noted, however, that a considerable
portion of the clioxin analysis performed by commercial labs is in support
of government programs.
Figure 3 presents the quality assurance schemes employed at the
laboratories listed, while Figure 4 displays the types of sample matrices
analyzed at the laboratories providing this information. Over 30 percent
of the laboratories listed reported that they participate in externally
moderated quality assurance programs. Specifically, 18 laboratories
belong to the CEC Community Bureau of Reference, 16 participated in the
WHO interlaboratory quality control program, 12 participated in the U.S.
EPA Contract Laboratory Program, while five laboratories listed were part
of the Troika. Although the information on matrices analyzed is incom-
plete (only 75 of the 108 labs listed reported the matrices analyzed),
most of these laboratories have expertise in the analysis of soil, water,
and tissue. The analysis of combustion sources, chemicals, and hazardous
wastes are generally common practices at these laboratories. The analysis
15
-------
of dioxins in food and vegetation is relatively scarce and only a few
selected laboratories reported these capabilities.
16
-------
TABLE 1. NUMBER OF LABORATORIES LISTED
BY GEOGRAPHIC LOCATION
Country
Number of
Laboratories
Listed
Canada
Denmark
Federal Republic of Germany
Italyi
Netherlands
Norway
Sweden2
United Kingdom
United States
Total
108
1 Includes the Commission of European Communities, Joint Research
Center, Ispra Establishment, Italy.
2 Observer Nation.
i/
-------
TOTAL NUMBER OF LABORATORIES LISTED = 108
FIGURE 1. LABORATORY AFFILIATIONS
18
-------
DC
O
O
O
UJ
CC
O
DC
O
CD
CM
UJ
CC
O
aiisn samoivdoavn do
19
-------
1 6
WHO
INTERLABORATORY
QC PROTOCOL
COMMUNITY BUREAU
OF
REFERENCE
12
CONTRACT
LABORATORY
PROGRAM
TOTAL NUMBER OF LABORATORIES LISTED = 108
FIGURE 3. QUALITY ASSURANCE SCHEMES EMPLOYED
FIVE LABORATORIES PARTICIPATE IN THE COMMUNITY BUREAU OF REFERENCE
AND THE WHO INTERLABORATY QC PROTOCOL PROGRAMS.
20
-------
45-
40-
35-
30-
Q
111
CO
Hj >
II
i°
3p
s!
111
Ed
25
20-
1 5-
1 0-
5 -
777.
45
42
(A
52
t-
25
z
O
CD
u;
o
m oc
00
U i/>
22
to
OI
11
MATRICES ANALYZED
FIGURE 4. MATRICES ANALYZED*
BASED ON 75 LABORATORIES INCLUDING INFORMATION ON MATRICES ANALYZED
21
-------
5.
THE LISTING OF LABORATORIES WITH EXPERTISE IN THE ANALYSIS OF
DIOXINS AND RELATED COMPOUNDS
22
-------
o
Q
J^ OJ
W CD
is oj
X3
O
O
1/1 (/) >O CD
U t/> PO .
C3J - LO
+J "O 3 ^^
(A ^ fO 0)
0> O W CO
C O W (A
"O
c
23
-------
«
c
i
n>
g*
£
U
C
o
*!*
o
l*_
£
,
c
o
£»
f-
1
"D
1/5
+J
O
£
v
O
2
T?
"
c
g
-
O
o
o
v)
to
>.
w
c
0
**
c
"-
<1>
I/I
+*
u
X
tfcj
.c
X
VI
^1
01
X 0
* C V
r (_ 0)
B 3 -C
3 » 0
O' V> tA
in T3
01 0>
U N
i!
(A
-»-l
tA
^
C
^
a
u
c
t_
a.
c
o
>D
O
X
4-»
c
o
CJ
^_ ^_ , r_
c c c c
U I_ t, W
QJ QJ m o
c "c ^ "c
L.
ttJ
cm oo
L.
