INVESTIGATION

 

CONSISTED OF SEVEN TIERS

TIER 

PRODUCTION SITES (AND ASSOCIATED
HASTE DISPOSAL SITES)

SITES HHERE HAS USED AS A PRECURSOR TO MAKE PESTICIDAL
PRODUCTS (AND ASSOCIATED NASTE DISPOSAL SITES)

SITES HHERE AND ITS DERIVATIVES HERE FORMULATED INTO
PESTICIDAL PRODUCTS

COMBUSTION SOURCES
SITES HHERE PESTICIDES DERIVED FROM HERE USED

PRODUCTION SITES FOR OTHER CHEMICALS HHERE FORMATION
MAY HAVE OCCURRED

BACKGROUND SOIL, FISH SAMPLES)

RESULTS



TIERS 1 AND 2 - PRODUCTION AND DISPOSAL SITES
TOO SITES IDENTIFIED (Fewer than the
400-500 projected)
21 RELATED PRODUCTION FACILITIES
- 79 ASSOCIATED HASTE DISPOSAL SITES (most are in Missouri)
THESE SITES GENERALLY HAD THE HIGHEST LEVELS AND GREATEST
QUANTITIES OF 
- IN A NUMBER OF CASES, OFFSITE MIGRATION HAS OCCURRED

- A NUMBER OF FISH ADVISORIES HAVE BEEN ISSUED AS A RESULT
OF CONTAMINATION

- FEDERAL, STATE AND RESPONSIBLE PARTIES HAVE INITIATED
ACTION TO ADDRESS CONTAMINATED SITES AND CONTROL
HUMAN EXPOSURE

- LACK OF DISPOSAL CAPACITY HAMPERS IMPLEMENTATION OF
PERMANENT REMEDIES

TIER 3 - PESTICIDE FORMULATORS

 

GENERALLY NOT FOUND TO BE EXTENSIVELY CONTAMINATED ABOVE THE 1 PPB LEVEL
(WITH THE EXCEPTION OF THO LARGE FACILITIES) - I.E. NAS
USUALLY DETECTED IN ONLY ONE OR TNO SAMPLES AT A GIVEN SITE.

EPA ESTIMATES THAT 10% OF THE 300-600 FORMULATORS OF PARTICULAR
PESTICIDES MAY HAVE LEVELS GREATER THAN 1 PART PER BILLION (PPB)


APPROPRIATE ACTION.

REGIONAL OFFICES ARE ALSO FOLLOHING UP AT LARGE FORMULATORS NOT ORIGINALLY
SELECTED FOR SAMPLING.

 . at -cL 0 --

TIER 4 - COMBUSTION SOURCES

TESTED FOR PRESENCE ISOMERS OF DIOXINS AND FURANS IN
ADDITION TO 

13 SOURCES TESTED (approximately $100k/test)

- SIGNIFICANT NARI-ABILITY IN EMISSION LEVELS AND
PROJECTED GROUND LEVEL CONCENTRATIONS

SECONDARY COPPER SMELTER HITH HIGHEST EMISSION

- EPA HORKING NITH STATE OF ILLINOIS TO FURTHER
EVALUATE HIRE RECLAMATION INCINERATORS

ASH SAMPLES HERE COLLECTED TO EVALUATE POSSIBLE USE AS A
LESS EXPENSIVE SCREENING DEVICE UNABLE TO ESTABLISH
SPECIFIC CORRELATION

SEPARATE REPORT TO CONGRESS ON MUNICIPAL NASTE COMBUSTOR (MHC)

INCLUDING GUIDANCE ON OPTIMIZING COMBUSTION 50 AS TO MINIMIZE
DIOXIN EMISSIONS PUBLISHED JULY 1987.

- EPA HAS PROPOSED TO REGULATE MNC EMISSIONS UNDER 
NEH SOURCE PERFORMANCE STANDARDS - OF THE CLEAN AIR ACT



TIER 5 - 2,4,5 TCP AND SILVEX USE SITES

 

SAMPLES COLLECTED FROM RANGELANDS, RICE FIELDS, FORESTS, RIGHTS OF HAY

8-TCDD FOUND MORE FREQUENTLY AT SITES

PREDICTABLY ,7
UN SITES (TIER 7)

THAN AT u?
SOIL ANO SEDIMENT CONTAMINATION NAs DETECTED AT 15 OF THE 26

USE SITES SAMPLED, GENERALLY IN THE LON PARTS PER TRILLION (PPT)
RANGE

- THE PRINCIPAL EXCEPTION HAS A SITE WHERE HERE TAKEN
AT A HERBICIDE AREA FOR HELICOPTER SPRAYING
ACTIVITIES

STATISTICAL EXTRAPOLATION NOT POSSIBLE DUE TO THE LARGE
VARIETY OF USE SITUATIONS

 



TIER 6 - CHEMICAL PLANTS

 

NOT EXTENSIVELY CONTAMINATED NITH 
- LEVELS GREATER THAN 1 PPB FOUND AT 3 OF 18 FACILITIES SAMPLED
-- 3 FACILITIES BELOW 1 PPB
-- 12 NON-DETECTABLE


..I

 - .TIER 7 - SITES

RARELY FOUND IN URBAN OR RURAL BACKGROUND SOILS
AT THE PPT LEVEL -

2 CONTAMINATION IN FISH ASSOCIATED WITH CHEMICAL.
I

.3. 
NDUSTRY ACTIVITIES AND THE PULP AND PAPER INDUSTRY
2

HAS DETECTED AT 112 OF THE 394 SITES

- HAS DETECTED IN 23 0F 29 GREAT LAKES FISH SAMPLES 
FISH ADVISORIES ARE ALREADY IN EFFECT FDR MANY AREAS DUE TO
AND 

HHILE LEVELS AS HIGH AS 85 PPT IN HHOLE FISH AND 41 PPT IN FILETS
HERE FOUND, ONLY FOUR SITES HAD LEVELS ABOVE 25 PPT (ONE FILET)

A NUMBER OF FISH ADVISORIES HERE IN EFFECT PRIOR TO THE STUDY
(E.G. THE PETENHELL FLONAGE IN WISCONSIN AND THE TITTABAMASEE RIVER
IN MICHIGAN. A NUMBER OF ADDITIONAL ADVISORIES HAVE BEEN ISSUED
AS A RESULT OF THE STUDY (ANDROSCOGGIN R. IN MAINE, RAINY R.
IN MINN. AND THE KANAHHA R. IN H.VA.I

- STRINGENT DISCHARGE LIMITS HAVE BEEN ESTABLISHED FOR THE.DOH
CHEMICAL COMPANY PLANT IN MIDLAND, MICHIGAN

STUDIES HAVE BEEN INITIATED
- PAPER INDUSTRY STUDY OF PULP AND PAPER INDUSTRY
- BIOACCUMULATIVE STUDY

4

_h .- .. 


..- 

 

REGULATORY ACTIVITIES

 

IMPOSED STRINGENT MANAGEMENT AND DISPOSAL REQUIREMENTS BY LISTING CERTAIN
DIOXIN CONTAMINATED HASTES AS HAZARDOUS.

- ADDITIONAL REGULATIONS PROVIDE FOR EVENTUAL BANNING OF SUCH HASTES FROM
LAND DISPOSAL UNLESS THEY ARE FIRST TREATED.

CANCELLED USE OF 

PLACED ADDITIONAL RESTRICTIONS ON USE AND PLACEMENT OF PCB TRANSFORMERS.:
INTENDED TO PREVENT EXPOSURE TO GENERATED DURING PCB FIRES.

IMPOSED ADDITIONAL USE RESTRICTIONS AND PRODUCT CONTAMINANT LEVEL
RESTRICTIONS ON HOOD PRESERVATIVE USES OF PENTACHLOROPHENOL (PCP),
INORGANIC ARSENICAL COMPOUNDS AND CREOSOTE.

INITIATED RULEMAKING UNDER THE TOXIC SUBSTANCES CONTROL ACT T0
REQUIRE PRODUCERS TO PROVIDE INFORMATION ON POSSIBLE CONTAMINATION
IN ADDITIONAL PRODUCTS AND WASTE STREAMS.

EVALUATING ADDITIONAL WASTE STREAMS FROM PCP HOOD TREATMENT OPERATIONS FOR
POSSIBLE HAZARDOUS WASTE DESIGNATION.

'1

NATIONAL DIOXIN STUDY

 

REQUESTED IN A 1984 CONGRESSIONAL APPROPRIATION
NATIONNIDE STUDY T0 INVESTIGATE EXTENT OF DIOXIN CONTAMINATION

STUDY CONDUCTED AS PART OF NATIONAL DIOXIN STRATEGY. STRATEGY HAS DEVELOPED TO
COORDINATE INVESTIGATIVE, REMEDIAL AND REGULATORY ACTIVITIES

THOUSANDS OF SAMPLES COLLECTED - DIFFICULT CHALLENGE TO PERFORM ROUTINE
PART PER BILLION AND PART PER TRILLION ANALYSES IN A VARIETY OF
ENVIRONMENTAL MATRICES

CONFIRMED CONTAMINATION DATA HAS PREVIOUSLY BEEN COMMUNICATED T0 APPROPRIATE
STATE AND LOCAL OFFICIALS

BACKDROP: HIGH LEVEL OF PUBLIC AND CONGRESSIONAL CONCERN
INDUSTRIAL ACCIDENTS - SEVESO, ITALY
NITRO, H.VA
RESIDENTIAL EXPOSURE - TIMES BEACH, MO.

LOVE CANAL, NY
JACKSONVILLE, ARK.

AGENT ORANGE LITIGATION BY VIETNAM VETERANS

SUMMARY

EPA HAS AGGRESSIVELY IMPLEMENTED A STRATEGY TO ASSESS
AND DEAL HITH THE PROBLEM OF 

FEHER SITES THAN ANTICIPATED HERE FOUND ASSOCIATED WITH
PRODUCTION AND HASTE DISPOSAL OF 

AS EXPECTED THE SITES GENERALLY POSE THE MOST
SERIOUS PROBLEMS AND ARE BEING DEALT HITH UNDER 
SUPERFUND PROGRAM.

HE FOUND FISH CONTAMINATION IN ABOUT 25% OF THE SAMPLES,
PRINCIPALLY ASSOCIATED HITH LARGER RIVER SYSTEMS AND

THE GREAT LAKES SUBJECT TO THE INFLUENCE OF INDUSTRIAL
ACTIVITY. A FOLLOHUP STUDY OF PULP AND PAPER INDUSTRY
DISCHARGES HAS RECENTLY COMPLETED.

BEYOND THE SITES AND SPECIFIC LOCATIONS HITH
FISH CONTAMINATION, IS NOT A HIDESPREAD
CONCERN IN THE ENVIRONMENT.

EPA, STATES AND OTHER AGENCIES ARE FOLLOHING UP WITH
REGULATIONS, HEALTH ADISORIES, TARGETTED STUDIES AND
RESEARCH.

 

 

 

The Office of Water, Office of Solid Waste and Emergency
Resgonse, and EPA's Regional staff have reviewed and concurred
with this report. The report sets forth the overall requirements

and the Quality Assurance Project Plan for the National Dioxin

'0

Study.

49% Edwin L. Johnson, Director

Office of Water Regulations
and Standards

f? 4/ 
Michael Cook, Chairman

77" Dioxin Management Task Force

Brossmam Quality

. Assurance Officer
Office of Water Regulations
and Standards

 

 

FOREWORD

 

This document serves as the Quality Assurance Project Plan
of the Environmental Protection Agency's (EPA) National Dioxin

Study for study tiers 3. S. 6, and 7.

The study is part of EPA's Dioxin Strategy (Ref. No. 1)
released on December 15. 1983, and is designed to determine the
nature of environmental contamination from 2378-TCDD, the most
toxic dioxin isomer. This document summarizes the important
elements of field and laboratory Quality Assurance and Quality
Control and sets forth the basic objectives of the study.
The format of the document is in conformance with the Office of
Water (0W) Work/0A Project Plan Guidance document (Ref. No. 2).
This document draws upon and provides a bridge between the study's
field and laboratory manuals. The laboratory protocol document
describes the analytical procedures to be followed and the field

sampling document recommends specific field sampling techniques.

