k United States
^£ Environmental Protection Agency
LOVE CANAL
EMERGENCY
DECLARATION AREA
HABITABILITY STUDY
FINAL REPORT
VOLUME IV
Soil Assessment-
2,3,7,8-TCDD
TECHNICAL REVIEW COMMITTEE
U.S. Environmental Protection Agency Region II
U.S. Department of Health and Human Services/
Centers for Disease Control
New York State Department of Health
New York State Department of Environmental Conservation
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VOLUME IV
Soil Assessment-
2,3,7,8-TCDD
Prepared for
U.S. EPA REGION II
26 Federal Plaza
New York, New York 10278
Prepared by
CH2MHILL SOUTHEAST, Inc.
P.O. Box 4400
Reston, Virginia 22090
Under Contract No. 68-01-7251
March 1988
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CONTENTS
Section Page
ACKNOWLEDGEMENTS iv
LIST OF ACRONYMS AND ABBREVIATIONS v
1.0 SUMMARY 1-1
2.0 INTRODUCTION 2-1
2.1 Background 2-1
2.2 Habitability Criteria 2-4
3.0 GOALS 3-1
4.0 DESIGN 4-1
4.1 Project Organization 4-1
4.2 Field Sampling 4-2
4.3 Quality Assurance 4-5
5.0 METHODS 5-1
5.1 S ample Collection and Homogenization 5-1
5.2 Sample Analysis 5-2
5.3 Data Validation 5-2
6.0 RESULTS 6-1
6.1 Sampling Activity 6-1
6.2 Quality Assurance Results 6-1
6.3 Analytical Results 6-6
6.4 Discussion of Results 6-10
REFERENCES
APPENDIX A: Field Evidentiary Audit Report A-l
APPENDDC B: Homogenization Laboratory
Evidentiary Audit Report B-1
APPENDDv C: Environmental Services Division
Quality Assurance Report C-l
u
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CONTENTS
(continued)
Page
Tables
6-1 Number and Type of Samples Generated 6-3
6-2 Archive Sample Results vs. Associated Original
Sample Results 6-5
6-3 Summary of Performance Evaluation Results 6-7
6-4 Distribution of Analytical Results with
Respect to Sample Locations 6-9
6-5 Summary of Analytical Results for
Samples with Detected Concentrations 6-12
6-6 Distribution of Analytical Results with
Respect to Concentration Ranges 6-15
Figure
2-1 Love Canal Emergency Declaration Area--
Niagara Falls, New York 2-3
4-1 Soil Assessment-2,3,7,8-TCDD
Example Grid Node Sampling Plan 4-4
6-1 Soil Assessment--2,3,7,8-TCDD
Location of Actual Sampling Points 6-2
6-2 Soil Assessment~2,3,7,8-TCDD
Location of Samples with Detected
Concentrations 6-8
6-3 Soil Assessment-2,3,7,8-TCDD
Frequency of MPC Values for Analyses
of Field Samples with Non-Detect Results 6-11
m
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ACKNOWLEDGEMENTS
The authors gratefully acknowledge the efforts of all organizations and in-
dividuals who assisted in the conceptualization, design, and implementation
of this study. Special acknowledgement for their continuing guidance goes
to the U.S. Environmental Protection Agency (EPA) Region II and the other
agencies composing the Technical Review Committee: the U.S. Department
of Health and Human Services/Centers for Disease Control, the New York
State Department of Health (NYSDOH), and the New York State Depart-
ment of Environmental Conservation.
Additional acknowledgement goes, in chronological order of their involve-
ment, to the following organizations: the Department of Health and Human
Services/Agency for Toxic Substances and Disease Registry for guidance
during the design of the sampling plan; the NYSDOH for obtaining proper-
ty owner permissions and scheduling the soil sampling; Cambridge Analyti-
cal Associates, Inc., for laboratory services supporting the field sampling;
Ecology and Environment, Inc., for field sampling andrelated logistical sup-
port; Black & Veatch, Inc., for field sampling; Horizon Systems Corporation
for sample tracking and automated data management; the University of
Nevada at Las Vegas for sample homogenization in the laboratory; the Na-
tional Enforcement Investigation Center and its contractor, Techlaw, Inc.,
for conducting evidentiary audits of the field sampling and sample
homogenization efforts; the EPA Region II Sample Management Office and
Contract Laboratory Program laboratories used for sample analysis; and the
EPA Region II Environmental Services Division for data validation.
IV
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LIST OF ACRONYMS AND ABBREVIATIONS
CDC Centers for Disease Control
CLP Contract Laboratory Program
DHHS U.S. Department of Health and Human Services
EDA Love Canal Emergency Declaration Area
EPA U.S. Environmental Protection Agency
ESD U.S. EPA Region II Environmental Services Division
LCIC Love Canal Indicator Chemical
MPC Maximum possible concentration
NEIC EPA National Enforcement Investigation Center
NYSDEC New York State Department of Environmental
Conservation
NYSDOH New York State Department of Health
OTA U.S. Congressional Office of Technology Assessment
ppb Parts per billion
QA Quality assurance
QAPP Quality Assurance Project Plan
QC Quality control
SMO U.S. EPA Region II Sample Management Office
TCDD Tetrachlorodibenzo-p-dioxin
TRC Technical Review Committee
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1.0 SUMMARY
The Love Canal Emergency Declaration Area; Proposed Habitability
Criteria (NYSDOH and DHHS/CDC, 1986) calls for three environmental
studies. This report describes the soil assessment for 2,3,7,8-TCDD (2,3,7,8-
tetrachlorodibenzo-p-dioxin, also referred to in this document as dioxin).
Two other reports describe the air assessment and the soil assessment for in-
dicator chemicals.
The habitability criteria document states that known and applicable
guidelines and standards will be used where applicable to assess habitability.
The known guideline for dioxin is the Centers for Disease Control (CDC)
level of concern of 1.0 part per billion (ppb) dioxin in residential surface soil.
The goal of the soil assessment for dioxin was to determine whether 2,3,7,8-
TCDD is present in the soil of the Love Canal Emergency Declaration Area
(EDA) at concentrations of 1.0 ppb or more. Sampling point density was
based on an analysis of the median size and shape of residential lots in the
EDA. A 69-foot-square sampling grid was developed in order to attain a
high probability of detecting a median-size contaminated lot. Specific
protocols were developed to select an alternative sampling point in the event
that a grid node fell on an area that could not be sampled. In addition, as a
response to public request, the Technical Review Committee (TRC), which
oversees the habitability assessment program, decided that a minimum of
two samples should be collected on each residential lot.
Samples were collected during November and December of 1986 and during
May and July of 1987. A total of 2,274 field samples were collected, and
593 quality control (QC) samples were prepared. Sampling locations (grid
nodes, alternative sampling points, and two-per-lot points) were surveyed
for precise identification of the sample site. The surface (2-inch depth) soil
samples were homogenized and sent to an analytical laboratory. The analyti-
cal laboratories used were those in the U.S. Environmental Protection
Agency's (EPA) Contract Laboratory Program (CLP). The U.S. EPA
Region II Environmental Services Division (ESD) conducted validation of
the analytical data.
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Over and above the 2,274 points sampled, 111 planned sampling points were
not sampled because of physical obstructions in the field or because of lack
of permission from property owners. A total of 14 samples (0.6 percent)
were not successfully analyzed during the course of the study because the
analysis did not meet QC criteria and in one instance, the sample contained
too much moisture.
A quality assurance (QA)/QC program was designed and implemented to
monitor and maintain the quality of the study relative to stated data quality
objectives. Results of the analyses of QC samples indicated that contamina-
tion had not occurred during shipping and storage. Valid results were ob-
tained for samples representing 99.4 percent of the sampled points. The QA
objectives for the study were met.
Dioxin was found at concentrations above the study target of 1.0 ppb at only
one sample location (0.04 percent of the sample locations). This sample of
surface soil was taken from a vacant lot in Neighborhood 4, and five aliquots
were analyzed as discrete samples. Dioxin was measured at concentrations
ranging from 17.3 to 21.2 ppb. Dioxin was not detected at adjacent sampling
points, indicating that contiguous dioxin contamination at levels above the
1.0-ppb level of concern may not be widespread. Access to the area sur-
rounding this sampling point has been restricted by a security fence. Further
sampling of this area will be conducted under the Love Canal remedial
program to identify the extent of contamination and to plan remedial ac-
tivities.
Dioxin was detected at 48 sample locations (2.1 percent of the sample loca-
tions) at concentrations below the study target of 1.0 ppb. Analytical results
for the remaining 2,211 sample locations (97 percent) did not contain detec-
table levels of dioxin.
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2.0 INTRODUCTION
This report is Volume IV of a five-volume series. Volume I provides an in-
troduction and documentation of the decision-making during the develop-
ment of the; Love Canal EDA Habitability Study. Volume II reports on the
air assessment for indicator chemicals. Volume in presents the results of the
soil assessment for indicator chemicals, and Volume V summarizes the sub-
sequent peer review of Volumes n, El, and IV and the responses to that peer
review.
This document summarizes the design and results of the soil assessment for
dioxin. It is presented in six main sections and contains three appendices.
Sections 3.0, 4.0, and 5.0 discuss the study goals, design, and methods,
respectively. Section 6.0 summarizes the study results. The appendices con-
tain reports from independent agencies summarizing the results of the field
and laboratory audits and the analytical data validation efforts maintained
throughout the study.
2.1 BACKGROUND
A detailed background of the history of Love Canal is presented in Volume I.
This section provides a brief summary to assist the reader in understanding
the overall intent of the Love Canal EDA Habitability Study and the role of
the soil assessment for dioxin.
The former Love Canal landfill was a rectangular, 16-acre tract of land lo-
cated in the southeastern end of the City of Niagara Falls in Niagara Coun-
ty on the western edge of New York State. The landfill takes its name from
William T. Love, whose plan in the 1890s was to dig a canal between the
upper and lower Niagara River to provide inexpensive hydroelectric power
for a proposed model industrial city. The model city project and the partial-
ly dug Canal were abandoned before the turn of the century. The abandoned
Canal was used as a chemical waste dump from 1942 to 1953. In 1953, the
site was closed. Subsequently, a number of homes were built around the
Canal, and the 99th Street School was built adjacent to the Canal. Soil from
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the Canal was moved to the 93rd Street School site where it was used as fill.
(Canal soil may also have been moved to other locations within the EDA.)
In the spring of 1978, following a series of complaints by local residents,
studies were initiated to investigate the health and environmental problems
at Love Canal. Under the direction of the New York State Department of
Health (NYSDOH), basement sump pits were sampled and analyzed, and,
under the direction of the U.S. EPA, air samples were taken at homes abut-
ting the Canal. These results revealed significant contamination, and in
August 1978, the first of two states of emergency was declared by President
Carter. Homes were evacuated and remedial efforts were underway by
October 1978.
Remediation at Love Canal has been extensive. Initial remediation con-
centrated on site containment. A clay cap was installed over the Canal area,
and perimeter drains were installed during the period from May to Novem-
ber 1979. A leachate collection system and a leachate treatment plant were
constructed during late 1979. Since that time, an extensive program for
removing dioxin-contaminated sediments from area sewers and creeks has
been underway. (Volume I of this report provides additional details on Love
Canal remediation efforts.)
Meanwhile, concern persisted about the habitability of the residential area
surrounding the Canal. In May 1980, President Carter issued a second emer-
gency declaration for Love Canal establishing the EDA as shown in Figure 2-
1, and more homes were evacuated. Eligible properties were purchased from
evacuating residents by the Love Canal Area Revitalization Agency.
In the summer of 1982, the EPA released a report assessing the extent of air,
water, and soil contamination in the EDA. The report was intended for use
as a basis for making recommendations regarding future use of the area (U.S.
EPA, 1982:). Later, the U.S. Department of Health and Human Services
(DHHS) reviewed the EPA study and other data to determine whether the
EDA was habitable. In July 1982, after considering comments by the Na-
tional Bureau of Standards on the procedures the EPA used and after further
consultation with the EPA, DHHS affirmed an earlier provisional decision
that the EE>A was as habitable as the areas to which it had been compared.
This decision was contingent on the provision that the storm sewers and their
drainage tracts be cleaned and that special plans be made to perpetually
safeguard against future leakage from the Canal.
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WfiOSTHKT
SCHOOL SITE
IUHDER SEPARATE srvn>>
VICINITY MAP
SOURCE:
EDA BOUNDARIES TAKEN FROM NEW YORK STATE
REAL PROPERTY TAX LAW ARTICU: 17. SECTION 1702
Figu-e 2-1
LOVE CANAL EMERGENCY DECLARATION AREA
NIAGARA FALLS. NEW YORK SCALE: 1"=750'
LEGEND
EMERGENCY DECLARATION AREA (EDA) BOUNDARY
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In December 1982, the U.S. Congressional Office of Technology Assess-
ment (OTA) was requested to examine the technical basis for and validity of
the habitability decision for the EDA. In June 1983, the OTA reported that,
with the information available, it was not possible to conclude whether or
not unsafe levels of toxic contamination existed in the EDA and that the
analysis of available data did not support the DHHS decision that the EDA
was as habitable as the areas with which it had been compared (OTA, 1983).