C t)
(U (J
LJ -r-
a> CD
4-J X 0
>i O 4-* O O
L. U-l -- r C
o o *-» o -C
4-1 ^B hi*] tn CO
U C_> X U 1
« - * 5 1 n 1
«-* O QC tJ ^ "3
*- O (D L- OJ (U
3 0> ^O OJ t- 4) "D OJ i
C T3 O fO C C O T3 -T) <_> C O
o c ^ _j ^ ---» o i- o - - ^ (_c
z^ujcoa-s zuj-_i 0:1-
"O
a;
c:
"Q *-»
C 0
"3 O
0 x_
W
(J
1
c
2
aj
O
a
s
o
t-
JJ
o
r_
tJ
c:
0)
__
tf>
d)
4-» (J
v> i-
» J
3 C
0 0
-a
U 4-*
(D cr> (U
to -O (/) £U *~~
x e w 4-» "-
O «- (O O
c
1
ft)
CO
ai
Q
L.
z
c:
*tJ
U)
OJ
i_
CD
w
L4-
o 3 ftf
C -*-»« OD *CW 3
24
-------
01
*-)
c
c
a
o
ro ^J
w J?
^ a>
x «
o -r,
o
o
t S
o *
£ -
4-» W
o r
*j °
° *
<-> u-
si °
Q
£
** ,^
Z -M
>t O
flQ 3 _C
3 Sfl L»
O irt *./1
C
QJ
C
IU 1_ +J
*
V)
x to
Z3
. l£)
I/I 1C
OJ
a; o
o i-
o o c
o
a> o
« E o
aj t_ i_
> m aj
c a) (O
^103
i-
o
.a
(U 4-1
6 E c o
c O O CNJ
O -*- ro
i- «7> - UP
o
(D -sr 3
r^j ao CD
£ g
E J=
C O
O
I- «
Q. »- 1
c co a;
O (U
l_3 4) J
< 41
> C -Q U-)
ro flj QJ i
QJ 01 (U
25
-------
I/I
T3
C
3
O
g'
o
g
w
+»
IO
01
oe
TJ
C
"C
W
C
X
0
Q
g
g.
1
(J
X
UJ
C
0
4-*
O
c
I
-*-»
*o
a
u
to
4->
c
c
o
1*
+J
crt
+*
O
Q.
to
X
O
CJ
-Xs
o
«f
z
O
(U
d
c
o
u
(O
o
c
1
§
^J
Q
0)
4-*
IB
0)
QC
-Q
C
4_»
^
g
X
UJ
.c
*»
>
M
m
t_
a
*0
1-
.8
1 U
+-> c <0
>o c
XL «t
IA
VI
^>>
ID
^
t
J_
«-*
i
i_>
^ fO
c c
(D OJ
CC *-i *J O
o c c x
OJ
3
1 1 1 (A
1 lit/1
j II-"-
lil-
i_
E
t. *-
? i
cr CT*
4) C *J
I- O -*- W
CO t-
4> :a
I- U.