This project plan is intended to provide specific guidance
to those participating in the National Dioxin Study (EPA Head-
quarters, Regions, Analytical Support Laboratories, and State
Agencies). The plan is designed to help ensure uniformity and
an understanding of study objectives so that a valid basis can be

established for performing a national assessment.

 

TABLE OF CONTENTS

   

FOREWORD

I I INTRODUCTIONBackgroundImplementationI QUALITY ASSURANCE PROJECT 



LA)

1.0




1
1

Project 

7.2.4 Tier 
7.3 Monitoring Parameters and Their Frequency
of 
Financial 
Schedule of Tasks and .
Project Organization and 
Data Quality Requirements and 

2.0 Project Requested 
3.0 Date of 
4.0 Date of Project 
5.0 Project 
6.0 Quality Assurance 
7.0 Project 
7.1 Basic 

7.2 Project Description by 
7.2.1 Tier 

7.2.2 Tier 

7.2.3 Tier 

11.1 Data 
11.2 Data .
11.3 Data 
12.0 Sampling 
12.1 Tiers 3 a 
12.2 Tier 
12.3 Tier 
13.0 Sample Custody 
14.0 Calibration Procedures and Preventive

15.0 Documentation, Data Reduction, and

16.0 
17.0 Performance System 
17.1 System 
17.2 Performance 
17.3 
18.0 Corrective 
19   
  

Introduction
Background
On December 15, 1983, EPA released the 'Dioxin Strategy"

(Ref. No. 1) which provides a framework under which EPA will:

1. study the nature of dioxin contamination and the associated

risks to humans and the environment;

2. implement or compel necessary clean-up actions at contami?

nated sites; and

3. further evaluate regulatory alternatives to prevent future

contamination, as well as disposal alternatives to alleviate current

problems.

To facilitate the implementation of the strategy, EPA defined
the following study tiers based on decreasing potential for 2,3,7,8-

tetrachlorodibenzo-p-dioxin (2378-TCDD) contamination:

Tier 1 - 2,4,5-Trichlorophenol production

sites and associated waste disposal sites.

Tier 2 - Sites (and associated waste disposal sites) where

was used as a precursor to make pesticidal

products.
Tier 3 - Sites (and associated waste disposal sites) where
as. and its derivatives were formulated into
. -
- 5 pesticidal products. {j



 

4 Combustion sources.

5 - Sites where pesticides derived from 

have been and are being used on a commercial basis.

 

Tier 6 - Certain organic chemical and pesticidal manufacturing
facilities where imprOper quality control on certain
production processes could have resulted in the



inadvertent formation of 2378-TCDD.

Tier 7 - Networks of existing ambient stations where fish
and soil will be sampled to determine whether 2378-TCDD
is wideSpread in the environment and, if so, at

what levels.

The strategy calls for a complete investigation (including
field sampling) at all sites in tiers and 2 because they are
suspected of being the most contaminated. A representative.
sampling of sites in tiers 3 and 6 will be done because the number
of sites in these tiers is in the hundreds and the potential for
contamination is much less. The work in tier 5 will focus on areas
where extensive use of pesticides derived from has been
documented. The work in tier 7 will use two national networks

for sampling ambient conditions.

The initial sampling work at sites in tiers 3-7 constitute

the basis of the National Dioxin Study and hence the development

   
 

 

this project plan covering all tiers except tier 4, which will
be covered under a separate project plan being developed by the

Office of Air Quality Planning and Standards.

Although the overall objective of the National Dioxin Study
is to study the nature of dioxin contamination, sites found to
be contaminated at levels of concern with 2378-TCDD will be
referred to the Superfund program for any necessary follow-up

work.

Implementation

 

The AA for the Office of Solid Waste and Emergency Response
(OSWER) is responsible for implementing the overall dixoin strategy.
OSWER will directly manage the investigations for sites in tiers
1 and 2. The Office of Water Regulations and Standards (OWRS)
will manage the study of tiers 3 through 7 - the National Dioxin
Study. Both efforts will be coordinated by the Dioxin Management
Task Force (DMTF). EPA's regional offices will be responsible
for conducting the actual sampling for tiers 3, 5, 6, and 7,

following the guidelines presented in this document.

A significant portion of this study involves measuring
2378-TCDD in environmental media, especially in soils and fish.
Two major laboratory programs will be involved in these analytical
determinations: (1) a configuration of three EPA laboratories

(Duluth, Bay St. Louis, and RTP) known as the Troika and managed

  

 

 

Office of Research and Development and (2) the Contract Lab

Program (CLP) managed by OSWER and consisting of commercial

laboratories under contract to EPA.

Work in all seven tiers will proceed in a concurrent, parallel

fashion.

While the basic National Dioxin Study is limited to two

years, the comprehensive assessment of sites in tiers and 2

will likely extend beyond two years, especially at sites where

enforcement actions and clean?up Options are complex.

II. Quality Assurance Project Plan

4.0

5.0

6.0

Project Name: "National Dioxin Study"

Project Requested by: U.S. EPA, as a part of over-
all Dioxin Strategy in response to a particular request
through the Congressional 1984 appropriation

Date of Request: October 1, 1983

Date of Project Initiation: October 1, 1983

Project Officer: Alec McBride, Chief, (202/382-7046)

Water Quality Analysis Branch, Monitoring and Data

. Support Division (WE-SS3), Office of Water Regulations

and Standards, Office of Water, U.S. EPA

Quality Assurance Officer: Martin Brossman 
Monitoring and Data Support Division Office of
Water Regulations and Standards, Office of Water, U.S.

EPA.

 
 
  
 

Project Description

 

7.1 Basic approach

 

There are 75 different chlorinated dioxins, divided into
eight homologues (groups). each with different physical and
chemical prOperties depending on the number and location of the
chlorine atoms. One of the 22 isomers with four chlorine atoms
is This isomer is the principal focus of the National

Dioxin Study for three reasons:_
(1) it is the most toxic of the chlorinated dioxins,

(2) it is the isomer most often associated with exposure

and potential health risks to humans, and

(3) there is sufficient information available on it to

allow a targeted study to be developed.

The data reviewed thus far indicate that is
inadvertently formed during the chemical hydrolysis of tetra-
chlorobenzene to make and that it is not formed through
any other properly controlled chemical manufacturing process.
EPA's scientific judgement is that most of the goes
into the still bottom wastes from this process, with the remainder
contaminating the product. The contaminated is then
used as a precursor to make other chemicals and
silvex) thereby ''carrying" the 2378-TCDD contaminant through

the chemical manufacturing tree. At each step, chemical measures

  
  

 

an be taken to llclean-up" the product remove impurities

like 2378-TCDD).

Once the chemical industry learned about the potential for
contamination, steps were taken to reduce the levels
of contamination. These measures typically resulted in lower

levels of contamination in both the product and the wastes.

Thus, the characterization of environmental contamination

of is believed to be two-fold:

A decreasing level of contamination with time from

the chemical manufacturing process, and

(2) a decreasing level of contamination down the chemical
tree is more contaminated than



The approach to the National Dioxin Study is based on tiers
or categories of contamination; the lower the tier number, the
greater the potential for higher levels of 2378-TCDD contamination
of both product and wastes. For this reason, all of the facilities
involved in making (tier 1) and derivatives
(tier 2) will be investigated. The investigation in the other
production tiers (3 and 6) will be based on a representative

sampling of facilities within these tiers because the potential

   
 

 

 

for significant contamination is low at tier 3 sites and even

lower at tier 6 sites.

Sampling at tier 4 will be conducted to determine the pre-
sence or absence of 2378-TCDD in combustion sources, both those
where material contaminated with 2378-TCDD may have been burned
municipal incinerators) and those where no 2378-TCDD
should have been present in the material being burned 
coal-fired power plants). The latter type of sources will be
sampled to investigate the theory that 2378-TCDD can be created
in certain combustion processes. As indicated earlier, a separate

work plan will be developed for tier 4.

Sampling at tier 5 will be conducted to determine the
prevalence of at sites known to be Sprayed with 2378~

TCDD contaminated herbicides.

Tier 7 is being investigated to determine whether 2378-TCDD
is widespread in the environment by a representative sampling
of fish and soils at control stations, stations not associated

with tiers 1, 2, or 3.

7.2 Project Description by Tiers

7.2.1 TIER 3
Objectives

Tier 3 consists of facilities which formulate pesticides
containing active ingredients which may be contaminated with

- 7 

  

dioxin. Certain locations within these facilities may have been

 
 

contaminated with dioxin if the active ingredients of concern
were Spilled during handling or formulation. Another possible
source of contamination would be the cleaning and disposal of
containers which had held the active ingredients. Many of the
formulators were probably not aware that they were handling
material potentially contaminated with dioxin; therefore, they
-would probably not have taken Special precautions for handling

and diSposing of materials.

The Dioxin Strategy (Ref. No. l) contends that significant
contamination is less likely at tier 3 facilities than at tier 1
and tier 2 facilities. The objective of the tier 3 study is to
determine what percentage of the facilities in tier 3 have concen-
trations of dioxin in soil above one part per billion (ppb) or
in other environmental media fish in nearby streams)
above approximately one part per trillion (ppt). This is a
very important question to address since the answer will provide
the Agency with an indication of what, if anything, should be
done about the hundreds of tier 3 facilities which are not being
sampled as part of the National Dioxin Study. This determination
will be based on sampling within each site in a manner which,
where possible, is directed towards those specific locations
within a site that are most likely to be contaminated. The

study will not be able to statistically compare contamination levels

   
 

across facilities since the field sampling at each tier 3 site
will be conducted based upon the characteristics of that

particular site.

The AgenCy does have information on production for many tier 3
facilities and will be collecting additional data from question-
naires sent to all of the facilities in this tier. It is possible
that these data will allow EPA to characterize contaminated and
uncontaminated facilities in terms of certain variables. Hopefully,
these characterizations will assist in directing any further
investigations beyond the national study which may be necessary

for tier 3.

Implementation

 

The methodology used to accomplish these objective includes:
1) identifying formulated compounds containing and/or
its derivatives, 2) identifying facilities that use these compounds
in pesticide formulation, 3) selecting an appropriate number of
facilities to sample so that results can be statistically extra-
polated to all other facilities in tier 3, 4) identifying which
locations to sample at each facility, 5) determining the type of
samples to be collected (soils, fish, etc.). and 6) determining
whether additional facilities should be selected for dioxin

sampling.

 

Six additional pesticide formulation compounds have been

  

identified to contain and/or its derivatives. They

are 2,4,5-trichlorophenoxyacetic acid silvex, erbon,

 

ronnel, hexachlorophene, and isobac 20. EPA has identified 583

facilities that potentially used these compounds or 

itself in the formulation of pesticide products:

I

258 facilities were identified from the FIFRA and

 

TSCA Enforcement System (FATES) which provides

production levels for each facility for the years

1976~1981.

325 facilities were identified from four other data

sources: (1) the Office of Pesticide Programs Regis?
tration file, (2) a report entitled Dioxins

(Ref. No. 3), (3) regional recommendations, and

(4) those originally identified in tiers and 2 but
which were found to be formulation rather than pro-

duction facilities of and its derivatives.

Fifty facilities were statistically selected for the initial

sampling program from the FATES database of 258 such that an

-extrapolation could be made to all the pesticide formulators

listed in FATES. If 10 percent of the facilities in tier 3 are

found contaminated, then the 95 percent confidence interval

for the percentage of all contaminated facilities in the FATES

 

   

atabase is between two and 18 percent. Large production facilities
were statistically represented in the sampling program by first
ranking facilities according to production and then selecting a
statistical sample of six facilities from the 31 largest. The
remaining 44 facilities were selected based on regional distri-
bution. This was accomplished by stratifying the facilities

into six clusters and selecting an appropriate number based on

calculated sampling weights for each cluster.

a.

An additional 37 facilities were identified by the regions
as being of particular interest and are also included in the
initial sampling program. The results from these 37 facilities
will not, however, be used in the extrapolation since they were

not randomly selected.