In August 1983, in response to the OTA report, the EPA established a TRC
composed of representatives from the EPA, NYSDOH, DHHS/CDC, and
New York State Department of Environmental Conservation to coordinate
and overset; the habitability study and remedial program at Love Canal. The
member agencies of the TRC asked NYSDOH and DHHS/CDC to develop
criteria that would be considered by the New York State Commissioner of
Health in his determination of whether or not the EDA is habitable. In 1986,
the Love Canal Emergency Declaration Area; Proposed Habitability
Criteria (NYSDOH and DHHS/CDC, 1986) was issued. The habitability
criteria document underwent peer review (Life Systems, 1986) and reflects
the concerns of the peer review panel.
2.2 HABITABILITY CRITERIA
The habitability criteria (NYSDOH and DHHS/CDC, 1986) stipulate that for
chemicals identified in environmental media to which residents and poten-
tial residents may have significant exposure, relevant Federal or New York
State standards, criteria, and guidelines will be used to assess the habitability
of the ED A.
Where relevant standards, criteria, or guidelines are not available, a com-
parison methodology will be used to assess the relative habitability of the
EDA. The habitability criteria call for a comparison of the results of the
residential soil sampling and air sampling for Love Canal Indicator Chemi-
cals (LCICs) in the EDA with the results of sampling for LCICs in similar
inhabited communities in western New York State. Neighborhoods within
the EDA were delineated during the development of the habitability criteria
to facilitate: the comparisons and habitability decision on a neighborhood
basis.
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The only known guideline for 2,3,7,8-TCDD is the CDC level of concern of
1.0 ppb in residential surface soil. As stated in the habitability criteria (NYS-
DOH and DHHS/CDC, 1986), "A review of all federal and New York State
standards, criteria or guidelines for chemicals in the Love Canal and the EDA
indicates that a relevant and applicable standard exists only for TCDD
(2,3,7,8 tetrachlorodibenzo-p-dioxin) in residential soils at this time." Since
a guideline is available for dioxin, comparison sampling was deemed un-
necessary for the soil assessment for dioxin. Therefore, according to the
habitability criteria, one of the conditions for a neighborhood in the EDA to
be considered habitable is that soil sample measurements of 2,3,7,8-TCDD
be less than 1 ppb.
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3.0 GOALS
The overall goal of the soil assessment for dioxin was to determine whether
2,3,7,8-TCDD is present at concentrations of 1.0 ppb or more in the EDA as
specified in the Love Canal Emergency Declaration Area; Proposed
Habitabiliiy Criteria Document (NYSDOH and DHHS/CDC, 1986).
At the direction of the TRC, a surface soil sampling plan was designed to
have a high probability of detecting an area of contamination approximate-
ly the size of a median-size lot. A 69-foot-square sampling grid was
developed based on an analysis of the median size and shape of residential
lots in the EDA. Additionally, the TRC decided that a minimum of two sur-
face soil siunples should be collected per residential lot. Decisions regard-
ing relocation of sampling points from the design location were also set forth.
The habitability criteria document (NYSDOH and DHHS/CDC, 1986) also
directed that areas contaminated with levels of dioxin above 1.0 ppb were to
be retested and/or remediated as appropriate. Thus, an implied operational
objective of this soil assessment was to provide sufficient information to plan
retesting and remediation efforts where appropriate.
Specific operational objectives of this study were to:
1. Collect samples at locations as specified by the design criteria, the direc-
tive of two samples per lot, and the relocation directives.
2. Use sample collection and analytical procedures that would identify
samples with 2,3,7,8-TCDD concentrations of 1.0 ppb or more.
3. Identify and locate sample collection sites with adequate precision to
allow more detailed investigations in case a value of 1.0 ppb or more
was detected.
4. Meet the QA objectives of accuracy, completeness, representativeness,
and comparability described in the study Quality Assurance Project
Plan (QAPP) (CH2M HILL 1987, Section 4).
Sections 4.0 and 5.0, respectively, describe the study design and methods by
which these objectives were attained.
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4.0 DESIGN
The design of the soil assessment for dioxin was directed by the TRC and
was based on the proposed habitability criteria (NYSDOH and
DHHS/CDC, 1986). Generally the design of a sampling study involves three
main elements: project organization, field sampling design, and QA design.
Each of these three elements are discussed below.
4.1 PROJECT ORGANIZATION
Project organization and responsibilities of key personnel are detailed in this
assessment's QAPP (CH2M HILL, 1986 and 1987). The assessment was
conducted under the direction of EPA Region II and under the management
ofCH2MfflLL.
The Department of Health and Human Services/Agency for Toxic Substan-
ces and Disease Registry assisted in the design of the sampling plan. The
NYSDOH obtained property owner permissions and assisted in scheduling
the field sampling. CH2M HILL, along with its associate firms Ecology and
Environment, Inc., and Black & Veatch, Inc., conducted the field sampling.
CH2M HELL's subcontractors, Cambridge Analytical Associates, Inc., and
Horizon Systems Corporation, Inc., provided laboratory services and com-
puter services, respectively, which supported the field sampling.
The University of Nevada at Las Vegas homogenized the fall 1986 samples
in its laboratory. The National Enforcement Investigation Center (NEIC)
through its contractor Techlaw, Inc., conducted evidentiary audits of the field
sampling and sample homogenization efforts. Contract laboratories in the
EPA CLP, under the direction of the EPA Region II Sample Management
Office (SMO), analyzed the samples. Finally, the U.S. EPA Region II En-
vironmental Services Division (ESD) validated the analytical data.
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4.2 FIELD SAMPLING
The sampling plan for this assessment called for samples to be taken in the
Love Canal EDA. (The LaSalle Expressway corridor, the Love Canal site,
and the 93:rd Street School site were not included in the study.) One of the
most likely hypothesized modes of transport for dioxin was considered to be
mechanical (e.g., movement of Canal soil for fill use). Based on this
hypothesis, the target size and shape was selected to be the median size and
shape of lots in the EDA. This median size and shape was analyzed statisti-
cally, and an equivalent elliptical shape and size was generated. (Elliptical
shapes were preferred for statistical analyses.) The target power of the sam-
pling plan was selected to be a 95 percent probability of detecting a con-
taminated area the size and shape of the equivalent ellipse (6,500 square feet
with width-to-length ratio of 0.525 [Gilbert, 1987]). Using this target power,
a 69-foot-s;quare grid pattern was developed with samples to be taken at the
intersection nodes.
The sampling design was based on the following assumptions:
• Dioxin contamination at the 1.0-ppb level can be reliably detected in
soil samples.
• A contaminated area (greater than 1.0 ppb 2,3,7,8-TCDD) will be at
least the size of the median lot in the EDA.
• Concentrations of 2,3,7,8-TCDD throughout a contaminated area
will equal or exceed 1.0 ppb.
The statistical development of the sampling design is discussed in detail in
the Love Canal Dioxin Soil Sampling Quality Assurance Project Plan
(CH2M HILL, 1986, Appendix B).
The sampling scheme had to be adapted to the EDA, where approximately
25 percent of the surface is pavement, structures, densely vegetated areas, or
swampy areas. The sampling grid was oriented to eliminate overlap with
EDA streets running north-south and east-west, as well as with one street
angled 45" west of north. The angle of rotation was selected to be an angle
unlikely to cause overlap of the grid with EDA structures and/or streets. A
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prime number of 13 was selected as the degree of rotation. An example of
the grid layout is shown in Figure 4-1.
At the direction of TRC members, the sampling protocol was modified to in-
clude relocation of a sampling point within specific distance criteria when
necessary. For example, in situations where nodes fell on nonsoil surfaces
(e.g., structures, pavement, or swampy areas), the sampling point was relo-
cated no less than 5 feet from any existing structures and no more than 35 feet
from the node. Five feet was selected as a minimum distance from existing
structures to minimize the effects of rooftop rainwater runoff. Thirty-five
feet was selected as a maximum distance to relocate a sampling point from
a grid node because that distance represents approximately one-half the grid
block length. If those conditions could not be satisfied, the node was not
used as a sampling point.
As discussed in Section 3, in addition to sampling points described by the
grid system, the TRC directed that a minimum of two samples be collected
in each residential lot. Sampling points to meet this criterion were incor-
porated into the sampling plan.
Under the direction of the TRC, the top 2 inches of soil were selected for
sampling. This selection was based on a consideration of the most likely ex-
posure mechanisms. Two common activities have been identified as a prob-
able means by which human exposure to soil would occur: (1) children
playing and (2) adults gardening, etc.
If the design could have been perfectly implemented, the 95 percent
predicted probability would have been achieved. However, as indicated in
the study QAPP, there are several factors that cause points to be moved or
not sampled. This could lower the predicted probability; however, given the
additional samples taken to provide two samples per lot, it is the opinion of
the TRC that the probability of predicting the target size hot spot is as high
as is reasonably achievable and meets the overall intent of the habitability
criteria document as expressed in the QAPP objectives.
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-—/ CENTER Rt>
GRID BLOCKS ARE 681 X 69"
Figure 4-1
SOIL ASSESSMENT—2,3,7,8-TCDD
EXAMPLE GRID NODE SAMPLING PLAN
SCALE: V'1501
LEGEND
CD STRUCTURE
PROPERTY LINE
404 ADDRESS
f GRID BLOCK NODE DESIGNATING
W SAMPLING LOCATION
SOURCE: QAPP (CH2M HILL, 1986 and 1987C)
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4.3 QUALITY ASSURANCE
As indicated in Section 3.0, Goals, the overall QA objective of the soil as-
sessment for dioxin was to produce data of known, defensible quality, based
on data accuracy, completeness, representativeness, and comparability. Ac-
cordingly, several types of QC samples were collected in the field or prepared
in advance and shipped to the laboratory along with the field samples. These
samples included field replicates, shipping and storage blanks, matrix spike
samples, and performance evaluation samples. After the samples were
received in the laboratories, all QC elements specified in the CLP "Dioxin
Analysis and User's Guide" (CH2M HILL, 1986, Appendices E and F) were
used. The following paragraphs describe the origin, timing, handling,
analysis, and use of each type of QC sample.
Field replicates were the only QC samples collected in the field; all other QC
samples were prepared in laboratories prior to field sampling. The field repli-
cates were; used to monitor variability introduced through sample handling
and laboratory analysis. The field replicates were collected from a hole im-
mediately adjacent to the last original field sample hole in each daily batch
of field samples. (A batch included 16 original field samples in 1986 and 20
in 1987.) The field replicates were then treated as field samples and shipped
to a laboratory along with the original field samples in that batch.
The shipping and storage blanks were samples of clean (uncontaminated)
soil and were used to indicate whether contamination occurred during ship-
ment from the equipment cleaning laboratory to the field, during storage in
the field, or during shipment from the field to the laboratories. The presence
of dioxin in blanks can increase uncertainty with regard to reported con-
centrations. If contamination was found in a shipping and storage blank, the
analytical results from the samples in the associated batch would be inter-
preted accordingly. After a batch of original field samples was collected, the
field samples were placed in the same cooler as the shipping and storage
blank and shipped to the analytical laboratory. The identity of the shipping
and storage blanks was not revealed to the analytical laboratory.
The matrix spike samples were used to assess overall data accuracy and to
provide an indication of the efficiency of the analytical process. These matrix
samples were used to monitor the extraction efficiency of the analytical sys-
tem and the effects caused by the sample matrix. Routinely lower or higher
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recoveries of matrix spiking compounds (i.e., dioxin) decrease the con-
fidence in the reported values; this may indicate a serious bias toward artifi-
cially lower or higher reported values. One matrix blank was added with
each batch of original field samples and sent to the analytical laboratory. The
analytical laboratory spiked 1.0 ppb of 2,3,7,8- TCDD into the matrix blank
and analyzed the resulting matrix spike sample along with the other samples
in the same batch. The matrix spike samples were prepared according to the
CLP "Dioxin Analysis Statement of Work and User's Guide" (CH2M HILL,
1986, Appendices E and F).
The performance evaluation samples were used to assess accuracy of the
analytical method and the performance of each analytical laboratory. The
performance evaluation samples were spiked with a known concentration of
2,3,7,8-TCDD, but the identity and concentration of the performance evalua-
tion samples were not revealed to the analytical laboratory. The performance
evaluation samples were then sent to the field where one performance evalua-
tion sample was added to each batch of original field samples before ship-
ment to the analytical laboratory. The performance evaluation samples were
prepared and analyzed according to the CLP "Dioxin Analysis Statement of
Work and User's Guide" (CH2M HILL, 1986, Appendices E and F).
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5.0 METHODS
Selection of the methods used for field sample collection and analysis was
based on the goal of identifying areas in the EDA that are contaminated with
2,3,7,8-TCDD at concentrations at or above 1.0 ppb. A field sample collec-
tion and homogenization method was developed to achieve this goal. The
selected analytical method was the standard procedure for the analysis of the
samples for 2,3,7,8-TCDD established by U.S. EPA for the CLP. Data
validation was conducted to assess and control the quality of the data ac-
quired through field activities and sample analysis.
5.1 SAMPLE COLLECTION AND HOMOGENIZATION
Surveys were conducted prior to sampling to locate the sampling points in
relation to a United States Geological Survey permanent benchmark.
Samples were collected by removing leaf litter and turf, taking approximate-
ly 2 inches of soil from a staked location using a stainless steel spoon, and
placing the sample into an 8-ounce sample jar. The sample was then shipped
to a laboratory for homogenization.