Wl Q JC
O
^ ' t/> CL
H-
o
t- t- V- I
Q CL Q Q
g
a>
en
o
c
u
u
u
4-> 4~»
^_ g
0> tJ
_ i o»
csj 5 c
a
UJ t- -C
O L>
"O i **- n
c " w
3 ^ a* *J u
I C 3 41 0
hj KJ CZ> D -4-* <7> 4-* O
^J f*> ' *-! CC CM
3 * 4-» 4_* « i n 0> CD ro
.C-MOIC4-* in (y «4- i/> ^-c o>
u - ^(-fD( t- T3 -Q cuc/)i^> aitAc o-*-*a> _< a> « -M LT>
J£ i > JZ"o ai c to 3 a»
Wl^JO - _i O (_ OJ CT f --- £ 21 C
tD x: to " ^ to ^ L_ +j CTI c u a> o o
«T «3 cs* o j<: O u ^) r^ £"Di-^-4»
trt t ji L O tT> O0ir»- OEO OJL.Q)^*'
«t O) l- *O r«» O -.- -^ ^ --~
CD CD < O UD ODt^cg cOXtO O^i^-Qt
H_ . -s
O *D
01
U =>
> >, c
rtJ *-" c -
Iw. J3 (Q *-
« ^ e g
01 a> 01 u
u_ cr <^ *
it! T-
c: c"
a> o
*-» +-*
c c
I '
QJ -
j3 C
t- ^
*n jC
^3 U r-
yi *
*D >T>
3E i^ CO
Q O O
o>
c
3
JC
o
X
c
U-l
"O
c
«J
a>
c
Z3 O Lfl CM
JZ C > < -^ CM
[j *- rO i-O
i/) cu i CM
I- 4-» --4 O) 1
D (/> CD OJ O CTi
tju. ^ r-» o^dou^uD
-------
g-
o
x
o
o
.0
TO
Crt
J!
CJ
yi
*
c
0
Csj
0
fO
0
00
_c
LJ
+-
i/>
o
Q_
o
00
+J
L-
=1
Jtf
C
ciT
OJ
21
t-
«-
CO
OJ
-C.
CJ
T3
^1
CO
c:
2
3
O
Q_
s
QJ
(_
Dl
C
i_
^i
01
CD
0
m
^
«o
3;
O
a
o
OJ
CNJ
CO
01
t~
0
_s^
O
l_
3
"4-
V*
13
4-1
-M
VJ
C
-
u
0}
T3
s
_C
U
o
a>
o
-o
c
o
oo
o
o
PO
J^
u
TJ
<-t-
4-J
V)
o
a.
^
w
3
(D
U
>*
'XJ
CO
o
oo
ID
CO
f\j
evj
kn
--,
fSI
01
o
OJ
1
27
-------
c
5
5 «
* Ij
11
o £
X *
o
S1
T3
V
_
4)
-M
C
0)
CTi
"O
nj
o o
m
c 3 ~
m £71
i m o
CO CO C^
*- O
0-
M O
C 4-1 O
to CM
Ol ^~
5, i
4-1 JJ O
(fl >»- O r
C 3 O UJ
d tr o <~
O u *O *O
> CO it-
5
o.
U in *rt C3
>* c
28
-------
01 >>
C I-
o
o
Q.
E
o
o
13
0)
I
C
o
0)
o
o
D O O
LJ C 01
^ (D O
O 1-
CD O
o
o (u
O IM Ol
it) C C
(X UJ
i
e en
-C OJ
I
o
I
cr>
^ o .
r> O O -
13 1- O 0)
h~ o cvj >
CJ
LU
o
O T3
. C
D C
5 3 e c
D Q. I- O
29
-------
^
T3
trt 3
a ^
c JI
3 C
1 ^
"O ^
* 3
t; o
,2 Q.
£ S
* 0
i |
c "oi
x ^
O -^j
^^ c
§ £
a) r^
5 0
fj
UJ *°
§ I
4-» y?*
0 <*
*c *"
1 ~
2 £
^ *_
0) *
J_» ^^
'c x
C ~S
o .t!