The regional offices sent information request letters under
CERCLA authority to each of the 87 facilities to be sampled to
verify existing EPA records as well as to obtain additional
information quantities of waste generated, the disposal
method, and location of disposal sites). A sampling plan will
be develOped by the regional offices for each site based upon
the results of these information request letters and on recon-

naisance site visits.

Site-specific sampling plans will identify the locations
within each facility to sample, focusing on areas most likely to
be potentially contaminated with.dioxin. These areas would

-11..

   
 

 

nclude areas where potential spillage and leakage occurs 
loading/unloading areas, storage areas, disposal areas, and
stormwater drainage areas). The reason for following a directed
sampling plan as opposed to a random one is the belief that only
a small portion of a site is likely to be contaminated and that
one can make a reasonable judgement as to where that portion of
the site is located. However, using a directed approach does
preclude the ability to extrapolate to all of the facilities the

levels of contamination fOund at the different sites.

At sites where the information is inadequate to establish a
directed sampling plan or where additional coverage is desired
in conjunction with directed sampling, a random sampling scheme

should be developed as described in Section 12 of this document.

EPA also intends to obtain the Office of Management and
Budget's (OMB) approval for a questionnaire to be sent to tier 3-
facilities not included in the initial 87 to be sampled as well
as to any other facilities identified by the Department of Defense
as Agent Orange formulators. Responses to these questionnaires
will be evaluated to determine if another list of candidate
facilities should be created, from which a second set of tier 3
facilities may be selected for investigation. Our initial hypo-
thesis is that most of the facilities not listed in the FATES

database may have registered to handle one of the pesticides of

 

   

oncern but never actually handled the pesticides. The question-
naire responses will be used to evaluate the hypothesis. The
Agency has not made any provisions for verifying the validity of

the questionnaire responses.

The tier 3 investigation focuses only on formulation facilities
and does not follow products through the distribution system
warehouses, retailers, storerooms of commercial applicators)
because of the lower potential for contamination and the limited

resources .

7.2.2 TIER 5

Objectives

Tier 5 consists of those areas where pesticides derived from
were used or are being used. Ideally, an investigation
for tier 5 would be designed to: l) initially identify all uses
and areas of potential pesticide use for all seven products of
concern: 2) conduct a detailed investigation identifying all
actual use areas and amounts used; and 3) select a probability
sample of sites from the pesticide use population. From this
type of study a determination could then be made identifying
which particular uses result in detectable levels of dioxin, and

subsequently. which uses might represent a human health risk.

However, the available information on uses of these pesticides

is neither comprehensive nor detailed enough to allow this type of

13 

a

  

 
 

approach. Therefore, the tier 5 study will focus on those areas
where extensive use of the pesticides and silvex has
been documented. The rationale for limiting the scope to these
pesticides is that, based on preliminary information from the
Office of Pesticide Programs, these pesticides have been more
heavily used and have a greater potential for human exposure
than the other five pesticides which are of lesser interest due
to: (1) low levels of active ingredient pesticide in the end?
products, (2) lack of use documentation, (3) use on very small
areas, or (4) a wide diversity of uses at low levels of application.
The study may include sampling at use sites (such as
leather tanneries or wood preserving facilities) if adequate

information can be developed on specific facilities which used

this compound as a pesticide.

Implementation

 

Candidate sites for investigation were compiled by head-
quarters and regional personnel working in conjunction with
state or local agencies. Selected sites include ones where the
major continuing and/or extensive past use of and silvex
have been documented rice fields, sugarcane fields, range-
lands, forests, rights-of-way, and recreational areas). The
selected sites will be sampled to get a general characterization
of each major use and will serve to determine if further investi-

gation of a particular use is required.

-14-

   
 

Media to be sampled will include soils, stream sediments,

fish tissue, vegetation, animal tissue, and/or any other appropriate
media as determined by the responsible regional office. Sampling 
location and methods will follow the detailed protocols in the

field guidance manual. Priority will be given to soil and sediment
sampling since dioxin applied to an area by pesticide use will

most likely reside in these media as a result of dioxin transport

and fate processes (Ref. No. 4).

The number of soil samples to be collected will be between
24 and 48 discrete samples randomly distributed at each of approxi-
mately 20 tier 5 sites (see Section 12 of this document). These
samples will be analyzed at the level of detection. This
approach results in a 70 - 90 percent level of confidence that
dioxin will be detected if it is present at five percent of the
area within the site. This approach assumes that one cannot
identify "hot spots" within a site and that there is either a
uniform or a random distribution of dioxin within the site. This
assumption is based on the application methods for or
silvex. Sampling plans will be developed by the regional offices

for each of the tier 5 sites.

  

   

7.2.3 Tier 6

Objectives

?Tier 6 of selected organic and pesticide manufac-
turing facilities share, under unusual or poorly controlled
operating conditions, dioxin may have been created. The objectives
for the tier 6 study are identical to those for tier 3: that is
.to determine the percentage of facilities which are contaminated
at levels of concern and where possible, to characterize those

facilities in terms of production variables.
Implementation

The methodology used to accomplish this objective includes:
1) identifying those commercially significant organic and pesticide
compounds where improper quality control on production processes
could result in the formation of 2378-TCDD contaminated products,
2) identifying facilities that manufacture these compounds, 3)
selecting an appropriate_number of facilities so that results
can be statistically extrapolated to other facilities, 4) identi-
fying locations to Sample at each facility, 5) determining the -
type of samples to be-collected (soils, fish, etc.), and 6)
determining whether additional facilities should be selected for

dioxin sampling.

Dioxins (Ref. No. 3) identified organic and pesticide com-

Pounds (totaling 125) whose production could inadvertentlf create. J1BE:
. . --. .

?f 

16.? I 

  

ioxin based on their molecular structure, process sequence and
commercial significance. The production of only 60 of these
compounds could potentially lead to 2378-TCDD formation. Dioxins
(Ref. No. 3) defined commercially significant products as those
produced in quantities in excess of 1,000 pounds per year and/or
wholesales reaching $1,000 per year. Most of the organic chemicals

identified are used as manufacturing intermediates.

EPA identified 60 facilities that manufacture these 60 com-
pounds using four sources of information: (1) the SRI Directory
of Chemical Producers (1977*1983). (2) FIFRA and TSCA Enforcement
System (FATES), (3) the Dioxins report (Ref. No. 3), and (4)

regional suggestions.

Nineteen facilities were statistically selected for the
initial sampling program based on regional distribution so that
extrapolation could be made to all these manufacturing facilities.
This selection was accomplished by stratifying the facilities
into five clusters and selecting an appropriate number based on
calculated sampling weights for each cluster. If 10 percent
of facilities in tier 6 are found contaminated, then the 95 per-
cent confidence interval for all contaminated tier 6 facilities

is between three and 23 percent.

Information collection and field sampling procedures (including

the number and allocation of soil samples) for tier 6 facilities

  

ll be identical for those used for tier 3 facilities. Particular
attention will be given to reported production levels, which for
the organics are not currently available. Sampling plans will be

developed by the regional offices for each of the tier 6 sites.

Tier 6 focuses only on production facilities as a potential
source of dioxin release into the environment. The potential for
dioxin contamination from these products at distribution facilities
warehouses, applicators and retail stores) is not expected
to be significant and sampling at these facilities is not included

as part of this tier.

7.2.4 TIER 7

Objectives

Tier 7 consists of areas other than those where known or sus-
pected sources of 2378-TCDD contamination are located. The basic
goal of the tier 7 study is to evaluate the extent and severity
of 2378-TCDD contamination in the environment. In addressing
this goal, the study will focus on contamination of soil and fish
tissue since these are the media which present the greatest
potential exposure to humans. Also, 2378-TCDD tends to adsorb

strongly to soil particles and to bioaccumulate in fish tissue.

Specific objectives of the tier 7 study are to: 1) determine
the percentage of sites in the EPA Urban and Rural Soil Networks

which have measurable levels of 2378-TCDD in soil and 2) determine

13 

  

he percentage of sites in the U.S. Geological Survey's National
Stream Quality Accounting Network (NASQAN) which have measurable
levels of 2378-TCDD in fish tissue. If is detected at a
significant number of locations (approximately 20 percent or more),
the Agency will attempt to determine what typical ?background"
levels are and whether they are related to Specific variables
describing the different sites. All tier 7 analyses - both for
fish and soil - will be done at approximately the level of

detection.

Implementation

 

Tier 7 consists of two phases: 1) a soil sampling survey,
and 2) a fish screening survey. Soils were selected for sampling
since dioxin reaching the soil will be strongly sorbed; bio-
degradability, plant uptake, and leaching are not believed to
be important fate processes (Ref. No. 3). Photodegradation is
limited to a near-surface phenomenon, and dioxin transport in
many cases is due to erosion of contaminated soil which is trans-
ported to the water environment. Dioxin is thought to enter the
atmosphere adsorbed to particulates, and that which is not photo-
degraded is subsequently deposited. As a result of these fate
processes, soil is an appropriate and informative medium to

sample in determining background levels of dioxin.

Soil sampling will be accomplished through use of the Office
of Pesticides Program National Soils Monitoring Program (NSMP).

- 19 

The objectives of this program are to monitor for the presence of
pesticide residues in urban and rural soils and to determine trends
of levels through time Ref. No. 5). (Refer to the National
Soil Monitoring Program Ref. No. 5) and Urban Soils Monitoring
Program Ref. No. 6) for a complete description of the network
designs.) The rural network consists of over 13,000 sites and is

a valid probability sample of-sites from the 1967 Conservation
Needs Inventory (CNI) of rural land areas in the conterminous
United States. Sample design and site identification have already
been done. For tier 7 sample selection, the network has been
ordered by EPA regions and states. Five systematic samples of
equal size (40) were randomly selected to yield 200 sample sites
from which various estimates of soil contamination can be made
describing the population of soils of the rural network. If 10
percent of the sites are found contaminated, then the 95 percent
confidence interval for all contaminated sites in the network is

between seven and 13 percent.

Although the rural network is a valid subsample of the CNI,
no valid structure exists to provide the basis for analyzing the
CHI, and therefore, the rural network data, except through arti-
ficial methods. Other restrictions in using the rural network
are: 1) sample numbers vary considerably from state to state
such that reliable estimates of average levels will not be available
for some geographic areas and 2) the CNI database is 17 years
old, and a number of locations may have changed characteristics.

- 20 -

Three hundred soil sites have been selected from the 20
Standard Statistical Metropolitan Areas (SMSAs) monitored in the
urban soil network. If 10 percent of the sites are found contami-
nated, then the 95 percent confidence interval for all contaminated
sites in the network is between eight and 12 percent. SMSAs were
ordered by EPA regions and states, and five random systematic
samples of 60 sites each were selected. In addition to the
selected sites, soil samples may be taken at one industrial site
in each these sites will be selected by regional personnel.
Sampling will follow protocols summarized in Section 12 of this

document and detailed in the field guidance manual.

Fish are known to bioaccumulate many compounds, including
dioxin, to much higher levels than surrounding waters.- In
addition, fish represent a direct route for human uptake via
ingestion. In estuarine and coastal areas, mussels or oysters
will be collected to determine background levels. Similar to
fish, shellfish are known bioaccumulators and represent a direct
route for human exposure through consumption. Although depuration
tends to be more rapid in shellfish than in finfish, the migratory
behavior of most marine fish may not reflect the actual conditions
of the collection site, thereby making shellfish preferred specimens
to collect to meet tier 7 objectives in coastal areas. As with
soils, sampling will follow procedures summarized in Section 12 of

this document and detailed in the field guidance manual.

Sampling protocols call for collecting specimens of bottom-
feeding and game fishes in freshwaters and mussels or oysters in
estuarine and coastal waters. Methods Specified serve to limit
variables reducing the difficulty in interpreting the data. These
include establishing target species (to reduce interspecies
variations), sampling fish of similar age where possible, and
limiting time of sampling to reduce seasonally-related differences
lipid content). Composite samples of whole bottom-feeding
fish, whole game or commercial fish, bottom-feeding fish fillets,
and game or commercial fish fillets will be collected. The
bottom-feeding whole fish composite will be analyzed first, and
if contamination is detected, the other samples will then be

analyzed.