As each s£imple was collected, a Sample Collection Form was completed in-
dicating the sample station number and street address along with other per-
tinent information. Data from the homogenization laboratory were similarly
recorded on a Sample Homogenization Form. The information provided on
these forms was entered into a data base. These forms are described in the
study QAPP (CH2M HILL 1986 and 1987, Appendix A).
The sample homogenization process was changed at the onset of the study.
The homogenization procedure adopted for the study required blending the
soil sample for 90 seconds in an electric blender and then inverting and shak-
ing the container. However, because of the physical nature of the samples
(especially the high moisture and clay content), the blending process was in-
effective. Therefore, all of the field samples collected during the first period
of sampling (November and December 1986) were homogenized at the
homogenization laboratory using a revised procedure. The revised proce-
dure entailed hand-mixing the sample with a spoon for 90 seconds. After
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homogenization, each sample was split, and each half was placed in a 4-ounce
jar. One half (original sample) was sent to the analytical laboratory and one
half (archive sample) to archive storage. Archive samples were kept in the
event that the original sample was lost or contaminated.
Because the homogenization procedure was changed to hand-mixing,
samples collected during later sampling periods (May and July 1987) were
homogenized in the field. Therefore, the samples were no longer sent to the
homogenization laboratory, but were sent directly to the analytical
laboratory.
A complete detailed description of the sample collection, sample
homogenization, and archive preparation procedures is available in the study
QAPP (CH2M HILL, 1986 and 1987b).
5.2 SAMPLE ANALYSIS
All samples collected during the study were analyzed by laboratories under
the direction of the EPA CLP. After homogenization, the samples were
shipped to the laboratories specified by the SMO of the CLP. The analysis
for dioxin was performed in accordance with the standard analytical proce-
dures for 2,3,7,8-TCDD established by the EPA for the CLP ("Dioxin
Analysis Statement of Work and User's Guide" [CH2M HILL, 1986, Ap-
pendices E and F]).
5.3 DATA VALIDATION
Validation of both field data and analytical data was conducted. The field
data were assessed to determine if the sampling method and plan were proper-
ly implemented and to verify sample locations. Analytical data were
validated to assess and control the quality of analytical data.
5.3.1 Field Validation
Implementation of the sample collection and homogenization methods was
audited by Techlaw for the U.S. EPA NEIC. Appendix A summarizes the
5-2
-------
findings of the evidentiary field audit performed during sample collection.
Appendix B presents the report on the evidentiary audit of the homogeniza-
tion laboratory. The conclusion of the audits was that both programs had
met required protocols and thus had passed their respective audits.
Sample collection and homogenization records were reviewed and compared
for accuracy and completeness. Since there are a large number of public and
private property owners in the EDA and since two samples were required per
residential lot, it was very important for sample locations to be properly tied
to lot boundaries. Upon a comparison of the street address on the sample
collection forms with the plotted location of the sampling points, discrepan-
cies between lot delineations on the base map and actual field observations
became evident. These sampling locations were field checked, and the Love
Canal basis map and data base were corrected. In addition, some points ap-
peared to be located on the boundary of two properties. Where possible,
these discrepancies were resolved using photographs taken during sample
collection. If the property on which a sampling point fell could not be deter-
mined, the results were flagged with this information and both addresses
given.
Implementation of the sampling plan was reviewed by an examination of the
surveyor's data on sampling points that had been relocated. The distance
that sampling points were moved because of field limitations (structure,
pavement., dense vegetation, etc.) was calculated. The actual distance moved
was compared to the criteria for movement of sampling points as set forth in
the study QAPP (CH2M HILL, 1986 and 1987). For sampling points that
were moved further than the criteria limit of 35 feet from the target location,
a designation of "M" was incorporated following the sample station number
(Example: 5280M). The original grid node was surveyed again and a new
sample was collected at the node with the original sample number (Example:
5280). In each case, both samples were analyzed, and both results were
reported.
5.3.2 Analytical Data Validation
Data validation was performed by the U.S. EPA Region n BSD in Edison,
New Jersey. The methodology used is reported in Appendix C of this report.
Analyses that did not initially pass validation were rerun to meet the QC re-
5-3
-------
quirements called for in the CLP "Dioxin Analysis Statement of Work and
User's Guide" (CH2M HILL, 1986, Appendices E and F).
5-4
-------
6.0 RESULTS
Results of the soil assessment for 2,3,7,8-TCDD are reported below in terms
of sampling activity and analytical results. Sampling activity is summarized
in Section 6.1. Section 6.2 discusses the results of QA activities. The
analytical findings are presented in Section 6.3, and a brief discussion of the
results is given in Section 6.4.
6.1 SAMPLING ACTIVITY
Sampling activity was initiated in November of 1986, and samples were col-
lected at 1,628 sampling points during November and December of 1986.
Sampling was discontinued because of inclement weather in December 1986
and was resumed in May 1987. A total of 608 points were sampled during
May 1987. Sampling activities were completed during July 1987 when
samples were collected at 38 sampling points. Sixteen original field samples
were collected in each daily batch during 1986, and 20 original field samples
were collected in each daily batch during 1987. In addition, four QC samples
were shipped with each batch.
A total of 111 of the planned sampling points could not be sampled. Forty-
two grid nodes could not be sampled (or moved in accordance with the reloca-
tion criteria) because of field limitations such as dense vegetation, creek bed
areas, or swampy areas. Sixty-nine grid nodes were not sampled because
permission to sample could not be obtained from the property owners.
In summary, 2,274 locations were sampled during the course of the study.
These points are shown in Figure 6-1. The count of each type of sample col-
lected and/or prepared during the study is given in Table 6-1.
6.2 QUALITY ASSURANCE RESULTS
As discussed in Section 4.3, the overall QA objective of the soil assessment
for dioxin was to produce data of known, defensible quality, based on the
6-1
-------
tgfgepl
t-... "•^%~. l^qfrriT---p3.t=a_y!gL •
s^r> '^ttorai^sy
^•CS.' >.„ -• V^ i » *• .u^^t^oi^..
^s^-v-r->-. "^-iSi.i H=i.-e.^i&-1
Figure 6-1
SOIL ASSESSMENT~2,3,7,8-TCDD
LOCATION OF ACTUAL SAMPLING POINTS
SCALE: i"«650'
LEGEND
•EMERGENCY DECLARATION
-FENCE LINE AROUND LOVE
SAMPLING POINT
AREA (EDA) BOUNDARY
CANAL REMEDIATION SITE
SOURCE: EDA BOUNDARIES TAKI-N FROM NEW YORK
STATE PROPERTY TAX LAW ARTICLE 17. SECTION 1702
-------
Table 6-1
NUMBER AND TYPE OF SAMPLES GENERATED
Sample Type Number Prepared
Original field samples (taken at field sampling points) 2,274
Quality contra! samples (samples prepared for quality control of shipping,
storage, sampling, and analysis):
Performance evaluation sample (prepared at laboratory prior to
shipment to the field) 152
Shipping and storage blank (prepared at laboratory prior to
shipment to the field) 152
Matrix spike blank (prepared at laboratory prior to shipment to
the field) 153
Field replicate (sample collected in the field immediately adjacent
to an original field sampling point) 136
Subtotal-QC Samples 593 593
Archive samples (splits of original field samples and replicate samples) 2,410
Total Samples 5,277
-------
data accuracy, completeness, representativeness, and comparability. The
analytical data were validated, and the samples were reanalyzed if the
analysis did not meet QC requirements. The results of the data validation ef-
forts are summarized in Appendix C. Overall, the QA objectives for ac-
curacy, completeness, representativeness, and comparability were met.
During the course of the study, a total of 279 archive samples were retrieved
from storage and analyzed along with 48 QC samples. These archives were
used for several purposes. One hundred and nine archive samples and 18 as-
sociated QC samples were analyzed to provide results for discarded original
samples that had not been analyzed successfully. One hundred and seventy
archives and 30 associated QC samples were sent to a new laboratory for a
QC check. However, some of the corresponding original samples analyzed
separately in another laboratory did not pass data validation. As a result,
101 of these 170 archives have valid results for both the original and the as-
sociated archive.
Of the 101 archive and original sample pairs with valid results, 5 archives
and their associated original field samples contained detectable levels of
dioxin. Ninety archives, along with their associated original field samples,
had results of non-detects. The analytical results for these samples are given
in Table 6-2. The relative standard deviation of the archive results versus
the original results was 16.3 percent, indicating relatively good agreement.
These results indicate that acceptable precision was achieved, considering
that the data include the variations from the entire measurement process (e.g.,
sampling, transportation, preparation, calibration, extraction, and analysis).
For samples that did not contain measurable dioxin concentrations for both
original and archive samples, the increased method variability at the near-
detection limit may increase the variability of the measurement process.
Of the 136 field replicate sample and original pairs collected, only one field
replicate sample and its associated original field sample were found to con-
tain detectable concentrations of dioxin. At Station No. 1700, analysis of the
original sample yielded a result of 0.07 ppb, and analysis of the replicate
yielded 0.07 ppb. No meaningful estimate of precision can be made because
of the limited number of results.
Dioxin was not detected in any of the 143 shipping and storage blanks as-
sociated with a batch of valid results. Based on these results, there is no
6-4
-------
Table 6-2
ARCHIVE SAMPLE RESULTS VS. ASSOCIATED ORIGINAL SAMPLE RESULTS
Sample Original Archive
Station Number Sample Result Sample Result
(ppb) (ppb)
3037 0.11a/0.16a 0.12
3409 0.20 0.19
5242 0.09 0.06
5254 0.09* 0.11
5277 0.23 0.19
aRerun of original sample
ND = Non-Detect
MFC = Maximum Possible Concentration
Note: Only those original/archive pairs in which both samples have valid results Indicating
detectable levels of dioxin are included in this table.
-------
indication lhat contamination occurred during shipping and storage of the
samples.
Accuracy of the laboratory procedure was measured through an analysis of
a performance evaluation sample and a matrix spike sample. A total of 143
performance evaluation samples were associated with valid results of field
samples. The performance evaluation sample results were reviewed to deter-
mine the range of the results and the median result for each spike level of the
samples. This information is provided in Table 6-3. Valid results were ob-
tained for 146 matrix spike samples. Five matrix spike samples were
analyzed twice to provide quality control on reruns of field samples. The
spike level in each matrix spike sample was 1.0 ppb dioxin. The range of
results was 0.68 to 1.4 ppb, and the median was 0.95 ppb 2,3,7,8-TCDD.
6.3 ANALYTICAL RESULTS
Of the 2,274 points sampled in the EDA, dioxin was detected at concentra-
tions above: the study target level of 1.0 ppb in samples taken at only one
sampling location. Analysis of the original sample indicated the probable
presence of TCDD above 1.0 ppb, but the concentration could not be quan-
tified. Therefore, the archive sample was split into five separate samples and
sent to a second laboratory for analysis. This sample was successfully
analyzed five times, yielding results of 17.3,19.9,21.2,20.9, and 20.2 ppb
2,3,7,8-TCDD. This sample was collected from a property on 100th Street
between Wheatfield Avenue and Colvin Boulevard directly across the street
from the Canal (see Figure 6-2).
A total of 2,517 valid results were obtained for the points sampled. Several
sampling points have multiple results for a variety of reasons including
analysis of field replicates, laboratory reruns due to suspected carryover
(cross-contamination), confirmation of detects by high resolution analysis,
and qualitative identification of dioxin followed by multiple confirmatory
analyses of original field samples, replicates, and/or archives. In cases where
no valid result was obtained for the original sample, the archive of the original
sample was analyzed. A summary of the counts of multiple results is given
in Table 6-4.
6-6
-------
Table 6-3
SUMMARY OF PERFORMANCE EVALUATION RESULTS
Number of Valid
Target Value Performance Evaluation Median of Reported Range of Reported
(ppb) Sample Results Values (ppb) Values (ppb)
aOnly one result In this target value range
0.76 1 (0.94a)
0.80 63 0.85 0.41-1.10
1.20 51 0.87 0.64-2.10
1.54 34 1.40 0.83-2.30
Note: Results are based on valid analyses of performance evaluation samples associated with batches of field
samples which have passed validation. A total of six performance evaluation samples were analyzed twice
to provide quality control on reruns of field samples.
-------
_1.0 ppt>
4258 SAMPLE STATION NUMBER
121.24) CONCENTRATION (ppb)
SOURCE: NEIGHBORHOOD BOUNDARIES ADAPTED FROM THE PROPOSED
HABITABILITY CRITERIA DOCUMENT (NYSOOH AND DHHS/ODC. S86J.
-------
Table 6-4
DISTRIBUTION OF ANALYTICAL RESULTS WITH RESPECT TO SAMPLE LOCATION
Number of Analytical Results v Number of _ Number of
Reported per Sample Location x Sample Locations = Analytical Results
"All analytical results included have passed data validation.
a
0 14 0
1 2,019 2.019
2 230 460
3 7 21
4 3 12
5 1 5
Totals 2,274 2,517
-------
Valid analyses were not obtained for samples taken at 14 locations (0.6 per-
cent of the; points sampled). One sample was not analyzed because of exces-
sive moisture in the sample. The remaining 13 samples were analyzed, and
the results were rejected because the QC requirements were not met. Several
of these samples were reanalyzed, but the results again did not meet the QC
requirements. The laboratory forms for these samples and location of these
sampling points were reviewed, and a decision was made not to reanalyze
these samples because the completeness objective stated in the study QAPP
(CH2M HILL, 1986 and 1987a) had been met.