f *
o £
i/>
ac -1
^ °
1 -
* u
t? J5 1=
r- L. flj
n tn u
Gr (n en
to "D
OJ 0>
U N
*- >>
«-»
(7) -C Ul
*r r-* o i
CM *- ^r
CM O trt
l i O tO
C7^ *»J O
Of * W d
~- (J « JT *O OO
Hj flQ ^f 01 CD Z l
C i O ' U ~ < «-H
0) ro .4-.^.. >,m
LJ Oi M ^* */> CXL-rt »~ro
ro c to < O1 ^0*0
O Q)>J - '-0)^C*J
*.*- . U M .. O "U Z 4-* J X O. ZX 4->**-L>JZ ^
*-* (0 -T- fD 3 U
i_ £E c> o> x "4- *j *o m r-, oj x
_J O O C 4> flJ -^- 3E ' fcT>C(U
z *c - cn i CD 0) ifl --ojcfl;
LU .J > CM Q_ 1^ t »-« 3» - c a*
C 31 E «5 CD
t/> O t_l CD O
V} O t_
OJ C O O 0)
(D c: c u
r- t_ -^ o
^ L Cj tj Z
d O C3 <^*< Q
o
J£ _j _j
OJ l_ => S
0
4-> 1/1^
*D Ol fM ll
u 01 to c c
01 i O O
O X 01 C C
o Q) ^r i-
*D O CT) » ft) (D QJ
tf) « (JJ ' CM J/l
&_ O *ti C O O +^ C - fO C
O 1 -^ QJ C«< ' O>O Z O
F- O> ' i O ^ M -*-> J N*
(- -- O UJ >* i O ^>, "-
*->4-»ocxQ!: ^x z "~
4->UOQJ*-JQJX'4- T3 O QJ
r-ou' to c aj at > oc >
(o m » o r^ ft) {y 41 i*~" ^ cr (y
0
a
CM
OJ QJ
0
c
dj fti
tn o
o
z: u.
01 >»
- (L
»~~ Kj (O
QJ t- '
*J "-
c u.
0
O -C
30
-------
-o
c
o
CD
O£
o
O
T?
O
^>.
O
e
.c
-> T3
O) &
U N
> e
LQ u-
o o
CX O_
O.
Q.
<
3E
-*- "U i-- ro i «
"
> -r~ o *J roc
'-+J[J-*J'O^^O
Ci/)iu U-CJ^-tVJQ-
O i/l O
OJ Irt O (D
3 3 ^ M
£ QJ
cn e -^
G> a) ^~
c_> c c o o c a*
t_l - O > CD
> t_ QJ flj
T3CSOT3T3W C to
C 1-
E 0) -*-" U>
T3 C ^
i- o e
4->
-
u *O »- QJ 3!
GjLxi . -
>OOucoo
- JD t fl) « OJ
O
o
C l-
TO O
^ B
S 5
3 0) 01 ^^
*- (D LJ O CO
O <-> X f)
C CD 03
- c S . o
31
-------
(A
a
c
o
6
U
a
u
«
0)
ac
13
C
C
X
o
Q
C
o
u
o>
i
u
UJ
I
4-*
O
H-
C
c
o
a>
*^
i i
o
^
55
^
o
.p_
NATO/CCMS P
T3
Q>
3
C
4*»
C
o
u
in
C
o
o.
I
1
0)
ex
c
Q
(A
C
X
o
°
o
Ifl
I/)
c:
c
V
*-»
&
X
UJ
.t
*-»
X
*ft
^
o
TO
t_
o
&
H-
o
f
u»
^J
x u
*» c J>
'Z- 2 5
"O
U 01
L> N
t-
«
+-»
^
TO
C
^_
Q.
U
o.
0
TO
O
o
4_t
c
o
o
ce
o
CD
V)
0)
o
t-
o
o
13
§
c
o
_c
1-
5»
Q-
o
t
^
Sclent if ic Researc
T3
3
c
4_»
C
O
u
" "
or of
CJ CJ
IU W QJ
>*-> U *-»
« L-
o o ui o
-6 -^ T3
j_ ^j ^ ^
nj do o ro
X E Q) X «-> *"
O £. ^ O
|
S ^
/^ CD
^ _^
, S > O 0
DI i ^ *-* r**
o . CT*. *-» o « cr-
f ^ ^o i ^ TO t- cn c^
I_>^; roO*"^ |0>O1O
d> ^- c *-* cn r~+.