As in the case of the soils survey for tier 7, sample design
for fish sampling also utilizes existing monitoring networks -
specifically the 0.8. Geological Survey's National Stream Quality
Accounting Network and Benchmark Network. One hundred stations
were statistically selected so that the results could be extra-
polated to the combined networks. If 10 percent of the sites
are found contaminated, then the 95 percent confidence interval for
all contaminated sites in the network is between five and 15 per-
cent. Replicate samples will be collected at 25 of these sites
in order to estimate the variability at a site. In addition,

approximately 315 sites were selected from the networks and from

additional locations of regional or national interest. These
additional sites represent locations of interest because of
nearby population centers, commercial or recreational fishing

activity, and availablity of relevant water quality information.
7.3 Monitoring Parameters and Their Frequency of Collection
1. (2378-TCDD).

This parameter will be measured in all samples which are
collected as part of the study. Media collected will include
wastewater, surface water, groundwater, sediment, soil, aquatic
organisms, and terrestrial specimens. The frequency of collection
will be defined in the individual regional site-Specific plans.

It is estimated that samples will be analyzed at the rate of 100
to 150 per month using the EPA Analytical Troika; the rate using
the CLP will be somewhat higher. All samples analyzed by the

Troika will be retained for possible further analytical work.

2. Dibenzo?p-dioxins and Poly-

chlorinated Dibenzofurans 

The extent and frequency of these measurements have not
been determined. The following groups of isomers are being

considered:

-23..

 

Group Number of Isomers
Tetrachlorodibenzo-p?dioxin 22"r
Pentachlorodibenzo-p?dioxin l4
Hexachlorodibenzo?p-dioxin 10
Heptachlorodibenzo-p?dioxin 2
Octachlorodibenzo-p-dioxin 
Tetrachlorodibenzofuran 38
Pentachlorodibenzofuran 28
Hexachlorodibenzofuran 16
Heptachlorodibenzofuran 4
Octachlorodibenzofuran 

Includes 2378-TCDD

The identification of Specific isomers within each group
depends on the availability of analytical standards and the ability
of the selected chromatography columns to resolve isomers. Most
determinations will be non-isomer specific total tetra-
chlorodibenzofurans, etc.) and semiquantitative (because analytical

standards are not available, the concentrations are estimates).

3. Percent Lipids
The lipid content of each contaminated fish and a repre-

sentative subsample of uncontaminated fish will be determined.
4. Percent Moisture

The moisture content of all soils and sediments measured at
the level will be determined by Troika; the results will be
reported on a dry weight basis. The moisture content will not be
determined for soils measured at the level by the CLP. The

results will be reported on a net weight basis.

- 24 

5. Fish Aging

ERL-Duluth will remove and store scale and otolith specimens
of each whole bottom-feeding fish sample. Depending on the levels
of dioxin found and the percentage of fish found contaminated,
OWRS will decide if fish age will be estimated. If aging is
necessary, each contaminated fish and a representative subsample

of uncontaminated fish will be aged.

6. Determination of weight, size, and species of aquatic



organisms and terrestial animals.

Each region will have the reSponsibility for determining the
weight, size, and Species for all aquatic organisms and terrestrial
animals.



A summary of the parameters discussed is shown in Table 1.

 

 

TABLE 1 - PARAMETER TABLE
Parameter Nunber of Sanple Method Sample Holding
Samples Matrix* Reference Preservation ?T?ne
- (Estbnate)
2.3.7.8-TCDD Unknown water 7 4?C/Dark 7 days - Extraction
40 days - Analysis
2 3 ,7 3800-7300 Soil/Sediment 7 ,3 4?C/Dark Indefinite
600 Fish 7 Freeze/Dark Indefinite
Unknown All 7 Sane as for Same as for TCID
TCDD
Lipid Unknown Fish 7 Freeze/Dark (Undetermined)
bbisture 980?1460 Soil/Sediment 7 4?C/Dark ('Do be performed at
time of chemical
analyses)
Speciation/
Weight/Size 600 Fish 9 None Indefinite
Aging Unknown Fish 9 Freeze/Dark Indefinite

 



 

 

 

 

 

Plant and animal tissue will also be evaluated on a site and issue specific basis.

-25-

8.0 Financial Information

 

The following resources have been earmarked for the National
Dioxin Study. They are funded in the Water Quality Monitoring

and Analysis program element of EPA's budget.

 

 

 

Current President's
Operating Plan Budget Request
FY 1984 FY 1985
FTE ACEC ELIE 
3(000) $(000)
Headguarters
a e,f
OWRS (Program office) 385.0 5.5 3400.0
(AH28)
(Troika) 835.0
(A1163)
(Troika) 50.0
(AHGO)
OPP (Troika) 350.0
(AH32)
Agency reserved . 165.0
(AH92)
OAOPS (Tier 4 work) 715.0
(AHS3)
Total 0 2500.0 5.5 3400.0
Regions
Region 1 1.0 75.0 1.0
2 1.0 175.0 1.0
3 1.0 125.0 1.0
4 1.4 200.0 1.4
5 1.4 250.0 1.4
6 1.3 200.0 1.3
7 1.4 200.0 1.4
8 .5 75.0 .5
9 .5 100.0 
10 .5 100.0 .5

Reg. Total 10.0 1500.0 10.0 0

Total EPA 10.0 4000.0 15.5 3400.0

- 27 



a Sources of Headquarters FTE estimates are:
FY84 -- Budget Request to OMB for FY85 (Form 
September 1983. FY85 -- OWRS Budget Plans, February 27, 1984.

Source of Regional FTE estimates is Regional WOrkload Model
for Water Quality Monitoring and Analysis, February 16, 1984.

Note that many EPA offices are contributing efforts toward
the National Dioxin Study which are not reflected in these

estimates, since these estimates were made prior to actual
initiation of the study.

$165,000 is being held in Agency reserve in exchange for
$165,000 in Salaries and Expenses funds allocated by the
Comptroller's office to:

OPP (AH32) 139,000
OEPER (AH63) 26,000

In addition to the $3.4 million, OW has earmarked $250,000 for
study of persistent and bioaccumulative pollutants in the FY85
President's Budget request.

Some portion of these funds will be allocated to other Head?
quarters offices and to the Regions in FY85.

Abbreviations:

Abatement Control and Compliances appropriation, commonly
referred to as "extramural."

AH Allowance Holder number.

FTE "Full Time Equivalent" employees.
9.0 Schedule of Tasks and Projects

The major items needed for completion of the National Dioxin

Study for tiers 3, 5, 6, and 7 are:

1. Overall regional plan will be prepared and will include: a

brief organizational section; information on how the region

23 

will arrange sampling in each of the tiers; a plan for
using all extramural funds; and a tentative schedule for

sampling. These plans were due by June 1, 1984.

Site-specific sampling plans will be prepared by each
region. These plans will include: information on sampling
site location (including latitude/longitude); site sampling
plan with discussion of rationale; and site-specific safety
and community relations issues. These plans will be sub-

mitted to OWRS for review prior to sampling.

Review and approval of site-specific plans occurs before

the region does any sampling at a site.

Samples are collected and shipped over a period of time
arranged with the Sample Control Center and Sample Management
Office consistent with Troika and CLP capacity to meet

holding times specified in Table 1.

All National Dioxin Study sites for tiers 3, 5, 6, and 7

are finalized prior to site~specific plan submittal deadline.

A certification and audit program for Contract Labs has been

developed and implemented by EMSL-LV for soil analyses.

In December, 1984, OWRS will prepare an interim report
describing the status of the study and presenting any results

available at that time.

-29-

8. OWRS will prepare a final report on the results of the study

by December, 1985.
10.0 Project Organization and Responsibility

The following is a list of key study personnel and their
corresponding responsibilities.

National Dioxin Study responsibility: Edwin L. Johnson
Director, OWRS

Dioxin Management Task Force Chairman: Michael Cook, OSWER
PrOJect Director: Alec McBride, 
Assistant Project Director: Stephen Kroner, 
Troika Laboratory Director: Norbert Jaworski, ERL, Duluth
Contract Laboratory Coordination: Stan Kovell, OSWER
Field Sampling Plan Review: Stephen Kroner, 
Quality Assurance Officer: Martin W. Brossman, OWRS
Quality Assurance Task Group: Martin Brossman, 
Richard Spear, Region II
Gerald McKenna, Region II
James Adams, Region 
Marsha Kuehl, Region 
Charles Hensley, Region VII
Robert KleOpfer, Region VII
Michael Dellarco, 
Data Management: Alec McBride (STORET)
Laboratory Audit Team (Troika): Two or three members to be desig-
nated by the Quality Assurance
Task Group
Field Audit Team: Regional QAO with selected support

Data Review and Validation (Total): Alec McBride

3o 

Peer Review (Concepts and Reports): To be determined by the Dioxin
Management Task Force

National Dioxin Study Regional Coordinators -

Region I - Bill Walsh
Region II - Rick Spear
Region - John Ruggero
Region IV - Rebecca Slack

Region - Howard Zar
Region VI - Dave Parrish
Region VII - Billy Fairless
Region - Bill Geise
Region Ix - Kathleen Shimmin
Region - Anita Frankel



11.0 Data Quality Requirements and Assessments

Table 2 summarizes the expected quality of the data in
~terms of precision, accuracy, and detection limits. Specific
details are given in the individual analytical procedures (Ref.
Nos. 7 a 8). For purposes of controlling data quality, a sample

set consists of the following:

TROIKA Egg
12 Environmental Samplesa 21 Environmental Samples3
1 Matrix Spiked 1 Matrix Spikeb
1 Performance Samplee 1 Performance Samplec
1 Method Blankd 1 Method Blankd
1 Field Blanke 1 Field Blanke

Including any field replicates needed

Provided by Regions through SMO

Provided by SMO (through 

Responsibility of laboratory

Provided by Regions (through Headquarters) for soils

II II

II II



The data quality of a given set of samples is assessed in

relation to the following criteria:

- 31 

Daily verification of isomer specificity.

Daily verification of response factor.

Qualitative criteria (isotOpe ratios and retention times) for
all positives.

All field blanks and method blanks must be free of any detectable
TCDD.

Performance sample must meet criteria (See Table 2).

Spiked sample must meet criteria (See Table 2).

For the CLP. the surrogate must be measured to i 40 percent

in every sample; for the Troika, the internal standard must be
recovered to i 30 percent.

For the Troika effort, one complete set will be split with a
contract lab on a quarterly schedule. The specific samples

will be selected by Troika.

- 32 -

TABLE 2

Summary of Quality Control Targets for 2378-TCDD Measurements

Target

Detection
Matrix/Lab Limit
1.0 

Ambient 0.03-.Animal - 5 
5 
Wastewater/TROIKA 










parts per billion

parts per trillion

Bias?a)

525%

530%

530%

530%

530%

530%

530%

Precision(b)
525%

530% if >6 D.L.
5100% if 5 6 D.L.

530% if >6 D.L.
5100% if 5 6 D.L.

530% if >6 D.L.
5100% if 56 D.L.

530% if >6 D.L.
5100% if 56 D.L.

530% if >6 D.L.
5100% if 56 D.L.

530% if >6 D.L.
5100% if 56 D.L.

As determined from in lab matrix spikes and expressed as

a percent.

As determined from within lab replicates and expressed as

relative standard deviation.

All TROIKA targets are subject to revision as additional

analytical work is completed.

- 33 

11.1

Data Comparability

Measures taken to ensure comparability of analytical work

performed by different laboratories include the following:

Standardized written sampling and analytical procedures.

Standardized field and compatable analytical data_forms. sample

identification tags, and chain?of-custody records.

All CLP laboratories will use the same certified standard
solution of 2378-TCDD as provided by Vegas for
preparation of all calibration standards. The Troika labs

will use a primary analytical standard which has been referenced
to the Vegas standard as well as other verified

standards.

All laboratories will be provided with performance evaluation

samples on a regular basis.

Standard handling and shipping procedures will be used for

all collected samples.

Replicate analyses will be done on samples in order to evaluate

both within and between?laboratory precision.