A total of 2,454 analyses (97 percent) were non-detects. The detection limit
for the analysis of each sample is described as the Maximum Possible Con-
centration (MFC) that could go undetected in the sample. The MFC varies
for each sample analysis due primarily to analytical process parameters, in-
strument performance, and matrix interferences. The CLP "Dioxin Analysis
Statement of Work and User's Guide" (CH2M HILL, 1986, Appendices E
and F) required the MPC in these analyses to be less than 1.0 ppb. Results
with an MPC greater than 1.0 ppb required reanalysis in order to meet this
criterion. The distribution of MPC values throughout the analysis of field
samples is: illustrated in Figure 6-3.
Dioxin was detected in a total of 63 analyses, representing a total of 49 sam-
pling points (2.2 percent of the sampling points). These analytical results
are listed in Table 6-5. The sampling points with detectable levels of dioxin
are indicated on Figure 6-3 with the highest analytical result for each sam-
pling point shown. The overall results of the study are summarized by con-
centration interval in Table 6-6.
6.4 DISCUSSION OF RESULTS
Dioxin was detected at levels above the CDC level of concern of 1.0 ppb at
only one sampling point (0.04 percent) of the 2,274 points sampled. The
remaining sampling points with detected concentrations of dioxin were
below this level of concern.
The detection of dioxin at one sampling point at a level equal to or greater
than the study target level of 1.0 ppb indicates that a contaminated area ex-
ists. Results of samples from nearby sampling points were non-detects. No
6-10
-------
HI —
^ w
Q_ LU
2 C/)
CEP
triu^
UJ Q <
CQ • CC
2500 -r
2000 -
1SOC T
1000 -
500 -
^0.2and<0.4 20.4and<0.6
.6 and <0.8
MAXIMUM POSSIBLE CONCENTRATION (ppb)
NOTE: Original field samples, replicates, and archives only.
FIGURE 6-3 SOIL ASSESSMENT-2,3,7,8-TCDD
FREQUENCY OF MPC VALUES FOR ANALYSES OF
FIELD SAMPLES WITH NON-DETECT RESULTS
-------
Table 6-5
SUMMARY OF ANALYTICAL RESULTS FOR SAMPLES WITH DETECTED CONCENTRATIONS
Initial Result
(ppb)
0.27
0.02
N/A
N/A
Rejected
0.03
0.02
ND(MPC = 0.04)
0.05
N/A
N/A
0.17
0.07
0.07
N/A
0.16
0.62
0.61
0.04
ND (MFC = 0.05)
0.01
0.11
0.06
0.04
0.07
MFC = Maximum possible concentration
ND = Not detected
N/A = Not available (lab decision to rerun sample)
Rejected = Data rejected by ESD
- = No analysis performed
Station
Number
1233
1427
1450
1479
1524
1550
1588
1657
1660
1675
1700
1811
1843
1932
1936
1969
1975
2034
2060
2061
2080
Type of
Sample
Original
Original
Original
Original
Original
Archive
Original
Original
Replicate
Original
Original
Original
Original
Replicate
Original
Original
Original
Original
Original
Original
Archive
Original
Original
Original
Original
Rerun Result
(ppb)
ND (MFC = 0.04)
0.05
Rejected
0.03
Comments
Sample reextracted and reanalyzed
0.15
0.05
ND (MFC = 0.02)
Rejected
0.06
ND (MFC=0.04)
Sample reextracted and reanalyzed
-------
Table 6-5
(Continued)
Initial Result
(ppb)
Rejected
Rejected
ND (MFC=0.04)
0.03
0.06
Rejected
0.11
Rejected
0.12
0.33
ND (MFC = 0.08)
ND (MPC=0.08)
0.02
0.03
0.04
0.03
Rejected
0.06
Rejected
0.09
Rejected
0.07
N/A
0.19
Rejected
0.08
N/A
MFC = Maximum possible concentration
ND = Not detected
N/A = Not available (lab decision to rerun sample)
Rejected = Data rejected by ESD
- = No analysis performed
Station
Number
2104
2135
2153
3033
3037
3115
3191
3199
3201
3259
3404
3406
3408
3409
3412
4010
Type of
Sample
Original
Replicate
Archive
Replicate
Original
Original
Original
Original
Archive
Original
Original
Replicate
Archive
Original
Original
Original
Original
Archive
Original
Archive
Original
Archive
Original
Archive
Original
Archive
Original
Rerun Result
(ppb)
Comments
0.12
ND (MFC = 0.05)
0.11
0.16
0.20
Rejected
0.01
Sample reextracted and reanalyzed
-------
Table 6-5
(Continued)
Station
Number
4097
4139
4225
4256
4313
4322
5138
5234
5242
5248
5254
5277
Type of
Sample
Original
Duplicate8
Original
Replicate
Original
Archive
Original
Archive
Original
Original
Original
Original
Archive
Original
Archive
Original
Archive
Original
Archive
Original
Archive
Initial Result
(ppb)
0.13
N/A
N/A
Rejected
0.17
Rejected
Rejected
Rejected
Rejected
Rejected
19.9
0.06
0.03
0.20
Rejected
0.63
N/A
0.06
N/A
ND (MFC = 0.04)
Rejected
0.11
N/A
0.18
Rerun Result
(ppb)
0.12
0.10
Rejected
ND (MFC=0.04)
Rejected
0.05
Rejected
Rejected
17.3
21.2
Rejected
20.9
20.2
ND (MPC=0.36)
ND (MFC = 0.19)
0.92
0.09
0.03
0.09
0.23
Comments
Duplicate analysis of rerun sample
Sample reextracted and reanalyzed
Sample reextracted and reanalyzed
Utilized high resolution technique
for rerun result
MFC = Maximum possible concentration
ND = Not detected
N/A = Not available (lab decision to rerun sample)
Rejected = Data rejected by ESD
- = No analysis performed
aDuplicate analyses are described in Appendix C.
-------
Table 6-6
DISTRIBUTION OF ANALYTICAL RESULTS WITH RESPECT TO CONCENTRATION RANGES8
Concentration
Range
(ppb)
ND
<0.2
> 0.2 and <0.4
> 0.4 and <0.6
> 0.6 and <0.8
> 0.8 and <1.0
2:1
Number of Sampling Locations
with Highest Result In
Concentration Range
2,211
40
5
0
2
1
1
Total Number of Results
Using All Reported Concentrations
for Each Sampling Location6
2,454
49
5
0
3
1
2,260
2.517
Sampling locations for which
analysis did not pass QC:
Total number of samples collected:
14
2,274
aAII analytical results presented have passed QC criteria.
blt is possible that one sample location could be represented in two or more concentration ranges if multiple analytical results were reported.
°These validated analytical results (for sample location at Station 4256) are 17.3,21.2,20.9, 20.2, and 19.9 ppb 2,3,7,8-TCDD.
-------
house is located on this lot, and the nearest detect is approximately 260 feet
away, with a concentration of 0.16 ppb 2,3,7,8-TCDD. The area surround-
ing the hit has been fenced and secured. Further sampling will be conducted
under the Love Canal remedial program to determine the extent of the con-
tamination and to plan subsequent corrective action.
6-16
-------
REFERENCES
CH2M HILL. 1986. Love Canal Dioxin Soil Sampling Quality Assurance
Project Plan.
CH2M HELL. 1987. Revisions to Love Canal Dioxin Soil Sampling Study
Quality Assurance Project Plan.
Gilbert, Richard D. Statistical Methods for Environmental Pollution
Monitoring. Van Nostrand Reinhold Company, New York.
Life Systems. 1986. Peer Review of the Proposed Habitability Criteria for
The Love Canal Emergency Declaration Area.
NYSDOH and DHHS/CDC. 1986. Love Canal Emergency Declaration
Area; Proposed Habitability Criteria.
OTA, 1983. Habitability of the Love Canal Area-An Analysis of the Tech-
nical Basis for the Decision on the Habitability of the Emergency
Declaration Area—A Technical Memorandum.
U.S. EPA, Office of Research and Development 1982. Environmental
Monitoring at Love Canal. Volumes I, II, and HI.
-------
APPENDIX A
Field Evidentiary Audit Report
Prepared by
U.S. EPA National Enforcement Investigation Center
Techlaw, Inc.
Lakewood, Colorado
-------
:ONTRACTOR
EVIDENCE
\UDIT
TEAM
December 31, 1986
Mr. Doug Garbarini
USEPA Region II
26 Federal Plaza
Room 737
New York, NY 10278
RE: Transmittal of Field Audit Report for Love Canal Dioxin
Soil Sampling
Dear Doug:
Enclosed are two copies of the field audit report for the Love
Canal Dioxin Soil Sampling conducted November 17-19, 1986.
The report was received and approved by NEIC and a copy has
been transmitted to Mr. Craig Rightmire of CH2M Hill as you
requested.
Also enclosed is an evidence audit Work Plan for this audit.
Thank you for requesting our participation in this study and we
were pleased to provide this evidence audit support on behalf
of NEIC. If you have any questions, please contact us at (303)
233-1248 or Rob Laidlaw at (303) 236-5122 (FTS 776-5122).
Best wishes for the New Year.
kffii^
Keith Wegner
Staff Consultant
KW:rls
Enclosures
cc: Rob Laidlaw, NEIC (w/enclosure)
Betty Malone, CEAT (w/enclosure)
IF: 222-068
TECHLAW. INC. • 12600 W. COLFAX AVE-. • SUITE C3IO« LAKEWOOD. CO • 80215* (303)233-1248
-------
FIELD AUDIT REPORT
LOVE CANAL
Dioxin Soil Sampling Study
Niagara Falls, New York
November 17-19, 1986
CH2M Hill
P.O. Box 4400
Reston, Virginia
(703) 471-1441
22090
Craig Rightmire
Sadia Kissoon
Ana Morera
Don Johnson
Field Team Manager
Document Control Manager
Field Auditor
Field Auditor
Horizon Systems Corporation
1800 Michael Faraday Drive
Suite 201
Reston, Virginia 22090
(703) 471-0480
Robert Meyer
- Document Control Technician
EPA - Region II
(212) 264-0722
Douglas Garbarini -
Love Canal Regional Project
Manager
REACT - Denver
(303) 233-1248
Betty Malone
Troy Sanders
Field Evidence Auditor
Field Evidence Auditor
-------
Ecology and Environment, Inc.
195 Sugg Road, P.O. Box D
Buffalo, New York 14225
(716) 633-9881
Sampling Team 1
Joe Jackson
Joe Chandler
Michael Michalowski
Mary Miller
Jon Nickerson
Field Team Supervisor
Sample Collector, Team 1A
Sample Collector, Team 1A
Sample Collector, Team IB
Sample Collector, Team IB
Sampling Team 2
Russell Short
Keith Keller
Pamela Gunther •
M.J. Parrel1
Thomas Ferraro •
Thomas Siener
Sampling Team 3
Scott McCone
Bret Maxwell
William Hall
Dale Dolph
Gene Florentine
Field Team Supervisor
Sample Collector, Team 2A
Sample Collector, Team 2A
Sample Collector, Team 2A
Sample Collector, Team 2B
Sample Collector, Team 2B
Field Team Supervisor
Sample Collector, Team 3A
Sample Collector, Team 3A
Sample Collector, Team 3B
Sample Collector, Team 3B
Black and Veatch
Pritchard Building
8205 West 108th Terrace
Overland Park, KS 66210
Sampling Team 4
Richard Gibbs
Teresa Shock
Gary Schnettgoecke
Jeff Dilley
David Munie
Field Team Supervisor
Sample Collector, Team 4A
Sample Collector, Team 4A
Sample Collector, Team 4B
Sample Collector, Team 4B
This work was conducted on behalf of the
Environmental Protection Agency's (EPA) National
Enforcement Investigations Center (NEIC) under EPA
Contract No. 68-01-7104 for Superfund Site No. 28.
-------
INTRODUCTION
On November 17, 18, and 19, 1986, NEIC Regional Evidence
Audit Contract Team (REACT) personnel conducted an audit to
observe document control and chain-of-custody procedures followed
during the collection of soil samples for the Love Canal Dioxin
Soil Sampling Study. An initial meeting was held in Niagara
Falls, New York on November 17, to discuss sampling procedures
and protocol. Present at the meeting were S. Kissoon, D.
Garbarini, T. Sanders, and B. Malone. On November 18 and 19,
sampling procedures and documentation were observed by REACT
personnel. The CH2M Hill sampling plan was also examined, and is
briefly described below:
Sampling Plan
A sampling plan (Quality Assurance Project Plan (QAPP)) was
prepared for the sample survey by CH2M Hill and was reviewed and
approved by the Region II EPA.
The soil sampling protocol contains:
1. Project description and background
2. Sampling procedures and custody
3. Documentation of sample collection
4. Quality Assurance Program
5. Site Safety Plans
The following documents were reviewed during the sample
collection phase of the audit: Sample Collection Labels, Sample
Collection Forms, Chain-of-Custody Forms, and field and
photograph logbooks.