t i*_ *>O C Ol O * C- .U^U^
O *** "^- rn TO tvj t_> f
i»_ ^~HI rn ts o *jr-»>^Ln ^^
O-t-JOOOtO) »" (DCVQJf^av
d QtD i»c otn^t
cajx m zaj c w_ex o
oEOuju-t ^_, o ccoi' x
r~*->CD'GC'~* u^ ^ » < o ca -a; --TO
I/I t_ *fc OS O I/I Q. *- X **-
TO - O JCXQ.CJ 3t O ' flU Q.OOCO Q. Qjr- ^ > O O r
- QJ -LDO ^ -QJOJ
a
(O
(U
*4-
o
>,
4-1
C
0)
u
QJ
1
LA
cn
c
4-1
,
L.
O
4-»
I
OJ
10
c
t/1
'O
-------
r U 0)
T3
c
3
O
I
o
QJ
Z)
CO
(rt
I
CO
fO
u
1
o
o
T3
c.
13
N
5
o
I/)
3
i
o
o
^ a
o
HI
T5
t:
"3
O
O
^1
a
01
I- (-
n3 us
z: <_)
T3
O
O
-C
u
s
i^:
-a
-a
C
^i a
T3 o
t-
O
TJ <
"
"O
u
o
. -CO)
o
^
CD
>, c
l«_ ^ -^
o a
VI
s- "u
a si (u
5 .2 *
33
-------
tf> T>
a> QJ
o £
§ ~
o £
a) r-
ro O
o
c
o
o>
c «
.2 »
o
>t-
c
2 ?
° .T;
II
"> u
« I
a
o
0*
c
Q.
*O 0)
C Q
O
a> £
Ot UJ >i
I- C
e o 3 a*
(/i 4-^
Z g
34
-------
o
OJ
*-!
2
01
cc
T3
c
<0
o
o
01
o>
I
o.
U
c
c rt
« kij
QJ
-C
01
o
4-»
U
E
o
c
i_
Q.
su
O
TJ
c
"-
o
Q
..
o>
.»_>
3
O
"O
t-
N
31
>, 0
3 *T
OJ O
(-
(U >>
CO r-
QJ
r « V
tn i-
tr^j co
ffj
C3
O
i
O
m
.
*-*
c
0
i_
^_
>
C
ix>
O
C
Q
>
Q
*D
*j
0>
O
t-
>
LU
in i~
QJ a
U U~
ET
- cu
t/J C
CJ
-*-J
c
0
o
CD
VI
01
o
o
OJ
-M
c
o
o
*D
Ol
t£)
i
CO
(V
l/l
^_-
00
o
3
O-
E
CJ
C
o
in
0)
r^
.»
Q.
-C
CD
o
rO
CM
LD
CXj
X
O
CO
o
a_
o
r*.
CM
CJ
a_
a:
PO
co
en
*
^
OJ O T3
c
3
o
35
-------
o
3
O
1
LJ
TJ
V
a
at
a:
"O
*-»
O
ATO/CCMS Pi
2C
1
c
4-»
C
o
in
o
c
3
CJ
TI
at
K>
u
OL
IB
(A
C
X
o
a
o
VI
1
c
i u
«§ j «
(A "Q
0) 0)
O N
£ 1
(O
"«
2?
1
S.
u
c
a.
c
o
M
3
£>
c
3
O
y
'o a.
t- -J
(A in
01 01
-~> o -- u
Q) 1_ V I
4-> 3 +-> 3
tn O (rt O
ZM W IX w
w «j o w *o o
30 30
O - *J O 4-"
fw ^_ "- >- _3 3
O * N CJ E «
O O 13 7X LJh~
^
£
U
>> z
Q.