A uniform supply of sampling containers will be utilized.

- 34 

The results for performance evaluation samples and inter-
laboratory duplicate analyses will be the primary means for
verifying the comparability of data within a single laboratory.
The Troika QC results will also be used to evaluate method

performance.
11.2 Data Representativeness

See Sections 7.0 and 12.0 for a discussion of data represen-

tativeness for each tier.
11.3 Data Completeness

The target for completeness of the data in order to meet the
project needs is 80%. and the measure to be used in meeting this
target is the percent of total reported data classified as valid

in the data validation process.

12.0 Sampling Procedures

 

12.1 Tiers 3 6

At most facilities the majority, if not all, samples taken
will be soil samples. Where there is a water body near the
facility, stream sediment and/or fish tissue samples may be taken.
Regional personnel will make the determination as to whether
samples taken from drainage ditches should be treated as soil

samples or sediment samples. A discussion for sampling sediments

locations more likely to be contaminated. it may decide to follow

a random sampling approach for the entire site.

A random sampling approach consists initially of dividing
the facility area into equal size grids with dimensions not
exceeding 50 feet by 50 feet. Samples are collected within
randomly selected grids (directly in the center of the grid).
Grids that are covered by buildings are excluded from the random
selection process. For a site which is sampled in a completely
random manner, if five percent of the site is contaminated, this
sampling approach provides a 70 percent confidence level of
detecting contamination with 24 samples and a 90 percent confidence

level of detecting contamination with 48 samples.
12.2 Tier 5

Although sampling at tier-5 sites may include several
environmental media, priority will be given to soil and sediment
sampling since dioxin applied to an area by pesticide use will

most likely reside in these media.

Discrete soil samples will be collected using identical
methods as in tier 3. Also. appropriate standard reference soils
will be supplied by OWRS and included in each sample set (as

'defined under Section 11.0) for shipment to the laboratory.

Specific sampling methodologies for sediments depend on the

nature of material to be collected, depth of water above the

-37-

sediment, sampling location, and equipment availability. Methods

will be determined by reSponsible regional personnel.

While sampling sediments for 2378-TCDD, it is important not
to disturb the t0p layers of sediment and to minimize loss during
sampling. Therefore, scoops and drag buckets are not considered
for use as sampling devices. In wadeable waters, the direct use
of?a Teflon core liner is preferred. Core liners can serve as
sample containers for shipment, thereby eliminating the need for
time consuming extrusions in the field. In waters of greater
depth, Ekman or Ponar grab samples are preferred. After retrieval,
the sample is to be subsampled with Teflon coring tubes. In
terms of volume, 500 grams of sediment is the minimum sample
mass to be collected. Sample handling, preservation, and transport
are to follow the protocols set forth in the sampling guidance

manual.

The number of soil and/or sediment samples to be collected
at each site will be between 24 and 48, and the sample collection
locations will be identified following the random sampling approach
described for tier 3 and 6 sites. Sediment samples will be

collected along equally spaced points on sampling transects.

33 

12.3 Tier 7

Fish samples (both bottom-feeders and game fish) are to be
taken at freshwater sites; shellfish samples only are to be taken

at estuarine and marine sites.

Enough fish of the same Species are to be collected at each
site to allow for a minimum sample mass of 500 grams for each of
'the following four separate samples: one composite of whole
bottom-feeding fish, one composite of bottom?feeding fish fillet,
one composite of whole game fish, and one composite of game fish
fillet. All filleting with be done in the laboratory, and skins

will be removed.

Target Species have been established to reduce interspecies
variability. Target species for bottom?feeding fish, in order
of perference are: Carp (Cyprinus carpio)

White sucker (Catastomus commersoni)

Channel catfish (Ictalurus 
Target Species suggested for game fish are:

Cold water stations: rainbow trout (Salmo gairdneri),
brown trout trutta), brook trout (Salvelinus

fontinalis), lake trout namaxcush):

39 

 Warm water stations: largemouth bass (Micropterus

salmoides), or other members of the sunfish family

(6.9., Pomoxis bluegill (Lepomis macrochirus), etc.

 

Cool water stations: walleye (Stizostedion vitreum)

 

or other members of the perch family.

Collection of fish specimens of similar age class (two or
greater) and limiting collection to non-spawning periods (such as
early fall) are required to reduce seasonally?related differences.
Each fish is to be wrapped in foil and placed in a plastic bag

and properly labeled for type of analysis (whole or fillet).

Target species for estuarine and marine sites are the bivalves

Crassostrea virginica (Eastern oyster), Mytilus californianus

 

and edulis (commom blue mussel). The minimum sample mass
(per Species) is 500 grams of tissue (excluding shell). Bivalves
should be individually wrapped in foil and placed in a plastic

bag for each site.

Specific sampling methodologies for fish and shellfish depend
primarily on water conditions, target Species for collection,
and avaliable equipment. Methods will be determined by appropriate
regional and field personnel. Regardless of the method employed,
a rapid collection technique is to be employed as not to cause
prolonged stress on the organism; in most cases, therefore,

active collection techniques are preferred.

40 

Soil collection techniques at rural and urban sites are
identical to those previously described for tier 3 tulip
bulb planter, four-inch deep core, 50' 50' grid, number of per?
formance samples and field blanks, etc.). At designated
sampling sites for urban sampling, one discrete sample will be
taken at the mid-point of the site. At designated rural lO?acre
sites, the area will be divided into equal sized grids-from
which one will be randomly selected. One discrete soil sample

will be collected at the mid-point of the grid.

Sample handling, preservation, and transport are to follow

the protocols set forth in the sampling guidance manual.
13.0 Sample Custody Procedures

Sample Control procedures will be in strict conformance with

those procedures provided in the Sampling Guidance Manual for the

 

National Dioxin Study (Ref. No. 9). Figure 1 is a flow chart of

sample control to be used in the study.

NEIC chain of custory procedures will be followed for all
tiers of the National Dioxin Study. Required chain of custody

forms will be provided through the regional study coordinators.
14.0 Calibration Procedures and Preventive Maintenance

Calibration and maintenance of field equipment is contained

in the Sampling_Guidance Manual for the National DioXin Study

- 41 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

.




. 
.11. .n

i



 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 



 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 




Inn-I- Sunni-0 1
In?! 
Ina-us 
WIHIAHLM 1
1 i
1
. 
I Guns: Lab
I 
I 1 
Sdlh- Find? i 
{sex-m 
San-n 

Cm
Elm

tam-am
unmvnuo. mun


tun-m 
i 

On HI.- Tr? In
van-nan of Rum owmu
(Tm: (sec:
Figure 1 NATIONAL DIOXIN STUDY. TIERS 1 WM 7 -

ME COLLECTION AND ?muss;

42?



(Ref. No. 9). Analytical instrumentation calibration and maintenance

procedures are included as part of the Analytical Procedures and

 

Quality Assurance Plan for the National Dioxin Study (Ref. No. 7).

In addition to the referenced SOP's above, each site sampled
should be documented in a bound field logbook. This logbook should
delineate the exact type and frequencey of field equipment calibration,
cleaning and maintenance. All repairs made during the course of the
sampling should also be noted. Specific model or serial numbers of
all equipment used should be listed, along with the lot or batch
numbers of all reagents used to treat or clean any-equipment in

contact with the samples.
15.0 Documentation, Data Reduction, and Reporting

Documentation, data reduction, and reporting will be in strict
conformance with the protocols Specified in references 7 and 8.
All data will be entered into the STORET system. The data quality
will be described in quarterly reports prepared by the Water Quality

Analysis Branch.

16.0 Validation

Data will be validated according to procedures Specified
in references 7 and 8. The data will be coded either valid or
invalid depending on adherence to the specified quality control

criteria. The CLP data is anticipated to be reviewed and vali-

9 (M

dated by EMSL-LV, concurrent with reporting to the regions. The
Troika data will be reviewed and validated internally (by Troika)
and also independently (by contractor) prior to reporting to

the regions. The regions are responsible for reviewing the data
for reasonableness based on a knowledge of the site character-
istics and the specific locations of individual samples. Any
disagreements between the reporting lab and the regional reviews

will be resolved by the Quality Assurance Task Force.
17.0 Performance and System Audits

Throughout the National Dioxin Study. audits will be conducted

by EPA personnel.

17.1 System Audits

 

The systems audit consists of an on-site visit to contractor
analytical labs by EMSL-LV for the purpose of evaluating laboratory
operations and quality control procedures. These site visits to
contract laboratories should be made prior to the reception of
samples, and periodically during active analytical work. EMSL-LV
(Ref. No. 8) provides the Standard Operation Procedure to be used

for the on-site laboratory evaluations.

An audit team consisting of 2 to 3 persons designated by the
Quality Assurance Task Force, including a representative from 
LV, will perform on-site audits of the three Troika laboratories

to assess the laboratory Operations in regard to implementation

44 

-. 

of this quality assurance plan. These audits will be performed

at least once a year.

The regional 0A0 and selected support will perform field

audits at least once a year.

17.2 Performance Audits

 

Performance audits will consist of the analysis of performance
evaluation samples supplied to contract laboratories, and in the
evaluation of the corresponding analytical results by EMSL-LV.
Initially, the laboratory must demonstrate their ability to analyze
for EPA will provide to each analytical laboratory two
or more performance evaluation samples. Results of these perfor-
mance evaluation samples must be determined to be within acceptable
limits before a laboratory is permitted to analyze any samples.
Contracted laboratories will be required to analyze performance
evaluation samples onla periodic basis as a continuing check on

performance.

The Troika will also analyze performance evaluation samples
with each set of samples. In addition, once per quarter, Troika
will select a complete set of samples to be analyzed by a qualified
independent lab approved by Vegas. The results will be
statistically compared by the 0A Task Group based or guidance
from QAMS, and any significant differences will be resolved

before other analyses are resumed.

17.3 Deficiencies

Any deficiencies or unacceptable performance noted in the
audits will be relayed immediately to the persons reSponsible.
A deadline for a plan of corrective action and its successful
completion will be given. Documentation of corrective action
will be required in the form of a follow-up on-site audit or

performance evaluation sample.

18.0 Corrective Action

 

Identifying, correcting, and documenting quality control
problems are the most crucial parts of a Quality Assurance Project
Plan. Two Systems for dealing with corrective action are needed.
The technical or analytical trigger points for corrective action

are defined in the ?Analytical Protocols and Quality Assurance

 

for the National Dioxin Study" (Ref. No. 7). Administrative

quality control lapses require a different scheme.

Three operational areas of the plan could trigger the need
for corrective action initiating from the administrative level:
field sample collection, document control, and the data validation
processes. When a ?defect" or deviation from the GA Project Plan
occurs in one of these areas. the following actions and docu-

mentation must occur:

can

1. Responsible person for the problem area as outlined in

Project Organization and ReSponsibility must document the

deviation/defect discovered.

2. This documentation must include:

Date and time deviation/defect noted

Date deviation/defect documented

Su5pected cause of deviation/defect

Preposed sequence of action to correct defect

Person(s) responsible for carrying out corrective action
Date action completed

Follow-up dates on effectiveness of action

Final approval of action by responsible person

3. All such documented deviations/defects should be readily

accessible to the on-site audit teams to verify that an

effective and timely corrective action system is Operational.

19.0 Reports

A series of reports and documents have been prepared which

provide background information and on?going guidance for the

National Dioxin Study.

The Dioxin Strategy published on November 28, 1983, covers

the total agency effort on dioxin including the National Dioxin

Study.

47 

The National Dioxin Study Work Plan of January 15. 1984
(Ref. No. 11). assigned to the regions the responsibility for
developing sampling plans. The work plan included a tentative
list of sites to be studied and underwent revision in a February 24.
1984 package. This list. with minor changes, contains the sites to
be sampled exclusive of tier 5 sites. Tier 5 sites were to be

selected by June 1, 1984 by the regions with approval by OWRS.

This Project Plan serves as the Quality Assurance Project
Plan for the National Dioxin Study and provides an overview of the
entire study. It also serves as a integrated description of
requirements in the field (Ref. No. 9) and laboratory (Ref. Nos.
7 and 8). The document provides Specific QA guidance to the

regions.