Accountable Field Documents
A tracking system is used, in which the following documents
are numbered and are accountable:
1. Sample Collection Form
2. Chain-of-Custody Form for Shelby Tubes
3. Field Logbooks
Incorrectly completed forms and those forms which are not
used are marked "Void" and returned to Ana Morera, a CH2M Hill
field auditor. Sample collection labels are not numbered.
A brief description of each of the documents reviewed during
the sample collection phase of the audit appears below. A table
listing specific documents examined during the audit appears in
the Appendix.
Page 1 of 6
-------
Sample Collection Labels
Sample collection labels were used in lieu of sample tags by
CH2M Hill during the sampling episode. A label was completed for
each sample collected. Each sample collection label contains the
following information: Project title, jar number, date, time,
collector, project number, client, chemical analyses, and
comments.
During the period of the audit, ten Sample Collection Labels
were selected at random and examined for completeness by the
auditors. All sample labels were completed and were consistent.
Sample Collection Forms
Sample Collection Forms were used by CH2M Hill with one form
completed for each sample collected. Each form, completed and
signed by the collector, contains information concerning sampling
locations, sample descriptions, shipping information, and samples
associated with blanks and replicates.
During the audit, one hundred Sample Collection Forms were
reviewed by the REACT auditors. The auditors noted that in forms
completed by one of the sampling teams on November 18, 1986, the
name of the sample collector appearing in the top portion of the
form was not the same name that was signed as the collector at
the bottom of the form. (REACT personnel recommended that the
incorrect name be changed so that both names are in agreement.
It was suggested that, as in the chain-of-custody forms, all
sample collectors' names be included in the top portion of the
form, allowing any one of the sample collection team members to
sign at the bottom of the form.)
REACT auditors also compared information from the sample
collection forms with the chain-of-custody records. The chain-
of-custody forms will be discussed in the following section.
Chain-of-Custody Form
EPA-type Chain-of-Custody Record Forms were used by CH2M
Hill, and were completed for all samples collected. These forms
accompanied the samples from their origin at the site to the
sample homogenization laboratory in Las Vegas, Nevada.
Information on these forms includes: Project name and number,
shipment information, sample collection information, and
signatures and dates denoting when the samples were relinquished
and received.
Eight completed chain-of-custody records were reviewed by
the REACT auditors. The following recommendations were made:
Page 2 of 6
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o the signature of the individual who initially relinquishes
the sample should also appear in the "Sampled By and
Title" portion of the custody record. This was correctly
completed on the majority of the forms examined by REACT
personnel.
o sampling team members should be careful to enter all
required information on the custody forms. The majority
of the forms were fully completed; however, several were
missing information such as the method of shipment, the
airbill number, and complete dates.
It was suggested during the debriefing that the sample jar
number from the Sample Collection Label be included under the
Remarks section of the chain-of-custody form, as an added means
of sample identification.
Information which appeared on both the chain-of-custody and
sample collection forms was compared for consistency. It was
noted that corrections made to the Sample Collection forms were
not made to corresponding entries on the Chain-of-Custody
Records. (REACT auditors recommended that the same changes be
made to both forms to ensure consistency.)
Field Logbook
The sampling team members recorded information pertaining to
the sampling effort in a field logbook. The initial page of each
entry was signed and dated by the author. The logbook was
project-specific for Love Canal. The logbook was numbered upon
assignment and identified as an accountable document.
Information recorded in the logbook included:
o Sampling site locations and station numbers
o Date of sampling
o Names of (samplers
o Weather conditions
o Temperature
o Deviations (i.e., broken sample bottles, equipment
malfunctions)
o Picture and roll numbers of photographs taken
REACT personnel examined logbooks completed by the eight
sampling teams. CH2M Hill field auditor Ana Morera was advised
that the sampling teams should be careful to sign and date each
logbook page and to fill in blank spaces with diagonal slashes.
It was also pointed out that logbook covers did not contain the
name of the person or organization to whom the book was assigned,
as specified in the CH2M Hill Quality Assurance Project Plan.
Page 3 of 6
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Photograph Logbook
A separate logbook was used to retain information regarding
photographs. The photograph logbook was not identified as an
accountable document. Information recorded in the logbook
included:
o Date and location of sample site
o Polaroid and 35 mm photo numbers
o Sample station number
o Serial number of 35 mm camera body and lens
o Preparer
(REACT personnel recommended at the debriefing that the
names of persons taking photographs be included in the logbook.)
Field Observations
Prior to the audit, a briefing was held on November 17,
1986, with the personnel listed in the introduction of this
report. Topics discussed included sampling procedures, sampling
documentation, the purpose of the audit, and health and safety
issues.
On November 17, 18, and 19, 1986, soil samples were
collected at Love Canal in Niagara Falls, New York. Eight
sampling teams, consisting of personnel from Ecology &
Environment and Black & Veatch, collected surface soil samples to
be later analyzed for Dioxin. At the end of each day's sampling
episode, all Sample Collection Forms and Chain-of-Custody forms
were reviewed by the CH2M Hill field auditor. On each following
day, data from the Sample Collection forms was entered by Horizon
Systems Corporation into a computerized database.
Custody of the samples was maintained in the following way:
During sample collection, the Field Team Supervisor (FTS) for
each sampling team remained in the respective team's sampling van
to complete documentation and to prepare the sample coolers for
shipping. When possible, samples were shipped at the end of each
day. If there were not enough samples collected in a day to
completely fill a cooler, the samples were locked up overnight at
the Ecology & Environment office in Buffalo, NY, and shipped the
following day.
REACT personnel examined documentation for samples collected
November 17 and 18, 1986. Documentation related to each day's
sampling effort was reviewed the following morning subsequent to
review of the documents by the CH2M Hill field auditor.
A debriefing was held on November 19, 1986. Details of the
debriefing are discussed below.
Page 4 of 6
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Debriefing
A debriefing was held at the Love Canal site on November 19,
1986. Craig Rightmire, Douglas Garbarini, and the REACT auditors
were present.
C. Rightmire was informed that the overall organization of
the sampling teams in collecting samples and completing
associated documentation appeared to be well conceived and
generally consistent with the sampling plan.
The following recommendations were made during the
debriefing:
1. Names of sample collectors appearing in the top and
bottom portions of the Sample Collection Form should be
in agreement.
2. The name of the person initially relinquishing the
sample should also be included as one of the sampling
team members in the "Sampled By and Title" portion of
the Chain-of-Custody Record.
3. Care should be taken to complete all information
requested on the Chain-of-Custody Record.
4. All pages of field logbooks should be initialed or
signed, and dated.
5. Information contained on logbook covers, such as the
name of the person or organization to whom the book was
assigned, should be included, to be consistent with that
specified in the Quality Assurance Project Plan.
6. The photograph logbook should contain the names of
persons taking photographs.
Summary
The following procedures were observed by the REACT auditors
during the sample collection phase of the audit:
1. An accountable document system was utilized for
documenting sample collection.
2. Project specific logbooks were utilized in which
pertinent information, such as sample locations and
field observations were recorded for collection.
3. Chain-of-custody procedures were being followed and
sample identity was maintained for sample collection
procedures.
Page 5 of 6
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4. Sample security was maintained by keeping samples under
custody or stored within secured areas when not in the
physical custody of the samplers.
5. The CH2M Hill Quality Assurance Project Plan was
followed except where field conditions warranted
deviations. Any deviations were noted in the field
logbooks.
Page 6 of 6
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APPENDIX
RECORD OF DOCUMENTATION USED FOR DIOXIN
SAMPLES COLLECTED NOVEMBER 18-19, 1986
-------
LOVE CANAL FIELD AUDIT
Record of Samples Collected
November 18-19, 1986
Station Number
4141
4140
3338
2200
3302
4262
1870
2222
1808
3300
4122
5256
1872
1809
4043
1812
1817
1815
5267
1919
2221
4263
1866
3339
3005
2007
1001
3001
5235
5249
4001
1004
1007
1013
2008
1011
4143
5251
3407
4002
2002
Sample Collection
Form Number
30183
30184
30177
30181
30092
30179
30100
30101
30087
30088
30091
30095
30098
30089
30090
30093
30094
30096
30097
30099
30178
30180
30182
30102
30027
30028
30030
30031
30021
30016
30033
30137
30139
30146
30141
30143
30216
30022
30020
30032
30029
Chain-of-Custody
Form Number
1011
1011
1011
1011
1011
1011
1011
1011
1011
1011
1011
1011
1011
1012
1012
1012
1012
1012
1012
1012
1012
1012
1012
1012
1004
1004
1004
1004
1004
1004
1004
1004
1004
1004
1004
1004
1013
1017
1017
1017
1017
-------
Station Number
4006
3004
4300
5234
3010
1010
4005
4223
2009
1012
5248
4177
4176
1871
1868
1920
3341
2176
1813
2174
3335
2219
1918
4173
1867
2220
1867
1816
3342
3301
4121
1807
1811
2010
5253
5274
3006
1006
1008
3009
4009
3426
3003
2004
1005
4007
Sample Collection
Form Number
30026
30025
30024
30023
30142
30140
30138
30034
30144
30145
30017
30211
30210
30206
30208
30204
30202
30199
30197
30195
30214
30215
30212
30217
30207
30213
30209
30205
30203
30201
30200
30196
30198
30068
30054
30056
30058
30061
30063
30065
30066
30157
30158
30160
30162
30164
Chain-of-Custody
Form Number
1017
1017
1017
1017
1017
1017
1017
1017
1017
1017
1017
1015
1015
1015
1015
1015
1015
1015
1015
1015
1015
1016
1016
1016
1016
1016
1016
1016
1016
1016
1016
1016
1016
1019
1019
1019
1019
1019
1019
1019
1019
1019
1019
1019
1019
1019
-------
Station Number Sample Collection Chain-of-Custody
Form Number Form Number
5236 30057 1020
5254 30059 1020
3007 30060 1020
4004 30062 1020
3008 30064 1020
1003 30067 1020
2005 30156 1020
2003 30159 1020
1002 30161 1020
1009 30163 1020
4008 30165 1020
4010 30166 1020
3037 30055 1020
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APPENDIX B
Homogenization Laboratory Evidentiary
Audit Report
Prepared by
U.S. EPA National Enforcement Investigation Center
Techlaw, Inc.
Lakewood, Colorado
-------
CONTRACTOR
EVIDENCE
AUDIT
TEAM
January 21, 1987
Mr. Doug Garbarini
USEPA Region II
26 Federal Plaza, Room 737
New York, NY 10278
RE: Transmittal of Evidence Audit Report for UNLV-ERC
Related to Love Canal Dioxin Soil Sampling Study
Dear Doug:
Enclosed is the audit report for the evidence audit conducted at
the University of Nevada, Las Vegas - Environmental Research
Center facility. The report has been reviewed and approved by
NEIC, and we are transmitting this copy to you.
With your concurrence we have also transmitted a copy of the
report to the UNLV-ERC Laboratory.
Please contact us if you have any comments or questions.
Yours sincerely,
Keith Wegner
Staff Consultant
KW/lkl
Enclosure
cc: Rob Laidlaw, NEIC (w/enclosure)
Betty Malone, CEAT (w/enclosure)
IF: 111-068/222-068
TECHLAW, INC. • 12600 W. COLFAX AVE., • SUITE C310 • LAKE WOOD. CO* 80215 • (303) 233-1248
-------
LABORATORY EVIDENCE AUDIT REPORT
UNIVERSITY OF NEVADA AT LAS VEGAS
QUALITY ASSURANCE LABORATORY
ENVIRONMENTAL RESEARCH CENTER
December 15, 1986
UNLV-Quality Assurance Laboratory
Environmental Research Center
4505 Maryland Parkway
Las Vegas, NV 88154
(702) 739-3142
Joseph Campana - Director, Quality Assurance Laboratory
Steve Ward - Chemist
Amy Smiecinski - Quality Assurance Specialist
CH2M Hill - Reston, VA
(703) 471-1441
Ana Morera - Sample Custodian/Auditor
Black and Veatch - Overland Park, KS
(913) 661-6421
Patrick Dunn - Sample Preparation Technician
Rodney Rowe - Sample Preparation Technician
Michael Boehler - Sample Preparation Technician
USEPA - Region II/New York, NY
(212) 264-0722
Doug Garbarini - Love Canal Dioxin Soil Sampling
Project Manager
REACT - NEIC/Denver, CO
(303) 233-1248
Keith Wegner - Evidence Auditor/Audit Team Leader
Betty Malone - Evidence Auditor
This work was conducted on behalf of the Environmental Protection
Agency's (EPA) National Enforcement Investigations Center (NEIC)
under EPA contracts68-01-7104 and 68-01-7369.
-------
An audit of laboratory operations pertaining to chain-of-
custody and document control procedures was conducted at the
Environmental Research Center of the University of Nevada Las
Vegas Quality Assurance Laboratory (ERC-UNLV) on December 15,
1986.
Soil samples collected during the Love Canal Dioxin Soil
Sampling (LCDSS) study are being prepared for analysis at ERC-
UNLV under a work assignment through EPA contract 68-01-7159.
The soil samples are being prepared using a team of ERC-UNLV and
contractor personnel. The contractor teams and their
responsibilities are described below:
• CH2M Hill - Receive and log in samples at the ERC-UNLV
facility. Sample custodian and document control
responsibilities.
• Black and Veatch - Receive logged-in samples from CH^M
Hill and prepare samples for homogenization in ERC-UNLV
containment laboratory. Processing, packaging, labeling,
shipping, and documentation responsibilities.