Q
>, 2
.a c
3 0
>
v> O
01 «J
o m
(Q Q
-M ^ -Q >^
tfS L> IT) O
>» .a c j *- c
J- 3 (U CO)
O in o) CT vi QJ CTI
-»-* «c co e e <
*^j O U~* QJ tt
OXOrOfO W O
HJ f -M '* l/l > +-1
_j u >^ a. CD o
T3 Q> Ol Q. C7t Cl 0>
>i c *J o c -» £ a> o o
(O Q) C C Z < <
C LC..OII C L--II
§*Q '> i 'coS P^O^'SS'V
c -TO ^fi ^ c c1 C71 |^fc *-f^
O OJ UJ c *-* O
O
O
u_
&_
(V
4-1
S
o
uO
OJ
±s
4/1
(/>
t
Waste/
VI
=3
f-
*O
KJ
S
w>
m
o
CJ
Sources
c
o
*-
IA
a
ja
o
-o
o
o
U-
1
o
c o
tu i_
C7\ (O
yi » O -M
01
-«->
O
Q-
o;
O 1- i
*-£'
O 09 UJ
\S^ if) **
O I! r ^J
^ C -M 3 -«->
O U uJ t_J -C
o =3 to a
L
36
-------
(/}
T3
C
0
Q.
5
T3
OJ
+*
i
» U
(o 3 .c
=J W O
CX «n t/i
w> T3
Of 0}
0 Nl
U «
4-» (0
Z *C
l/i
>.
o
c
'O
Q.
O
c
t_
Q.
O
^j
"3
0
_J
i-
C
U
O
CJ
r
C
t.
c
^^ (J
0) U
t/) O
«O CO
3 60
c
UO ,
U
c
:-, a>
4-J
PJ C
t- O
o -- ui
^3 +j r-i
03 o <
_J Qj CD
0 O
CJ t-
U Q- S.-
> i 0
t. rt> trt
O -i-J 00
U"> C T3 -
a> (0 ac .
-- e o co co
o c cxr - co u>
r i- c 4-1 i i
O -- o - to r*.
5 uj C C trt
O 3 *o --- -
> (/> CTi C " *
LiJ t^> Qi CSJ ^ ^-- ^^
CO
*0 -Q
*J H3
01 73
13 «-
(U 4-*
o
JI U
a.
i
O
u
O
o>
c
trt
h- »
GO CM
CO fO 00
C r-, ^-J i
Ex c\j
§0 - t\J
CO CT
*" ° ^
> 0 - 0
c: -0 c\j
LjJ d- LfcJ ^-^
r^
C
01
c
?>
V)
h-
>^
01
Ol
a
o
Q
n.
01
Q
U2
>^ a
«-> ro
^ C\J
in m
QJ *ti
> TD
3 O
(U U.
-*-»
-*- fl>
-s i
-- ^
0 ^
~ TO
u_ ^~-
r
flj
c
t-
0
°
c
0
j;
£
^
i
o
01 Cxi
3 0
I- 3 CNJ
O L/l
(_> 1 «
"O - O CO CO
C *- m co
(U C 1 i
"D t- O CO if)
§+-> +-» *T T
trt O> C\J Cy
u- C
£1 CM l-O
t/> o trt o >
O *U f\J Lt.
r^
C
0)
*-»
c
a
o
o
U-
c
<0
y
u
3
i-
co
tJ
^
1-
a
>,
c ;-
o
«- o
«-> «)
1/1 1-
o
c +-
11
3
L- *-)
0 U
C *-"
o
o o
Li_ d
id <£
O Q^
t/> *- 1
Z3 CJ ^
(U
Qt fP
-M (O
go O ^- ^~
_C r», r*.
un * t t t
r*"> rO rO
LT> l/>
4-J O CO rO
Crt CTi
3 L> CSJ i/)
O _C rO U.
37
-------
TJ
1
I I
o
o
, >
o I
- I
C
JC.
1
JZ
u
C QJ
O or
00 O
o en
c -- r*»
- x o
E O CM
T3 Hi r-»
<
U. C/l
CTi O «* *-
l>0 r
(D TO *
l£»
O CM
o en
<\j
38
-------
o
c
10
-C
4-J
I
M
111
L-
o
vi cji en
»
-o
00 O
>> cn LD
O
-M c
-------
-8
c
?