Two types of regional plans are required; each region will

provide an overall work plan and a series of site-specific plans.

Contents of the regional work plan are to include: (1) a brief
organizational section; (2) a tentative schedule for sampling
at tiers plan for using all the extramural
funds; (4) arrangements ESD, FIT. contractor, states,
etc.) for sampling within each tier; and (S) a tier 7 sampling
plan. Regional work plans were due to Headquarters on June 1,

1984.

UNITED STATES ENVIRONMENTAL AGENCY
WASHINGTON. D.C. 20460

 

MAR 18 3
2?3 If??

Wm

Freedom of Information Act
Request RIN 1102-87

Ms. Carol Van Strum
Route 2, Box 190
Tidewater. Oregon 97390

V9

   
   

Re-

Dear Ms. Van Strum:

This letter is in partial respons to your Freedom of
Information Act (FOIA) request of Febru ry 27, 1987, received
by the Agency on March 4. It addresses'ltem 2 of your request.
Items 1 and 3 are being answered by separate response.

We are treating Item 2 of your letter as a new request.
Based on the information supplied with this request, we are
granting your request for a waiver of fees.

Item 2 of FOIA Request

 

We are providing the records you requested relating to
the joint EPA/paper industry screening study of dioxin in pulp
and paper mills as follows. Please note that since your
request includes two items marked and two marked 
we have changed the second set of and to and 
respectively.

a. We are sending you, under separate cover, all draft
protocols and quality assurance project plans which have been

iQprepared to date (as well as a listing of them). These draft
?#94 documents are subject to revision to reflect, among other things,

jg? the final analytical methods chosen. In addition, we are
providing the individual site sampling plans for the five
mills participating in the study. No other records are
responsive to Item 2a.

b. and c. EPA possesses raw data_sheets and draft data
reports on samples which were analyzed as part of the process of
- develoPing analytical methods to meet the objectives of the study.
That is, when the study was initiated,_we recognized that there
g?

WIN

EHHBEFA



foam,?
UNITED STATES ENVIRJNMENTAL PROTECTION AGENCY
WASHINGTON. o.c. 20450
my?

OFFICE OF
WATER

MAR  8 987

Ms. Carol Van Strum
Route 2, Box 190
Tidewater, Oregon 97390

Re: Freedom of Information Act
Request RIN 1102?87

Dear Ms. Van Strum:

This letter is in partial response to your Freedom of
Information Act (FOIA) request of February 27. 1987. received
by the Agency on March A. It addresses Item 2 of your request.
Items 1 and 3 are being answered by separate response. 

We are treating Item 2 of your letter as a new request.
Based on the information supplied with this request. we are
granting your request for a waiver of fees.

Item 2 of FOIA Request

 

We are providing the records you requested relating to
the joint EPA/paper industry screening study of dioxin in pulp
and paper mills as follows. Please note that since your
request includes two items marked and two marked 

we have changed the second set of and to and 
respectively.

a. We are sending you, under separate cover. all draft
protocols and quality assurance project plans which have been
prepared to date (as well as a listing of them). These draft
documents are subject to revision to reflect, among other things,
the final analytical methods chosen. In addition, we.are
providing the individual site sampling plans for the five
mills participating in the study. No other records are
responsive to Item 2a.

b. and c. EPA possesses raw data sheets and draft data
reports on samples which were analyzed as part of the process of

developing analytical methods to meet the objectives of the study.
That is. when the study was initiated, we recognized that there

Page A


Page EXHIBIT
P0322 - MEMORANDUM

 

 

-2-

were likely to be some problems in performing reliable laboratory

analyses including 1) achieving the very low detection levels

needed to identify potential sources of dioxin within the mipls
(the.study's target detection level for wastewaters is 10 parts
per quadrillion. or approximately 1,000,000 times lower thaniis
generally achieved on analyses'of organic compounds in waster
waters); 2) being able to separate the dioxins and furans 
the large number of interfering compounds found in pulp and paper
mill wastes; 3) being able to distinguish among the many dioxin
and furan isomers. The problems were interrelated and often
compounded each other, as we discovered during some preliminary
runs where we had levels of detection that were much higher than
acceptable, ie., we wanted to be able to detect at much lowek
levels of occurrence. Therefore, the initial focus of the 
analytical phase of the study has been to perform a number 0
experiments to attempt to develop reliable analytical method
These experiments involved using different sample preparatiq
and clean-up procedures to remove interfering compounds andl
modifying the analytical instruments to improve their ability

to distinguish among the different dioxin and furan isomers.


s.

 

This experimentation process involved performing multiple
analyses of individual samples. Accordingly. the data reports
provide different results for the same samples, including at
least one case where both "detected" and "nondetected" results
were reported for a sample.

Therefore, the raw data and draft data reports which we
have thus far generated only provide information about these "test
runs," rather than providing information for use in the study
itself. In short, the data you are being provided is essentially
that collected during test method development and validation.
Most of it was generated using test methods that were found to be
inadequate and will not be used. EPA believes most strongly
that other use of these data (such as to characterize the Samples)

 

 

_is incorrect. EPA does not know if these test results show

 

what is actually in the samples. The study data do not yet
exist, except to the extent that we eventually may be able to
use one or two data points from the test runs. While we are
not certain whether you are interested in the test run data.
we are sending them to you in case you are. We are in the
process of collecting the raw data sheets and draft data
reports for this response. We'expect that they will be ready
to be sent to you within the next two weeks. 

 

At the time the samples were collected, certain physical
characteristics were measured and noted. These included such
factors as pH and temperature.; We do not plan to send you this
information since we understood your request to seek dana related
to dioxins and furans. However, should you wish to have thhs.
information as well, please let us know. 

d. We have had a number of verbal discussions about

Page 
Pace AFFIDAVIT
4 .MFMORANDUM 

 

9' -

-3-

possible sources of dioxins inipulp and paper mills, but EPA
has not prepared nor received any written record concerning the

.generation of dioxin in these mills. Much of our discussion

has focused on the chlorine bleaching process, which is reflected-
by the emphasis on bleach plant wastewaters in the siteTS?mpling
plans (see records responsive to Item 2a) and in some of??he

correspondence responsive to Item 2h. EPA expects that th35results
of the study will identify where in the process dioxin is being
generated or introduced. At this time, no records exist 

to Item 2d.

e. In response to this item, we are sending, under separate
cover, all records, including laboratory reports, data summaries
and miscellaneous dOCuments, which contain information on levels?
of dioxins in pulp and paper mill wastewater treatment sludges.

A list of these records also is being sent. In addition,
some of the correspondence provided in response to Item 2h
also may be considered to be responsive to 2e.

f. and g. We have verbally speculated about possible i
alternatives for reducing or eliminating dioxin discharges from
pulp and paper mills, but there have been no written records
on this. EPA is awaiting the results of the study to identify
the sources of dioxins before undertaking investigations of,
control alternatives. Therefore, there are no records responsive
to Items 2f and g. 

h. All records responsive to this item are being sent to
you under separate cover. The relevant correspondence begins
with March 5, 1986 letter sent under authority of
Section 308 of the Clean Water Act. The industry response to
this letter precipitated discussions resulting in the joint
study. .

i. No decision documents have been prepared concerning
the conduct of further studies of dioxin in pulp and paper mills.
Based on the findings of dioxin in sludges (see response to Item
representatives met in February of 1986 and decided,
as a first step, to conduct a detailed study of the mill
described in the Section 308 letter mentioned above. While
there are no documents responsive to this item (because there
are no documents reflecting "decisions") some of the records
provided in response to Items 2e and 2h discuss alternative
courses of action.

j. No documents exist which are responsive to this item.
k. No documents exist which are responsive to this item.

We are providing lists of documents identifying all records
responsive to Items 2a through of your request. Please
note that while we believe we have accounted for all responsive
records, we are checking with our regional offices to make

?Pads AFFIDAVIT 3 rm "fr


Page - MEraosAno'r-n

 

Page

certain that no records have been missed. If any additional

:records are located we will be notified within the next two

weeks and will inform you of whether those records
will be released or withheld.

If you have any questions concerning these records, please
contact Alec McBride at (202)382-7046.

. Sincerely,

. -rh.
Will1am A. Whitti gton, Director
Office of Water Regulations

and Standards



Page i? Page i 

Page 1Q - MEMORANDUM

 9 UNITED 


3. 

ENVIRONMENIAL PROT

saerL-m DISTRICT OF-TICE 

25089 RIDGE 

WESTLAK E. CHIO 4-11-15

1.


October 3, 1986 . 

-Mr. Russell 0. Blosser

National Council of the Paper Industry - .1
for Air and Stream Improvement, Inc. 

260 Madison Avenue 

New York, NY 10016

?7-35! .

Re: Industry Cooperative

Dioxin Screening Study
March 1986 Preliminary samples

Dear Mr. Blosser:

Today I received Dr. Tierdan's analytical method development report
for the preliminary samples collected in March 1986. The full report has

-been sent under separate cover to Frank Thomas and Larry LaFleur for

quality assurance review. The purposes of this letter are to advise you
of the results for the preliminary samples contained in the analytical
methods report (see attached handwritten data tables), and to request
that NCASI secure from the papbr company the analytical methods report
and results for in-plant preliminary samples. Copies of that report

should be provided to Frank Thomas, Larry LaFleur, and me as soon as
possible.

The attached data, along with the results of external quality control
samples for Episode 3018 (Dow Chemical analyses) suggest that the tetra-
chlorinated dioxins and furans are the principal species present in these
samples. If this is confirmed.by data from another mill, I believe we
should reevaluate our analytical strategy and direct more resources at
Dioxin 1 analyses and less at the more costly Dioxin 2 analyses.

 

i

if;



1






3017?? 94%"

30310

(loouori'YL UJOAUKL q!

- 2.0m;

Chomp. Wt Lech

a!

04.2,

.9125 M976 .


hdecu? 631



 

1
Per my conversation with Jim McKeown, I suggest we conduct a
conference ca11 during the afternoon of Hednesday, October 8, 1986, to
discuss this further.

Sincere1y yours, 

?ag 

Gary A. Amendola
Technical Project Manager

Enclosures
cc: A1ec McBride

James McKeown
Ray Hhittemore

 .

?sscro omm?wvwom aw-aa WW 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

(auto-0) Orv @100) or1 jQpO
(1,2017) (10' (9/00) 00' 3Q) 5H
(222m) 00? (2100) 60' 35(1ij
an 
257 cm 203'0 
"52.810 90'! (W00) 60? QEVO ?2,922 .
?ts/'0 lswo - Q0130 
. 
(1,2007 on! (5)00) 00? 
(5100) 00 5'qu 
(5)00}de ?Qd?j 
oze'O' 00' 1 ?([0630be $350 50953.1.
nub) 252'0 (woquc' (sac-3?0) 3'57 


Q?L??Pdva MEL-9638 snawvj? 
o/g' "663' ?74"303 2099093798 "or? 3:7de Ira/35'?
Ami? zwwm?u?w?d?f?g ?97%,me - 
7w?; 7 man: 2 6mm" .5 erIw-S?
$.in WI 
7876/ ?974/ awn/whip AmenSEd
i I
sum-w 

 

WW 

- 
5 zed-st.
i
/93?
Rcsuc?rs (J PM. Tmcuw

?093779 ?.waP
(Extras/{6M

 

.
4534 JAMPM Ma. 896806309 .309-

 

- WJH .rmm no. W644i -

72M 77w: 57"?


71f. 9_ 
(2:932 . a 01m) . -

.. 

no :90 
149 c.1303 no (4-H) +29 



 

 

OCDD - 33.9." 6/:2 I - 

2.769 278 5

 

334 we:

 

up (225) no (34.6)

 

 

ch-DF: up (22.0) 09 (24.0) - i 
up (454) pp I

 

ocID up no 

 

 

 




Lk?v BLANC- 0.0353!