• ERC-UNLV - Receive processed samples from Black and Veatch
and perform actual sample homogenization in ERC-UNLV
containment laboratory. Sample homogenization and
tracking documentation responsibilities.
During the audit, the audit team examined the procedures and
accompanying documentation related to the following: sample
receiving, sample storage, sample tracking (from receipt to
completion of preparation), and document organization and filing.
SAMPLE RECEIVING
Sample shipments were received by ERC-UNLV personnel. A.
Morera of CH2M Hill is currently unpacking the shipments and
logging then in.
All samples received at the ERC are recorded in an ERC-UNLV
Sample Receipt Logbook. This bound logbook contains the
following information:
1. Shipment number
2. Airbill number
3. Date
4. Cooler number
5. Number of coolers
6. New UNLV cooler numbers
7. Condition of seals on coolers
8. Signed and dated pages
For Love Canal soil samples received under this work
assignment, two additional document logs are completed. The
Page 1 of 6
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first log is titled LCDSS Homogenization and Unpackaging
Notebook, which contains the following information:
1. Date
2. Cooler number (Julian date format)
3. Station number
4. Resealed date
5. Number of paint cans
6. Signed and dated pages
A second log, the Sample Log-in Sheet, is also completed.
This log-in sheet contains the following information:
1. Sample custodian's signature
2. Date
3. Batch number
4. Case number
5. Airbill number
6. Storage area
7. Delivering agent's signature
8. Document control number
9. Custody seal - present/absent, intact/not intact
10. Chain-of-custody record - present/absent
11. Sample tags - present/absent
12. Sample tag numbers - listed/not listed on chain-of-
custody record
13. Sample Management Office (SMO) forms - present/absent
14. Date received
15. Time received
16. Chain-of-custody record number
17. Client/SMO sample number
18. Corresponding sample tag and laboratory sample numbers
19. Agreement of information on documents
20. Remarks
LCDSS samples are received at ERC-UNLV in shipping coolers
containing vermiculite and samples individually sealed in paint
cans. There is one eight-ounce sample bottle inside each paint
can which is sealed with custody seals and wrapped in plastic
zip-lock bags. The paint cans also had custody seals affixed to
the outsides of the cans. Chain-of-custody records accompanied
each cooler received. Airbills received with the coolers are for
each shipment, and one airbill may relate to multiple coolers in
the shipment.
All coolers were numbered as they were received, and a
record is kept (the unpackaging log, described earlier) to track
which samples were shipped in each cooler. Tracking the coolers
and samples in this fashion allows the homogenized samples to be
shipped for analysis in the same coolers in which they arrived at
ERC-UNLV.'
Standard operating procedures (SOPs) for sample receiving
and the sample custodian's duties and responsibilities are
Page 2 of 6
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documented in ERC-UNLV's Chain-of-Custody Standard Operating
Procedures (3-21-86). The auditors read these SOPs, and they
generally reflected the procedures used for sample receiving for
this project.
SAMPLE STORAGE
Samples are stored in sealed shipping coolers located in the
laboratory hallway and sample receiving room. The laboratory
facility conforms to the requirements of a secure area in that
all outside access doors are locked at all times; visitors must
sign a visitor log and be escorted while in laboratory areas.
The front door of the laboratory is equipped with a code key
entry system which may also be operated by the receptionist from
her office. All visitors must pass through the reception area
prior to entering the laboratory.
Samples stored in the coolers are identified with sample
labels containing the following information:
1. Station number
2. Date
3. Comments
4. Time
5. Collector
6. Project number
7. Client
8. Love Canal number
9. Preservative
10. Analysis required
Each homogenized sample is placed into two, four-ounce jars
designated A and B. The A jars are placed into archive storage,
and the B jars will be sent to Contract Laboratory Program (CLP)
laboratories for dioxin analyses. The four-ounce jars are
labeled in the same fashion as the eight-ounce jars, and sample
tags are also attached to the sample jars.
SOPs for sample storage and security are documented in ERC-
UNLV's Laboratory Security Standard Operation Procedures
(3/21/86) and Chain-of-Custody Standard Operating Procedures
(4/22/86). The auditors read these SOPs, and they generally
reflected the sample storage and security procedures used by the
ERC-UNLV for this project.
SAMPLE TRACKING
Samples may be tracked through the laboratory from receipt
to completion of the homogenization procedure by using the
following documents:
1. ERC-UNLV Sample Receipt Log
Page 3 of 6
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2. LCDSS Homogenization and Unpackaging Notebook
3. Sample Log-in Sheet
4. Field chain-of-custody records
5. Laboratory chain-of-custody records .
6. LCDSS Sample Homogenization Form
7. Preparation Laboratory Notebook
8. Cross-Reference Logbook
The dates of receipt, receipt signatures, and custody and
sample sample condition information is recorded on the ERC-UNLV
Sample Receipt Log, LCDSS Homogenization and Unpackaging
Notebook, and the Sample Log-in Sheets. (These documents were
described earlier in the report). The field chain-of-custody
records contain the custody transfer dates and signatures,
laboratory receipt signatures and dates, sample numbers, and the
airbill numbers.
Prior to transferring the samples from the ERC-UNLV facility
to CLP laboratories for analysis, and inter-laboratory chain-of-
custody record is prepared for each shipment. These custody
records contain the following:
1. Name of unit/address
2. Sample number (Love Canal number)
3. Number of containers
4. Sample descriptions
5. Person assuming responsibility (date/time)
6. Sample number
7. Relinquished by
8. Received by
9. Time
10. Date
11. Reason for change of custody
Sample homogenization information is documented, by sample,
on the LCDSS Sample Homogenization Forms, Preparation Laboratory
Notebooks, and the Cross-Reference Logbooks. These documents
contain the information described below:
LCDSS Homocrenization Form
PART I
1. Station number
2. Form number
3. Name of mixer
4. Date
5. Time
6. Comments
PART II
7. Sample number
8. Laboratory name (CLP lab destination)
Page 4 of 6
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9. Chain-of-custody form number
10. Dioxin shipment record from number
11. Date shipped
PART III (Archive Samples)
12. Sample number
13. Laboratory name (CLP lab destination)
14. Chain-of-custody form number
15. Dioxin shipment record form number
16. Date shipped
PART IV
17. QC sample type
18. Previous blank (Love Canal number)
19. Associated sample number with blank
20. Signature of preparer
Preparation Laboratory Notebook
1. Station number
2. Custody seal condition
3. Cooler ID number
4. Assigned number
5. Reseal date
6. Box number
7. Signature/date
Cross-Reference Log
1. Station number
2. Love Canal number
3. Archive number
4. Hand mix (method)
5. Signature/date
SOPs for sample tracking are currently being developed and
will be included in the LCDSS Quality Assurance Project Plan
(QAPP). A copy of these procedures was not available for review
during the audit. Analytical and quality assurance/quality
control procedures are included in the LCDSS QAPP.
DOCUMENT FILING
Project documents are filed by type in project notebooks.
These documents will, according to A. Morera, be incorporated
into the master project file at CH2M Hill at the completion of
the project.
During the audit, the auditors reviewed all available
project documents received by ERC-UNLV for this project. The
following deficiencies were identified:
Page 5 of 6
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1. Airbills were not signed and dated.
2. SMO forms are not used on this project. The Sample
Log-in Sheets should thus be marked "N/A" rather than
"absent" for the SMO forms receipt indication.
3. Custody records II-4-5/1038 and II-10-9/1145 need to be
signed and dated.
SOPs for document control and organization specify the use
of a document control inventory for sample receiving documents.
These documents are currently being numbered and inventoried as
they are received. Because the documents will become part of the
comprehensive LCDSS project file at CHjM Hill, it is not required
that ERC-UNLV number and inventory their project file documents.
They are only required to produce their project documents to CH2M
Hill at the conclusion of the project.
SUMMARY
At the conclusion of the audit, a debriefing was held with
ERC-UNLV, CHjM Hill, and Region II personnel. During this
debriefing, the REACT auditors made the following comments and
recommendations:
1. Chain-of-custody and document control procedures are in
place and have been implemented. ERC-UNLV appears to
be adhering to these procedures with the following
exceptions:
a. Airbills were not signed and dated.
b. Custody records II-4-5/1038 and II-10-9/1145 were
not signed and dated.
c. SMO forms are marked "absent" on the Sample Log-in
Sheets rather than "N/A" (not applicable).
d. Sample tracking SOPs were not available for review
during the audit. (According to 3. Campana and A
Morera, these SOPs will be incorporated into the
updated QAPP).
2. It was recommended that the airbills accompanying EPA
sample shipments be signed and dated upon receipt by
the laboratory.
3. It was recommended that all custody records be signed
and dated by the laboratory as required.
4. It was recommended that SMO forms be noted "N/A" rather
than "absent" on the Sample Log-in Sheets. >
Page 6 of 6
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APPENDIX C
Quality Assurance Report
Prepared by
U.S. EPA Region II Environmental Services Division
Edison, New Jersey
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
DATE; MAR 10 1988 RE6ION"
SUBJECT: Love Canal Dioxin Soil Sampling Study: QA Report
Lloyd Kahn, Quality Assurance Officer
FROM: Air and water Section (2ES-MM)
T0: Douglas Gabarini, Project Manager
New York/Caribbean Remedial Action Branch (2ERRD-NYCRA)
Attached is the final report entitled "Quality Assurance Report, Love Canal
Dioxin Soil Sampling Study".
I hope that you will find this draft acceptable. Please, call me at
FTS 340-6709 if you have any questions.
Attachments
REGION II FORM 132O-1 (9/85)
-------
QUALITY ASSURANCE REPORT
LOVE CANAL DIOXIN SOIL SAMPLING STUDY
Introduction
The objective of this report is to describe the quality assurance
program designed to ensure that the data produced for the Love
Canal dioxin soil sampling study were comparable, and were of
known accuracy and precision. This report covers the following
activities:
1. Development of an approved quality assurance project plan
(QAPjP) prior to the initiation of sampling and/or analysis,
2. Evaluation and approval of laboratories capable of handling
the analytical requirements and workload in a timely fashion,
3. Submission of performance evaluation samples and matrix
blanks,
4. Evaluation of analytical data, and
5. Technical systems audits to verify that field and laboratory
personnel adhered to the approved QAPjP and CLP protocols.
Quality Assurance Project Plan Development and Implementation
The QAPjP for the study was developed by the contractor, CH2M
Hill, and submitted to the Region II project officer for review
and approval. Subsequently, this plan was revised in response to
Region II comments. Pertinent parts of the plan dealing with
sampling and analysis were approved by the quality assurance
officer before sampling was started.
This approval did not include the required homogenization
procedure. This part of the QAPjP was developed by
the University of Nevada Quality Assurance Laboratory
Environmental Research Center (UN-LV) under a contract
arrangement with EPA's Environmental Monitoring Systems
Laboratory at Las Vegas (EMSL-LV). The procedure was submitted to
the Region II project officer and approved by the quality
assurance officer prior to the start of homogenization of the
samples. The homogenized samples were then submitted by UN-LV to
the laboratories for analysis.
-------
Evaluation and Approval of Laboratories To Perform the
Dioxin Analyses
Four CLP laboratories were employed for the routine analysis of
2,3,7,8-TCDD by low resolution GC/MS. These were the
Environmental Testing and Certification Laboratory (ETC) of
Edison, New Jersey; Eagle Picher of Miami, Oklahoma; Kansas City
Scientific Inc. (KCSI) of Kansas City, Missouri; and TMS
Analytical Services of Indianapolis, Indiana. The
Enseco/California Analytical Laboratory of West Sacramento,
California (ECAL) was used to perform additional 2,3,7,8-TCDD
analyses under a CLP Special Analytical Services (SAS) contract.
However, most of the analyses were conducted by ETC.
At the start of this study, ETC was the only laboratory which had
been awarded a contract for the dioxin analysis. The laboratory
was audited on January 8, 1987 by Region II personnel to check
its capability to perform the dioxin analyses. The team doing
the inspection concluded that the laboratory could produce
acceptable 2,3,7,8-TCDD data. EMSL-LV performed an audit of ETC
on March 20, 1987. The auditors found only minor deficiencies in
the laboratory's modus operandum.
EMSL-LV audited Eagle Picher on January 7, KCSI on January 6, TMS
on January 8 and ECAL on June 17 - 18, 1987. All laboratories
were found to be capable of producing acceptable 2,3,7,8-TCDD
data.
As a condition of obtaining a CLP contract, each of the
laboratories was required to analyze a performance evaluation
sample within the acceptable limits determined by EMSL-LV.
Performance Evaluation Samples and Matrix Blanks.
Performance evaluation (PE) samples are samples prepared by the
addition of weighed amounts of an analyte to an environmental
sample which did not contain that analyte, or an environmental
sample contaminated with the analyte, but for which the analyte
concentration was determined by multiple analyses and a mean, or
target, value was calculated. For each case, stanmdard
deviations are calculated from the multiple analyses and limits
for acceptability statistically established. The samples are
submitted as unknowns to the laboratories.
For this study, the analyte in the PE samples was 2,3,7,8-TCDD
and the samples were either supplied by EMSL-LV or were prepared
by an EPA contractor, NUS. The respective PE samples contained
target values of 0.8, 1.2 and 1.54 ug/kg 2,3,7,8-TCDD.