^»
CE
V)
c
X
0
o
§
fi)
ai
c
X
LU
O
o
]c
-
f-
o
4-1
c
0)
+_i
^*i
c
o
40
M
JO
.,_
a.
o
o
3C
^^
0)
C
c
o
-D
C
I
<0
QC
o
5
c
*~
X
o
o
o
u)
J,
c
at
x:
(T
'*~
41
(O
4->
O3
d
X
U->
'5
u
L.
O
1-
_l
M-
o
tTI
C
4-f
*n
_j
a>
>. u
3 v> o
O
2
T3
OJ
c
u
fc-
0>
-»-»
0)
o
u
l_
0)
«/i
0)
C£
OJ
*o "O
i-> ID
D m
-Q a; o
3 (M
o
i_ C 3
I- " O
to crt .-<
IQ . ..- .
*-» ro Z 3
C O O ro
UJ C* O
j ^
OJ
3
.5
*-»
c
o
u
TO
c
0)
*-"
UJ
CO
(0
*
(0
--^ D
I/) O
ID L.
U
U-
^
Q
Q>
to
OJ
U
£ £
« i i
>i o cn
c in t£>
t*~ 5
fO £
O *-
§UI
H c: 3
COD
*0 t- _j
to
O C *J
-o
c
L,
OJ
*j
C
1
1_
c
1
r:
+j
(U
c:
c
OJ
^
L-
Q
0
^ r«.
*J r»-
CM
Tl
OJ TO
X C
r~ 1
tO (A O
*J (J l-
(U W (_J
e >*
c _c ^:
o Q. 4-»
t_ O k-
*- o
> CO Z
c
UJ t-
|Q .^
it- r i_
O 3 O CVJ 'r~ O^ Ol
C CM U . i «
"« « >S ^H t 1 I
0> *- *-* cn
r U O X -C ^T 00
«D C *-> O U U*) tjD
C CU tl CD l-
O *" *- *O "* j^~*
*J t/1 A O V* «-"> ^~
ro
U I]
QJ 4/>
4-J (rt
«o *- o
at >- co
cn
tn
O
L.
VD
i
Z
L-
0
c
a
0
c
_l 0
*- o
ID *
>\ CQ
(D U CO
J* »-* "J~l
in v> CO
in -^ to
l- E
Q (1) -, 4J X Z
-*-> C c - r-x
(rt E . O C *T
ai u r- o -
>
u)
a>
Q£
-o
C
t-
0
4-»
(Q
U
0
X3
tD
_ i
t_
0
n-
(^
OJ
c:
x:
'ddswort
0
t-O
jl
fO
OJ
31
4-
0
4->
I
4-1
I-
&
£
OJ
-------
TJ
w
T> "°
g| C
^5 Q.
111 §
02 3
g -o
s «
« *
c ».
-. **
° "D
S S
C ,_
0 g
, *
1 »
3 »
tn "j_
.M o
Q "*"
^ 1
"> 5
5 ^
" o
° 0.
s a
d
o>
>> o
3 Irt U
Gr */> *vi
i/1 T5
U N
r- >,
L. i
4-1 IJ)
£ i
to
i»
>i
n3
C
«t
T3
Q.
(J
C
t-
Ck-
I
4-1
Q
_l
>-,
4-»
C
13
O
(_>
(U
(U
S-
Hj ,_ ,_ r_
U- (O *o *o
tu c c c:
or ik t_ t.