 

 

 

 

 

 

 

 

 

 

 

 

 

AMGWJOM

PRCUMLJAAY MMCII 
pg5ucrs nJ 
#6444965 yam.) 0w: CLAY you: 1215 4mm Jawcmg 
USQPA Mo. SH 8:3 512.
wJu do. . 
59140-2 89546 swab?r SPMA 5M:
$23.73 no 3.3a amass!) no (0-707)
TC-DDY ?19 (0.433) .JI) (0.430)# 52,3 UQ (0.494) do (0.623)
CD95 

MW. h- 
OCDD
237a -TCDF up (0.707) 00(03275) up(o?9a) up(o.443) u0(o.e.52:
(0.575) 100 (0.499) 00mm.) 00 (0-440) no (0.688)


H9 

 

()ch

 

 

 

 

 

 

 

- . .
i -. 1 
5"

to

B?c?w
- 50mm 7340? 

asem {mm Ma 5115-8

.- 00$? 100- ?awe-$29 .
spa?4 - - - -- -
713w 571.. 3.23:1? CIPL . -

. 
CED: 
A. no

 

 

 

 

 

 

 

 

 

 

 

 

H9 DD (0.9) i 

m" 

Z378 - 4.2.3

31hr.

IJD C63)

.09 

H9QDR up (0.3)

(3ch no 

- 1 

I 


 

 

 .- .

Q5 UhuTEo STATES - . . _Hun.
3% ENVIRONMENTAL PROTECTION AGENCY
3 REGION 
DIISTRICT OFFICE
25059 CENTER RIDGE ROAD

WESTLAKE. OHIO 44145

September 16, 1986

Mr. Russell 0. Blosser

National Council of the Paper Industry
for Air and Stream Improvement, Inc.

260 Madison Avenue

New York, NY 10016

?t

Re: Industry Cooperative
Dioxin Screening Study
Episode 3018

Dear Mr. Blosser:

Per our September 15, telephone conversation, please find
enclosed the results of external quality control analyses for four samples
conducted by the Dow Chemical Company at USEPA's request. Also attathed
are the associated wastewater flow data for samples DE020915 and DE020922.
Note that sample DE020923 is the NCASI quality control sludge. The
laboratory analytical package for these samples will be sent directly to
Larry LaFleur and Frank Thomas for quality assurance review as soon as I
receive it from Dow Chemical. 1n the interim, these data should be
treated as preliminary results subject to quality assurance
rev1ew.

I suggest that we conduct a conference call after you evaluate these
data for the purpose of reviewing the analytical priorities established
for Episode 3018 and subsequent sampling programs.

I look forward to hearing from you soon.

Sincerely yours, 

may

Gary A. Amendola .
USEPA Technical Project Manager

Enclosures

cc: Alec McBride, USEPA (NH-553) 
Frank Thomas, USEPA, CRL
James J. McKeown, NCASI
Larry LaFleur, NCASI

4% DOW CHEMICAL U.S.A.

 

manou
September 4 1 9 8 6 MIDLAND, MICHIGAN 48640

Mr. Gary A. Amendola
U.S. EPA - Region 
Eastern District Office
25089 Center Ridge Road
Westlake, OH 44145

Dear Gary:

Enclosed are the final results of the Paper Industry
samples from our Analytical Laboratory.

If you have any questions about these results, please donit
hesitate to call me.

Sincerely,

mIUO/ps/

J. M. Rio, Manager
Environmental Services
628 Building

636?2646

/pe

Enclosure

AN OPERATING UNIT OF THE DOW CHEMICAL COMPANY Means-Mote 

 

 

 

REF: m-mp?uz

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

rm mom mousmv mm new mm uzsuus "3
MUS GUADRILUIN: mm mulou:
Based on fatal :37an weight (liquid solids) Based on calculah-d sample dry weight
DE 02095: m2 Df 020922: mm: a or 020920: souo or 020923: soup 5
3050-1504 can 01 3050-50-2 cm '2 30504503 coo -: 30504504 coo-4
DIOXINS [793.73 163:.55 5.053 8.90, DRY 150m MIRCINNUIEZ:
2378-1100 I50 '73 I7 240 Im Specific
"om-mun: Way 721 66: 6?57: 877.
a nd 25 Unimmln Speci?city
"mm-Prue; Ram 70: 861 70;: IN:
.25739- awe nd (20) nd (20) nd (71 6 [saver Specific
nd (Is) rd (7) 2 a 1m ?pecific
223478-9030 nd nd (5) nd (7) I 1mm Specific
797. 62% 761 641
Imam-mo 45 no) 30 (6) no (6) I50 Iaamcr SpKifl't.
. ?may 56: 701 581 85,!
?on 220 (40) 220 (an) 59 (9) I400
"(3.000 1 7871 B97 751 34%
I H20 Content (weigh? lass andrying at For ~21 hrs) 66.41 10311410
DE or 020922: mum: as (Hummus or 020923} sous"
Bloc-b-l (or '1 aos-a-z (or '2 31053-3 cur-3 jun-N ans '4
1793.73 1631.53 5.053 ow 8.903 autumn NOTE5
zm-rcoF 500 000 5m 2 500 speci?city
"c-zm- TIDF Raway 32;: 62% an as;
23476-PEDF 23 (3) 16 3 (I) 55 Unkmm Speci?tify
Izava-ncor 27 (3) 16 3 :40 Wn Speci?city
"mm-m 1mm 791 as; 
?3451'?? "4 z) 3 L'nkmn spaci?di?,? 
mam-near Specificity
mane-Hm 9 5 20 0mm 5pm'?afy
I234 . Unkmm Spai?cny
85: 103:: 39,: 691 
mam-mar nd nd no) nd (5) 5 (2) [saw Speci?c
mum-HM so (5) 7 (7) 2 (2) harm Speci?c
Uc-Izmva-Har?my 79Farm-d mm Whafman GHC soul? frachm - Den en: 5mm, rum/arr - lax benjem in Imam lizard/117w; afrac/s (mallard
n'cr?aoh'd on "harm afgc Wars 0:173:27: Md. nporkd an my basis.
Nahrq am harm-5 corrcded ?r sfandaro? mom as for each conga/per mp; excepf oar-v warned m1 recovery
vang- are mm of och-(hon - 2.5:me fa rail: mm ?'90ch region of mags chroma ram; m' - mi den-cm.
A Dmah: my momfared lb, no Interference gimfemal pmserxe of ch/orinafcd dam.- I .

mm: was)?: (?mm/Hm; of large 'mrr- nitric-rem: mm]: accurate quam: arm.



TABLE 2

U.S. ENVIRONMENTAL PROTECFION HILL INDUSTRY
UIUXIN SCREENING STUUY

Episode: 3018

Sample Date: 6/24-25/86

Sample Number: DEOZU 801 806 807 811 915 921 922 821
om ne om ne om ne omb ned omb ned lna
Pulping Recovery Paper Bleach Untreated Hastewater Landfill
Recaust Plant Machine Plant Hastewater Effluent Leachate

Field Data Smwnary

 

amp 9 ype
Date 6/24- 6/24- 6/24- 6/24- 6/24- 6/24- 6/24/86
25/86 25/86 25/86 25/86 25/86 25/86

Time 1706/ 1945/ 1940/ 1720/ 2005/ 1955/ 1440
1525 1700 1617 1545 1550 133n

Field Parameter

OH

Ran s.u.

on uct um 05
an 
vera 

em erature
an 
vera 

Sample Type: 24 EVC - 24-Hour Equal Volume Composite
Meter malfunction. - Grab

  
  
  

 
  

:1 

12 'ig?f?i. 
I 1 .1.
32;, 

  
    

    

. i"
.
. 9

.a-Epi?? 
33:35.?14r12? 

?3 

   
 
 
 
 
  

 

 

 

 

  

 

   
 
     

   
  
 
 
  
 

?2 

. 
1

 



      



 

 

 
 
  

   
 
 
      

     
   

 

    

          
  
 
 

   
 

     
 
  

   
 

3'

11"? . -
mu(niggrr?hrm: . w-
?tm?tgg?in?lh3:141WEST COAST REGIONAL CENTER

I PO. Box 456

CORVALLIS. OR 97339

cas (503) 754-2015

NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT, INC.

January 9, 1987

MEMO To: Russell Blosser and Gary Amendola
FROM: Larry E. LaFleur 4?7


SUBJECT: Chlorophenol Analysis Reports For EPA/Paper Industry
Cooperative Dioxin Screening Study Episodes 3010 (Boise
Cascade, International Falls) and 3021 (Crown
Zellerbach, Wauna).

Enclosed are reports summarizing our chlorophenol analysis
results for the first two co?operative study sampling episodes.
Should you have questions about the reports or the data please
don't hesitate to contact me.

All the tables were prepared from spreadsheet files
and could be provided on disk if that format would be more useful
to your purposes.

 

 

II


IV

TABLE OF CONTENTS

INTRODUCTION

ANALYTICAL METHODS

QUALITY ASSURANCE
RESULTS 
LITERATURE REFERENCES 

 

 

Page

h) r4 

RESULTS OF NCASI ANALYSIS OF CROWN ZELLERBACH, WAUNA
SAMPLES FOR SELECTED CHLORINATED PHENOLIC COMPOUNDS

I INTRODUCTION

The Crown Zellerbach, Wauna, Oregon, mill was the second
mill sampled in the USEPA/Industry Cooperative Dioxin Screening
Study. The sampling took place from September 8 to 9, 1986.
Samples of selected wastewater streams and effluents which were
designated for chlorinated phenolics analysis were split and sent
to the NCASI West Coast Regional Center. This splitting provided
external quality assurance on the contract laboratory and, since
no analytical protocol had yet been developed by the Wright State
University laboratory for the analysis of chlorinated phenolic
compounds, provided added assurance that at least some data would
be available. The following summarizes the results of the
analysis of those split samples.

II ANALYTICAL METHODS

All samples were analyzed by NCASI Method 
Chlorinated Phenolics in Water by In Situ Acetylation/GC/MS
Determination, as described in NCASI Technical Bulletin No. 498
(1) except two stable isotope internal standards were used 0
improve the quantitation. The and 1 C6-
pentachlorophenol internal standards were spiked into the sample
prior to acetylation and extraction. The quantitation technique
described in EPA Method 1625 (2) was used except a three point
calibration procedure was used. The recoveries of the internal
standard were calculated based on calibration using the 3,4,5-
trichlorophenol internal standard normally used for quantitation.
The stable isotope internal standard recoveries are helpful in
assuring meaningful spike levels were used (that is, the contri-
bution of the native ion to the internal standard quantitation
ion was minimal), that there were no major interferences with the
stable isotope internal standard and where the analytes were not
detected, as an in sample demonstration of method recovery.

QUALITY CONTROLLQUALITY ASSURANCE

A method blank was run concurrent with the acetylation and
analysis of the samples. None of the analytes were detectable in
the blank.

Sample 86?37-4644 (untreated wastewater) was selected for
quality assurance duplicate and native spike since it represented
the combined bleach plant sewers and was amongst the most diffi-
cult matrices. The duplicate and native spike recovery data is
summarized in Table 1. The relative percent differences were all
less than 20 percent except for two of the chlorinated vanillins.
These relative differences were higher as would be expected for

9?

results near the detection limits of the method. Although two
native spikes were conducted, the spike levels were at 
different levels therefore additional information on the preci-
sion of non-detected analytes is not available. The recoveries
were, however quite satisfactory. Future sample sets will
include true spike duplicates to provide information on the
precision of the method for analytes which are not routinely
detected.

IV RESULTS

The results of the analysis of the samples are summarized in
Table 2. Although detection limits for individual analytes are
not specifically calculated, we estimated them ug/L range. Although the relatively low recovery of 
dichlorophenol in samples 86-37-4601 and 86?37?4617 suggests some
volatilization losses, they still fall within the range that
would be acceptable in EPA Method 1625 and the remaining recov-
eries seemed satisfactory.

LITERATURE REFERENCES

(1) NCASI Technical Bulletin No. 498, NCASI Methods For The
Analysis of Chlorinated Phenolics in Pulp Industry
Wastewaters (July 1986).

(2) EPA Method 1625, Revision B., Semivolatile Organic Compounds

by Isotopic Dilution Federal Register, Vol. 49 No.
209.