A PE sample was submitted with each batch of samples to evaluate
whether the laboratory was able to analyze the sample within
acceptable limits. A set of data was rejected if the PE sample
result was not within the acceptable limits set by EMSL-LV.
with each batch of environmental. A reanalysis of the rejected
batch was then required.
-------
A matrix blank is a sample of similar physical nature as the
environmental samples, but which does not contain a measurable
amount of the analyte in question. Two matrix blanks were
submitted with each set of samples. The CLP contract requires
that each laboratory add a known amount of 2,3,7,8-TCDD to one
of the matrix blanks. This is called the matrix spike. The
laboratory must then analyze the matrix blank and the matrix
spike and calculate the percent recovery of the 2,3,7,8-TCDD.
This procedure establishes that a laboratory (1) is not
inadvertently contaminating the samples with the analyte and (2)
is getting acceptable recoveries of the added 2,3,7,8-TCDD, which
indicates that the sample matrix is not interfering with the
analysis. An out-of-limits recovery of the matrix spike analyte
will not by itself cause data to be rejected, but is an
important factor, taken together with the signal-to-noise ratio,
method blank and internal standard recovery in evaluating the
acceptability of a set of data.
Evaluation of Analytical Data
All analytical data were evaluated by Region II analyst/
reviewers trained in GC/MS analysis and having specialized
knowledge in dioxin analysis. The protocol used for the reviews
is described in Region II's SOP No. HW-5, "CLP Dioxin (2,3,7,8
TCDD) Data Review", Revision II, dated 12/14/87. This, and its
earlier versions, are based upon the requirements of the IFB WA-
86-K357 "Statement of Work, Attachment A" for dioxin analysis.
The validation of data is based upon the completeness of the
deliverables in the CLP contract, proper qualitative and
quantitative calibration practices, and the attainment of the
criteria for chromatographic column resolution, signal-to-noise
ratios, maximum possible concentration, matrix blank and matrix
spike recoveries, the percent difference between laboratory
duplicates, and PE samples.
Reanalysis, also, was required for each sample for which a
laboratory was unable to achieve a "maximum possible
concentration" of at least 1.0 ug/kg.
Since data sets were rejected and reanalyzed when the PE sample
results were not within acceptable limits, all PE samples
accompanying data batches had acceptable 2,3,7,8-TCDD values.
Table I shows the values obtained on duplicate results. Of the
duplicates analyzed, only 5 were above detectable limits and
showed good repeatability.
-------
Field and Laboratory Audits
The audits performed on the laboratories performing the 2,3,7,8,-
TCDD analyses have been discussed above.
In addition, Techlaw, Inc., of Lakewood, Colorado, a contractor
employed by EPA'S National Enforcement Investigation Center at
Denver, Colorado, did a field audit of the CH2M Hill Love Canal
dioxin soil sampling operation on November 17 - 19, 1986 and a
laboratory evidence audit of UN-LV in December, 1986.
The auditors concluded that both organizations followed the QAPjP
and performed their tasks in an acceptable fashion.
Sample/Station
Number
1969
2153
3199
4097
4225
All Remaining
Samples (137)
TABLE I
DUPLICATE SAMPLE RESULTS
Original Result
ug/kg
0.04
0.12
0.03
0.12
0.17
ND
Duplicate Result
ug/kg
0.03
0.11
0.02
0.10
0.17
ND
ND = Not Detected
-------
SOP NO. ttf-5
CLP DIOXIN (2,3,1,8 TCDD) DATA REVIEW
REVISION II
J/ - / /
£
Stelios Gerazounis
Monitoring Management Branch
CONCURRED BY; r*\0*<^<*1yLv~^*^'4*v** DATE;
Louis Bevilacqu
Monitoring Management Branch
APPROVED BY; /st^**^*-^ ^\Y*— X/-.^.,.. DATE;
Gerard F. McKenna, Chief
Monitoring Management Branch
-------
STANDARD OPERATING PROCEDURE Page 1 of 15
Date: Dec. 1987
Number: HW-5
Title: CLP Dioxin Data Review Revision: 2
1.0 Introduction
1.1 This procedure is applicable to dioxin data from contractor laboratories working
under the Hazardous Waste Site Contract Labortory Program (CLP).
1.2 The data validation is based upon analytical and quality assurance re-
quirements specified in Solicitation, Offer and Award No. IFB UA-86K357.
2.0 Responsibilities
2.1 The reviewers will complete and/or file the following:
2.1.1 Data Review Log - Each reviewer will fill in the following information in
the log book for each data package:
a* date of start of case review
b. date of completion of case review
c. site
d. case number
e. contract laboratory
f. number of samples
2.1.2 Rejection Summary Form - Fill out as necessary using a ratio format. The
numerator would indicate the number of dioxin data rejected; the denominator
would indicate the number of dioxin fractions containing rejected compounds.
File in the appropriate folder*
2.1.3 SMO Report - This form is intended for use in improving the laboratories1
performance. Record all reasons for having rejected data along with any
contract violations which may or may not have lead to any rejections. Make
four copies. Give secretary four copies with instructions to mail to Num-
bers 1, 2, 3 on the SMO nailing list and to the office corresponding to the
region where the lab is located. File the fifth copy in the appropriate
folder.
2.1.3.1 In lieu of SMO Report, comments may be appended to end of review narrative
under "Contract Problems/Non-Compliance". Do not make copies for above
distribution.
2.1.A Telephone Log - All phone conversations must be Initiated by the data review
manager or the deputy project officer. If a phone call has been made, fill
out stating the bare facts of the conversation. Give two copies to secretary,
one to go to the laboratory and one to go to SMO. File the third copy in the
appropriate folder.
-------
STANDARD OPERATING PROCEDURE Page 2 of 15
Date: Dec. 1987
Number: HW-5
Title: CLP Dioxin Data Review Revision: 2
2.1.5 Data Assessment Checklist - Attachment 1 of this SOP must be completed along
with the Data Assessment Narrative.
2.1.6 Forwarded Paperwork - The following are to be forwarded to the Surveillance
and Monitoring Branch (8MB) upon completion of the review:
a. data package
b. completed data assessment checklist (original)
c. Contract Compliance Screening (CCS)
d. CLP Re-analysis Request/Approval Record (original and 2 copies)
2.1.7 Filed Paperwork - The following are to be filed within MMB files:
a. SMB Review (Copy)
b. Narrative part (Para. 6.0) of data assessment checklist (copy)
c. SMO Report (original)
c. Telephone Record Log (yellow copy)
d. Rejection Summary Form (original)
e. CLP Re-analysis Request/Approval Record (copy)
3.0 Data Completeness
Incomplete data packages must be brought to the attention of the data review
manager or the deputy project officer (DPO) whenever the lack of any information
would cause the rejection of data.
4.0 Rejection of Data
All values determined to be unacceptable on the dioxin analysis data sheets
should be lined over with a red pencil*
5.0 Acceptance Criteria
In order that reviews be consistent among reviewers, acceptance criteria as stated
In Attachment 1 should be used. Additional guidance may be found in National SOP
for data review.
6.0 Reviewer Corrections
All corrections to reviewed data made by reviewers must be Indicated in red pencil.
-------
STANDARD OPERATING PROCEDURE Page 3 of 15
Date: Dec. 1987
Number: HW-5
Title: CLP Dioxin Data Review Revision: 2
7.0 SMO Contract Compliance Screening (CCS) and FIT Preliminary Review
This is intended to aid reviewer In locating any problems, both corrected
and uncorrected.
8.0 Request for Reanalysis
Data reviewers aust note all iteas of contract non-compliance within Data
Assessment Narrative (see page 15 of this SOP). If holding times and
sample storage times have not been exceeded, the Data Review Manager or DPO
may requet ~. ^analysis, if items of non-compliance are critical to data
assessment. Requests are to be made on "CLP Re-Analysis Request/Approval
Record".
-------
STANDARD OPERATING PROCEDURE Page 4 of 15
D; : Dec. I9b7
Number: HW-5
Title: Attachment 2 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
SURVEILLANCE AND MONITORING BRANCH REVIEW
Project Name/Site:
Case Number:
Type Investigation (Circle One): - Remedial Site Other
Contract No.:
Laboratory:
Sample Identification Numbers:
Aqueous:
Soil/Sediment:
Superfund Account No,
Comments:
-------
STANDARD OPERATING PROCEDURE Page 5 of 15
Date: Dec. 19b7
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
NOTE TO THE REVIEWER; The attached SOP is for a "Total" Review of the 2,3,7,8-TCDD
data. Its purpose is to facilitate the validation of the data reported by the contracting
laboratory and also to assure that the data is being reviewed in a uniform manner.
Please read each item carefully and check YES if there is compliance and NO if there is
no compliance.
Th" reviewer must red-line unacceptable data on Sample Data Sheets (red-lined does not
imply the compound is not present).
Red-lined or rejected data means that the data is unusable and that the sample may need
to be reanalyzed by the same laboratory. If the laboratory already has analyzed the
sample twice or the sample cannot be analyzed by the method, a reanalysis must be done
by another laboratory.
Please notify immediately the Deputy Project Officer (DPO) or the Data Review Manager
concerning problems and inadequacies with regard to laboratory sample data.
1.0 Deliverables
1.1 All deliverables must be clearly labeled with the SMO case number and
the associated sample/traffic number. Review the data package to assure
that all items listed below are provided. Missing, illegible or
Incorrectly labeled Items must be checked off. The contractor should
immediately be contacted and requested to submit the missing or incorrect
items.
1.2 Are the following forms present? YES NO
a. TCDD Data Report Form (Form B-l)
b. Initial Calibration Summary (Form B-2)
c. Continuing Calibration Summary (Form B-3)
d. A Chronological List of all Sample Analyses
GC/MS Displays
a. SICP's for the Initial Triplicate Analysis of the Four
Concentration Calibration Solution
b. SICP for Each Performance Check Solution
c. SICP for Each Shift Standard
-------
STANDARD OPERATING PROCEDURE Page 6 of 15
Date: Dec. 1967
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
YES N0_
GC/MS Displays
d. Plotted Concentration Calibration Curve
e. SICP's for Each Sample Ban
WERE THE FOLLOWING CRITERIA MET?
2.0 Instrument Performance
2.1 Performance Check Solution Requirements - The performance check
solution must be analyzed at the beginning and at the end of
each 12 hour shift. __
2.1.1 Chromatographic Resolution
- The valley between 2,3,7,8-TCDD and the peak of all other
TCDD isomers must be £ 25%.
- Recalculate the valley (I) between 2,3,7,8-TCDD and the peak
of the least resolved adjacent isomer using the following
equation: x
Z Valley - ~y xlOO
Where: y - peak height of 2,3,7,8-TCDD
x - measured height from valley
of the least resolved adjacent
Isomer to the baseline.
2.1.2 Ion Critera
- The ratio of integrated ion current for m/z 320 to m/z 322
for 2,3,7,8-TCDD must be X67 and £.90.
- The ratio of
m/z 334 for
the Integrated ion current for m/z 332 to
13c122,3,7,8-TCDD DU8t ** I'67 and I*90*
ACTION: 1) If the 25X valley requirement is not met, red-
line all data collected within the shift associated
with the performance standard. No action is taken
if any of the other requirements are not met; and
2) if the performance check solution was not
analyzed in the required frequency, use professional
judgment to determine the effect on the quality of
the data.
-------
STANDARD OPERATING PROCEDURE Page 7 of 15
Date: Dec.
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
YES NO
3.0 Calibration
3.1 Initial Calibration - Initially, 2,3,7,8-TCDD Standards
of 0.2, 1.0, 5.0, and 20.0 ng/ul solutions will be injected
in triplicate. Each solution also contains 0.028 ng/ul of
37C1A2,3,7,8-TCDD (surrogate), lue/ul 13C122,3,7,8-TCDD
(internal standard) and 0.6ng/ul *3C,21,2,3,4-TCDD (recovery
standard,. The concentration of these solutions may vary
only slightly from time to time. The calibration standards
must be analyzed using the same GC conditions that were used
to analyze the performance check solution and must meet the
following criteria.
- Scanning time must be ^ 1.5 seconds.
- The ratio of the integrated ion current for m/z 320 to 322 for
2,3,7,8-TCDD must be X67 and X90.
- The ratio of integrated ion current for m/z 332 to m/z 334 for
13C122,3,7,8-TCDD and 13C121,2,3,4-TCDD must be X).67 and <0.09.
- The signal to noise ratio for ions 332 and 334 must be
>_ 10.
- The signal to noise ratio for ions 259, 320, 322, and
328 must be > 2.5. •
must maximize simultaneously
as 332, 334 of 13C12-2,3,7,8-l
- The ions 259, 320, and 322
and within 3 seconds of ions 332, 334 of XJC10-2,3,7,8-TCDD.
For each concentration level, recalculate the response factor
for unlabeled 2,3,7,8-TCDD relative to 13C12-2,3,7,8-TCDD:
RRFn- Ax X Qis
Ais X Qx
Where: Ax - of the sum of integrated ion abundance of m/z 320
and m/z 322 for unlabeled 2,3,7,8-TCDD.