OJ
Cw -Q -M
_J H) _J C C C
tJ _l O *
l/J CO
0) OJ
'-^ O O *-*. '^
0* I- U. 01 0)
^_t 3 3 *j 4-"
V) O O W CO
nj t/> t/i fla ea
3c w 3: w 3
^ C C r-
ui m o o oo 03 en
3 O 3 U 3
Q .r- 4_» ^_* O - O
a>"oEi/)w "ae a> ~o
l-=II_aiI3Z)i- U QJ (_ 1-3 (-
4-*---i/JONLJE g 4^ NO ---»-» 4-i^-(O N
40 O '" O >4 O O*DO *0 Oi3 ifl O '~ tj
3ELOI Lj.1 O O3EUO Z t/131 3Et/1h I
JI
4-»
o
"D 1>
[At- ^
3 U
*-' i/l fl>
iu o x: z
;r _i +-»
(J O
3C O - t>
z c:
1J C 4>
O C 01 t_
> *- ^ 1= *
iD CO O TO
C3 «t T 31
I- t_ l_ U t-
o s: a: o o
i/) C
OS S- - -C U
ill C
> -*J ru 3 *
C I- O
i/) Qj O
_J 1- I- 1 Od 4-*
-c: 01 o i- cj c N C -4-> t- *$ *-* T3 CD
T3 i) S ^" r< '"" c 3 CO C
> tfl t_ CT3CM LJOU>- w»Ct*^ O
dJOJ'DCT> i*jn3 GO f O 13
*- T3 ;> CO t- O -CUfD iOO Oi>-^ O '" O t-tDCa-O O
4-1*0 rO t£j(U^^ E36 ' i^O »[rtO^ oO^r-^-i iTJ.C^ U_tO 4-»« CCD O
E u fO ro uiui-n 4-"t_JC co tnojxoo ui
i/iciicjtr^ c^irt^r c ---oonscM -r-^o+Jto
$- O 2: QJ a,cU3 QJ*-'O *" L) T3 flJ O£ t~* (Q . . S *i «~ LD fsj t- *t B C\J CVJ '»"
-~>C3i/)O CDOL-- 1 UOOX'O''-^ XIGOOC:-^ "D
(~CU^for^ -ro>>rO UOU3O"-r~» (0CsJ- O X rn DQ 2: IX »-« CL t/7 * C3C
w
03
'0 TJ
4-* I-
« X
3 O
41
-------
VI
T3
d
73
Q
0.
0
-
4J
T3
OJ
or
"9
TS
i/"-
C~
X
o
O
c
o
OJ
01
c
TJ
_c
CJ
X
LkJ
d
O
-trJ
P
i_
0
<4-
C-
na
c
a
*"!
*0
C
S-
01
c;
c
0
>^
-c
3
4_)
«-n
"5
Q_
*J~»
^.
t~)
O
0
1
z:
_-^
T3
a>
^j
*"
c
Q
L3
i/)
o
r~
13
a
d
E
O
O
o
a>
^->
>TJ
a>
ez:
T3
C
*0
*A
C
X
0
C3
0
V)
t/>
>v
*D
C
«I
OJ
JZ
^_I
c
OJ
iA
"~
t_
- m e
^ -, ^
13 ifl U
*
t_ '
4_J fQ
a> C"
i: \
U
a.
o
^_j
*D
ij
0
>,
(_
4-1
C
13
O
O
m
c
i-.
4>
c
S-
OJ
113
rt
UT
2
0)
L.
"D
C
QJ
F
t>
^-j
t_
0
*0
c
1
c
0
t-
.>
c
Q
C
*D
!/>
U
L
a
*c U
i_ C ro
0 ~ T
JD CO
(D - ro
__t 1^ ^-,
0)
X U X
CO
C L
<0 OJ
> tn O
ro
«-^
^T
CO CO
u~
<:
c~
t_
> r--,
C (J>
to
C3^ C «
C OJ -H
- > in
*j <; in u~>
f/> CO
a> ^ TT
r * SI C7i
OJ '
>> ? -
C OJ
r- CS) - (
i to *j i£>
\ Id en
eu
>
<
QJ
_i£
O
. i JO
O CN*
m o
t_ tr>
OJ CO
o
"O rO
a> o
01
i*- r--.
D>
C '
r~ fO
Q, !*«
ul
"I
O
>*
42
------- |