 

 

 

 

 

TABLE 1 SUMMARY OF DUPLICATE AND RECOVERY DATA
FOR SAMPLE 86-37-4644
Duplicate Data Recovery Data
Relative
Percent ug/L Percent ug/L Percent
Analyte Rep #1 Rep #2 Difference ?piked Recovery Spiked Recovery
2-Chlorophenol ND ND NA 48.9 99 39.1 97
2,6-Dichlorophenol ND ND NA 43.9 107 35.1 95
2,4-Dichlorophenol 10.7 8.8 19.0 34.2 110 27.4 82
3,4-Dichlorophenol ND ND NA 39.3 109 31.4 98
2,3-Dichlorophenol ND ND NA 43.7 112 35.0 105
2,4,5-Trichlorophenol ND ND NA 39.8 119 31.8 88 .
Pentachlorophenol ND ND NA 40.3 126 32.2 98 
4,5-Dichloroguaiacol 4.4 5.2 17.0 34.7 117 27.7 94 
3,4,5?Trichloroguaiacol 8.7 9.0 3.0 23.8 100 19.0 97
4,5,6-Trichloroguaiacol 3.2 3.3 3.0 40.6 112 32.5 111
Tetrachloroguaiacol 6.2 6.3 2.0 25.9 107 20.7 127
5-Chlorovanillin 1.9 2.5 27.0 28.1 107 22.5 130
6-Chlorovanillin 6.5 6.4 2.0 39.0 121 31.2 112
5,6-Dichlorovanillin 2.1 1.2 53.0 33.5 113 26.8 131
Isotope Percent Recovery
2g3?2 4-Dichlorophenol 75 91 94 
1 CG?Pentaohlorophenol 110 108 81 102

ND Not Detected
Not Applicable

TABLE 2 SUMMARY OF RESULTS OF ANALYSIS OF CROWN ZELLERBACH, WAUNA

Concentration Detected

3

 

 

 

jug/L)
86-37- 86-37? 86-37- 86?37- 86-37- 86-37? 86-37- 86?37- 86?37-

Analyte 4601 4613 4614 4615 4616 4617 4644 4645 4646
2-Chlorophenol 2,6-Dichlorophenol 2,4-Dichlorophenol ND 9.7 ND 43.6 3.7 ND 9.8 0.2 ND
3,4-Dichlorophenol 2,5-Dichlorophenol 2,3-Dichlorophenol 2,4,5?Trichlorophenol Pentachlorophenol 4,5-Dichloroguaiacol ND 4.8 1.4 196 15.9 5.6 4.8 ND ND
3,4,5-Trichloroguaiacol ND 14.3 6.6 351 31.5 11.3 8.9 2.3 ND I
4,5,6-Trichloroguaiacol ND 7.3 0.9 146 68.5 11.8 3.3 1.7 ND 
Tetrachloroguaiacol ND 14.1 4.8 170 81.4 21.0 6.3 2.8 ND I
5-Chlorovani11in ND ND ND 24.4 15.0 4.6 2.2 1.9 ND
6-Chlorovanillin ND 5.6 ND 163 19.6 8.9 6.5 4.2 ND
5,6-Dichlorovanillin ND 6.1 ND 97.0 64.8 14.7 1.7 3.2 ND
Isotope Percent Recovery
2H3-2,4-Dichlorophenol 13C5-Pentachlorophen01 Not Detected

 23 

t"

UNITED-STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. DC. 20460

 



OF
WATER
MEMORANDUM
SUBJECT: Bioaccumulation Study Project Plan and Related
Materials
FROM: Alec McBride, Chieprhk/
3. Water Quality Analysis Branch 

TO: Regional Study Coordinators

Attached are the final project plan for the bioaccumulation
study (Attachment 1) and a memorandum from Bill Whittington,
OWRS Director, to the BSD and Water Division Directors (Attachment
2), which summarizes the background. objectives, and management
framework for the study. 

The project plan incorporates the major issues resolved at
the Dallas meeting. The list of analytes has undergone further~
revisions which included dropping chemicals that: l) have BCF 
values less than 300. since the projected human exposure from
consuming fish is less than that from drinking water, 2) are
quickly metabolized in fish or hydrolyzed, and 3) have anal ical
difficulties, such as lacking analytical standards.: The lis is
still somewhat flexible as compounds may be removed due to
operational analytical difficulties or added if they are of .
concern and standards and methods are available or can be developed.

Most of the sites each region recommended are included in th_
study. Fish sampling sites associated with paper mills using the 
bleach kraft process, however, are not included as part of this
study. Instead, by August 15 we will review the list of 145 mill
identified by NCASI as those which use the bleach kraft process
(Attachment 3) and identify which had fish sampled neanby during
the dioxin study. For the remaining mills on the list Which are
active dischargers, we would like you to arrange to collect and
analyze fish samples through the Wright State contrac
manaiid by ORD-Duluth. Funding adjustments will be made in FY87

 

to that these analyses can be completed. 
As discussed previously, we have deposited the remaining 1
dioxin study funds in the Wright State contract. Each region 1 

. 

 2 

  
  

- a couple of previously negotiated exceptions) has approxi-
mat' $15,000 available in that contract for analytical support,
and those funds need to be spent by May 1, 1987. In order to use
y0ur funds, first contact Dr. Tom Tiernan (513?873-2202) at
Wright State to discuss your-needs and the estimated hours and
dollars for each task. After consulting with Tom, fill out a
work assignment form (Attachment34) and send one copy to Fred
Freeman, Project Officer, ORB-Duluth.and one copy to us. Fred
will see to it that the assignment gpes through the proPer contract
channels. A fish sample analysis for 2.3.7.8-TCDD only should
run about $600.

The Sample Control Center (SCC) will track the sampling and
analytical effort for both the fish samples from below paper
mills and for the bioaccumulation study. Prior to sampling,
please contact Jim King with the SCC (FTS 557-5040) to obtain
identification information and shipment records for each site.
We will be working with ORB-Duluth to set up a data management
system for accessing the analytical results. We hope to have this
system working by November, which is the earliest we expect data to
be available.

Please let me know if you have any questions regarding
implementation of the study or its funding.

Attachments

cc: Doug Kuehl
Pete Redmon
Martin Brossman 
Dave Terpening 
Bob Kleopfer
Fred Leutner

Gary Amendola 1



a


. 

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

 



MEMORANDUM

SUBJECT: Description of the Bioaccumulation Study

TO: Regional Water Division Directors
Regional Environmental Services Division Directors

The Monitoring and Data Support Division (MDSD) will soon
initiate sampling for a two-year study designed to investigate
the bioaccumulation of selected toxic pollutants in fish. This
bioaccumulation study is, to a large extent, an outgrowth of
EPA's National Dioxin Study, which investigated the extent of

- contamination in soil, fish, and air. Some of the
samples collected during the dioxin study will be reanalyzed for
this study. The focus of the study is on pollutants which are
potential human health threats primarily through fish contamination,
as opposed to pollutants which are more likely to affect humans
through other exposure routes such as drinking water.

The impetus for the bioaccumulation study was the increasing
awareness that fish consumption may be a significant human exposure
route for toxic pollutants and the concern that there may be a
number of uninvestigated pollutants with properties similar to
which could bioaccumulate in fish. In addition, as
part of its response to a petition from the Environmental Defense
Fund (EDP) and the National Wildlife Federation (NWF), EPA committed
to conducting an aquatic monitoring survey for other chlorinated
dioxins and dibenzofurans to support regulatory decisions relating
to a number of provisions under the Clean Water Act.

The major objectives of the study are: to indicate the 13w
overall prevalence and concentrations of approximately 70 selected

pollutants in fish from locations statistically selected from 4!
ambient monitoring networks, in relatively undisturbed back- .

ground areas, and in areas with high concentrations of indus- I:

trial discharges and/or high bioaccumulation potential; (2) to 

determine the levels of a limited subset of these pollutants in 
fish in the immediate vicinity of specific potential sources; and

(3) to evaluate potential effects on human health.
i
Potential candidate chemicals came from several sources
including lists of priority pollutants, non-convential pollutant
pesticides found in effluents from pesticide manufacturing

 

facilities, chemicals identified by the Carcinogen Assessment
Group (GAG) or the International Agency for Research on Cancer
(IARC) as known or potential cancer?causing agents, organic
compounds identified in human adipose tissue, pollutants identified
as non?biodegradable in industrial and POTW effluents, and various
compounds recommended by regional and laboratory personnel.

A total of approximately 400 compounds were screened for
bioaccumulation potential in fish. Compounds not expected to
bioaccumulate to a significant extent were removed from the list.
The remaining chemicals were screened for potential toxic effects
in humans and for projected biochemical fate in fish and the
aquatic environment. Compounds that are quickly hydorolyzed or
metabolized were also removed from the list. Finally, a few
pollutants were drOpped from the list based on analytical difficul-
ties (extensive methods development needed or lack of analytical
standards). The target list of approximately 70 analytes (Attach-
ment 1) is not completely final since compounds may be removed
due to operational analytical difficulties or added if they are
of particular concern and methods can be developed.

For most of the analytes, MDSD was able to estimate fish
tissue concentrations of concern to human health. These levels
were derived from data on chronic toxicity or carcinogencity
using procedures normally applied to water quality criteria
development. These estimates were done to ensure that the
analytical detection limits for each analyte were low enough to
detect levels of concern as well as to assist in evaluating the
results.

The initial subset of pollutants for which targeted sampling
will take place include chlorinated dioxins and furans and hexa?
chlorobenzene. The targeted sites were selected jointly by MDSD
and the regional coordinators, who are listed in Attachment 2.

As results from the study becomes available, additional pollutants
will likely be selected for targeted sampling.

The study will be conducted in much the same way as the
dioxin study was conducted. Overall study design was done primarily
by MDSD, while site selection was done by both MDSD and the
regional coordinators. MDSD will provide funding to the Regions
to ensure that the field work is done and will provide access to
sampling contractors where necessary. In most cases, the regional
coordinators will use state agencies to do the field work. MDSD
will also provide funding to 0RD to provide analytical support.
All participants will provide input to the final report, which
MDSD will compile. We hope that this process will be as successful
as it was for the dioxin study.

 

I will be sure to keep you updated as the study progresses.
Please feel free to call me or Alec McBride (FTS 382?7046) if
you have any questions or comments on the study. We do have some
flexibility in how we proceed, and I would appreciate any thoughts
you might have on things we should be investigating.

Attachments

William A. Whitti?gton, Director
Office of Water Regulations and

Standards (WE-551)

 

Attachment 2.

Region
I

II


IV

VI
VII


IX

?if

Regional Bioaccumulation Study Coordinators

Bill Walsh, BSD

Rick Spear, BSD

John Ruggero, BSD

Ron Raschke, BSD

Howard Zar, Water

Dave Parrish, BSD

Billy Fairless, BSD

Dean Gillam, ESD
Kathleen Shimmin, Toxics

Lori Cohen, Air and Toxics

Attachment 1.

Biphenyl
Butachlor
Chlorbenzilate
Chlordane, cis
Chlordane, trans

Chlorinated Dioxins
Furans:
2378-TCDD


123789-HXDD
123478-HXDD




123678-HXDF
123789-HXDF




Chlorpyrifos

Dicofol (Kelthane)
Dieldrin
(DEHP)
Diphenyldisulfide
Endrin

List of Target Analytes

Heptachlor
Heptachlor epoxide
Hexachlorobenzene (HCB)
Hexachlorocyclohexanes (BHC)
including Lindane

Isopropalin

Kepone

Mercury



Mirex

n?alkanes 

Nitrofen

Nonachlor, cis

Nonachlor, trans

Octachlorostyrene



Pentachloroanisole

Pentachlorobenzene

Pentachloronitrobenzene

(PCNB)

Pentachlorophenol

Perthane

Biphenyls:

Mono-Decachlorinated

Biphenyls



S?Tetrachlorobenzene
-Tetrachlorobenzene
?Tetrachlorobenzene
richlorobenzene
-Trichlorobenzene
1,3,5?Trichlorobenzene
Trichloronate

Trifluralin

Triphenyl phosphate


HU?lah




Total PCBs