Ais - the sum of integrated abundance of m/z 332 and
m/z 334 for 13C12-2,3,7,8-TCDD
Qx - quantity of unlabeled 2,3,7,8-TCDD
Qis - quantity of 13C12-2,3,7,8-TCDD
-------
YES NO
STANDARD OPERATING PROCEDURK Page 8 of 15
Date: Dec. 1987
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
Recalculate the response factor for 13C,2~2,3,7,8-TCDD relative to
13C12-1,2,3,4,-TCDD:
RRFj- AAs x Qrs
Ars x Qis
Where Ars - the sum of Integrated abundance of M/Z 332 and M/Z 334
for 13C12-1,2,3,4 - TCDD
Qrs - the quantity of 13C12-1,2,3,4 - TCDD.
- The variation of the RRF for unlabeled 2,3,7,8-TCDD
at each concentration level must not exceed 10Z RSD
- The RSD of the 4 - mean RRFs for unlabeled 2,3,7,8-TCDD
must not exceed 10% RSD.
- The RSD of the 4 - mean RRFs for 13C122,3,7,8-TCDD must
not exceed 10Z RSD.
- The mean of the 4 - mean RRFs for each compound established
In the Initial calibration must be used for concentration
calculations.
ACTION: 1) If the required initial calibration data were not
supplied, notify the laboratory. If they are unavail-
able, red-line (reject) all data; and 2) if any of
the calibration curve standards fail to meet any of
the above acceptance criteria red-line all data
associated with the calibration curve.
3.2 Calibration Check Standard - At the beginning of every 12-hour
shift, a calibration standard of a concentration of Ippb must
be analyzed using the same GC conditions that were used to
analyze the performance check standard. Were the following
operating MS conditions met?
- Scanning time must be <_ 1.5 seconds.
- The ratio of the integrated ion current for m/z 320 to 322 for
2,3,7,8-TCDD must be >_.t>7 and £.90.
- The ratio of the Integrated Ion current for m/z 332 to 334 for
_Cl12-2,3,7,8-TCDD OUBt be I*67 and I'90*
- The ions 259, 320, 322 for 2,3,7,8-TCDD must maximize
simultaneously and within 3 seconds of l3Cj,~2»3,7t8-TCDD.
-------
STANDARD OPERATING PROCEDURE Page 9 of 15
Date: Dec. 1987
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
- The signal to noise ratios for ions 259, 320, 322, and 328
must be >^ 2.b.
- The signal to noise ratios for Ions 332 and 334 must be >^ 10.
Check calculations for the response factors
for unlabeled 2,3,7,8-TCDD relative to 13C12-2,3,7,8-TCDD
and for 13C12-2,3,7,8-TCDD relative to 13C12~1,2,3,4-TCDD.
- Are there any errors?
- The response factor of 2,3,7,8-TCDD relative to
13C12-2,3,7,8-TCDD must be within +_ 10% of the mean value
for the initial 4-point calibration curve*
13,. -5
The response factor of 1JC^2-2,3,7,8-TCDD relative to
13C12-1,2,3,4-TCDD must be within^ lny —-« «=i..« «*
initial 4 point calibration curve.
ACTION: 1) If the required number of analyses of calibration
check solutions were not submitted notify the con-
tracting laboratory. If they are unavailable, reject
all data without an associated calibration check
standard; and 2) if the calibration check standard
fails to meet any of the acceptance criteria, reject
all the data associated with this standard.
A.O Sample Data
4.1 Qualitative Requirements
4.1.1 The RT
of the
of 2,3,7,8-TCDD must be within 3 seconds of the RT
13c12-2,3,7,8-TCDD.
4.1.2 The Integrated ion currents for m/z 259, 320 and 322 must
maximize simultaneously.
4.1.3 The integrated ion currents for m/z 259, 320, 322, and 328
must be at least 2.5 times background noise and must not
have saturated the detector.
4.1.4 The internal standard ions m/z 332, 334 must be at least
10 times of noise level.
4.1.5 The ratio of the integrated ion currents m/z 320 to m/z 322
and m/z 332 to m/z 334 must be X67 and £.90.
YES NO
-------
STANDARD OPERATING PROCEDURE Page 10 of 15
Date: Dec. 198?
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
4.1.6 When 2,3,7,8-TCDD is not present, the ratio of internal
standard ion m/z 332 to mlz 334 must still be >.67 and
4.1.7 If the 2,3,7,8-TCDD was not qualitatively Identified in the
sample, the MFC (detection Units) oust not exceed 1 ppb.
ACTION: 1) if the 2,3,7,8-TCDD qualitative criteria
were not met, 2,3,7,8-TCDD was not qualitatively
identified, red-line positive value; 2) if the
detection limit exceeds 1 ppb, red-line ND (not
detected) dioxin value; 3) if the signal to
noise criteria for ions m/z 328, 332, 334 were
not met, red-line positive or ND dioxin values;
and 4) if the ratio of ion m/z 332 to m/z 334 is
outside the acceptance criteria, red-line positive
or ND dioxin data.
4.2 Quantitative Requirements
4.2.1 Recalculate the concentration of 2,3,4,7-TCDD which was
found in the sample using the equation:
Cx - Ax X Qis
Ais X RRFnX W
Where: Cx - the concentration of 2,3,7,8-TCDD in micrograms/Kg
Ax - the sum of Integrated ion abundance for M/Z 320 and
M/Z 322 for unlabeled 2,3,7,8-TCDD
Ais • the sum of integrated ion abundances for M/Z 332
and M/Z 334 which are the characteristic ions for
the internal stanard 13C12~2,3,7,8-TCDD
Qis - quantity of the internal standard (in nanograms)
added to the sample before extraction
RRFQ - calculated mean response factor for unlabeled
2,3,7,8-TCDD relative to 13C12-2,3,7,8-TCDD
W - weight (in grams) of wet soil or sediment sample
YES NO
-------
STANDARD OPERATING PROCEDURE Page 11 of 15
Date: Dec. 198?
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
YES NO
4.2.2 Recalculate the concentration of the internal standard
1^C12~2'^'7>8~TCDD uslnS £he formula:
Cis - Ais x Qrs _
Ars x RRF x W
Where: Cis - the concentration of the l3C12-2,3,7 ,8-TCDD in ug/kg
or ug/L
Ais - the sum of integrated ion abundance for M/Z 332 and
334 for 13C12-2,3,7,8,-TCDD
Ars - sum of integrated ion abundances for M/Z 332 and
334 for 13C12-1,2,3,4-TCDD
Qrs » quantity (in ng) of 13C12-1 ,2,3,4-TCDD added to the
sample before injection
RRFj - calculated mean response factor for *3Cj2~2,3,7,8
-TCDD relative to C12~l ,2,3,4-TCDD
W » weight (in grams) of wet soil or sediment sample
or volume of water extracted (in mL)
4.2.3 The recovery of the internal standard must be within the 40 and
120 percent recovery window. _
ACTION: These are advisory limits. View outliers in con-
junction with surrogate recoveries and other data.
4.3 Recalculate Maximum Possible Concentration - When no unlabeled Dioxin
is detected, the lab must calculate the estimated detection limits which
is the concentrations required to produce a signal with an area or
peak height 2.5 times the background signal area or peak height. To
recalculate use the formula:
MFC - 2.5 X Ax2 X Qis
Ais2 X RRFn X W
Where: MFC - Estimated maximum possible concentration for unlabeled
2,3,7,8-TCDD in ug/kg or ug/L.
Ax2 • peak height or integrated ion abundance for
M/Z 320 or 322
Als2 » integrated ion abundance or peak height for
M/Z 332 when M/Z 320 is used or M/Z 334
when M/Z 322 is used to determine Ax
-------
STANDARD OPERATING PROCEDURE Page 3.2 of 15
•\\:x. i...;. 1987
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
Qis = same definition as in A.2.1
RRFn » calculated mean response factor for 2,3,7,8 -TCDD
relative to 13C12 - 2,3,7,8 - TCDD
W - same definition as above
YES N0_
NOTE: The use of the area or peak height for M/Z 320 is
preferred to M/Z 322 except when there is Inter-
ference for M/Z 320 but not for H/Z 322
ACTION: If variation in the calculations are found be-
tween the contractor's results and the regions
recalculated results, the contractor must be
informed and the discrepancy resolved. If the
calculated amount of unlabeled Dioxin is out-
side the linear range obtained by the Initial
calculation (100 ppb for the A points) reject
the data.
A .A Estimated Maximum Possible Concentration - For samples where
Interference is observed for both M/Z 320 and 322 or when an
unacceptable ratio prevented identification of unlabeled
2,3,7,8-TCDD, use equation in Section A.2.1 to estimate the
maximum concentration that could be represented by detected
signals.
5.0 Quality Control
5.1 Blanks - Field Blank/Reagent Blank
5.1.1 One field blank must be extracted and analyzed for each
batch of samples
5.1.2 One method blank must be extracted and analyzed for each batch
of samples or each time a group of samples are extracted.
5.1.3 Acceptable laboratory method blanks must not contain any
signal at 320, 322, or 259 which is greater than 2Z of the
m/z 332 response within +5 scans of the m/z 332 peak maximum.
If the method blank that was extracted along with a batch of
samples is contaminated, the associated positive samples must
be rerun. (See Exhibit C.)
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STANDARD OPERATING PROCEDURE Page 13 of 15
Date: Dec. 1987
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
YES NO
ACTION: 1) If the proper number of reagent blanks, were
not submitted notify the contractor. If they are
unavailable, reject all positive sample data;
2) If the field blank is missing, notify the DPO
and discuss the action to be taken; 3) if the
contamination of Dioxin in the reagent blank or
in the field blank is >.l ppb all positive dioxln
data must be rejected; and the sample results <10
times the blank, contamination. 4) if the contami-
nation of Dioxin in the blank is <•! ppb no action
is taken; and, 5) If the detection limit in the
blank exceeds 1 ppb red-line positive data in all
samples associated with the blank.
5.1.4 Matrix Spikes Requirements - Each batch of samples must con-
tain a sample of uncontaminated soil/sediment which is
fortified before analysis with a quantity of 1 ug/kg of
unlabeled Dioxin, 50 ng of 13C12-2,3,7,8-TCDD and 10 "8 of
37Cl4-2,3,7,8-TCDD.
5.1.4.1 Is the percent recovery of 2,3,7,8-TCDD within the 60 to
140 percent range?
ACTION: If the recovery is outside the 60 to 140 percent
range, no action is taken in regard to the accep-
tability of the data. It may be used, however, as
a criterion to decide questionable cases. The
contracting lab must be notified, however, and the
problem discussed.
5.1.5 Duplicate Analysis Sample
5•1.5.1 For every batch of samples, is there a sample designated
as duplicate?
5.1.5.2 Results of laboratory duplicates must agree within 501
relative difference.
ACTION: No action Is taken if relative difference is
>50%. The contracting laboratory must be
notified, however, and the problem discussed.
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STANDARD OPERATING PROCEDURE
Page 14 of 15
Title: Attachment 1 -
CLP Dioxin Data Assessment Checklist
(GC/MS Analyses)
Date: Dec. .1987
Number: HW-5
Revision: 2
5.1.6 Performance Evaluation (PE) Sample - A performance evaluation
sample which is provided by the region must be analyzed with
every batch of sample.
5.1.6.1 Do the analytical results fall within the 99% EMS-LV
acceptance criteria?
YES
NO
Sigma
Code
14
16
17
18
24
25
26
Target ppb
7.7
10.0
5.0
3.3
1.0
1.0
10.0
11
8
23
48
0
44
57
00
25
5.7
6.7
4.1
3.4
— —
0.84
7.9
1.5448
1.5448
0.92
0.61
0.54
0.57
____
0.16
0.66
0.22
0.22
Windows ,
90%
(3.9-7.4)
(5.4-7.9)
(3.1-5.0)
(2.4-4.3)
95%
(3.5-7.8)
(5.1-8.2)
(2.9-5.2)
(2.2-4.5)
99%
(2.6-8.7)
(4.4-8.9)
(2.5-5.6)
(1.8-4.9)
(0.56-1.1) (0.51-1.2) (0.40-1.3)
(6.8-9.0) (6.6-9.2) (6.2-9.6)
(1.10-2.00) (0.88-221)
(1.09-2.00) (0.72-2.37)
ACTION: 1) The PE raw data oust be reviewed as if it were
an environmental sample; 2) if 2,3,7,8-TCDD was not
qualitatively identified reject all data; 3) if the
reported value for PE sample exceeds the upper
acceptance limits, reject all positive Dioxin values
in the entire associated batch of samples, but not
the ND values; and 4) if the reported value exceeds
the lower acceptance limits, all positive and nega-
tive (ND) values are rejected.
6*0 Holding Times (For water sample only).
6.1 Have any holding times have been exceeded for aqueous samples
1°
a. Todays to extraction from verified time of sample receipt
b. 40 days after extraction for analysis
Action: If these holding times are exceeded, red-lined the
value on the data sheet (including detedtlon limits)
indicating rejection.
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STANDARD OPERATING PROCEDURL Page 15 of 15
Date: Dec. 19«7
Number: HW-5
Title: Attachment 1 - CLP Dioxin Data Assessment Checklist Revision: 2
(GC/MS Analyses)
CASE// LAB Site
7.0 Conclusions: (NOTE: Reviewers mist red-line unacceptable data on sample data
sheets; red-line data does not imply the compound is not present)
7.1 Data Assessment Narrative
7.2 Contract Problems/Non-compliance
Reviewer's Signature: Dates
Verified By: Date:
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