EPA-560/13-80-030
July 1980
MIDWEST RESEARCH INSTITUTE
MRI
EPORT
DETERMINATION OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE RESIDUES
TASK 12
FINAL REPORT
July 29; 1980
EPA Prime Contract No. 68-01-5915
MRI Project No. 4901-A12
Prepared for
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Dr. Frederick Kutz, Project Officer
Ms. Sandra Strassman-Sundy, Task Manager
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MRI- NORTH STAR LABORATORIES 10701 Red Circle Drive, Minnetonka, Minnesota 55343 612933-7880
MRI WASHINGTON, D.C. 20006-Suite 250,1750 K Street, N.W. 202 293-3800
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EPA-560/13-80-030
July 1980
DETERMINATION OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE RESIDUES
by
Duane Lakings
Wilma Subra
John Going
TASK 12
FINAL REPORT
July 29, 1980
EPA Prime Contract No. 68-01-5915
MRI Project No. 4901-A12
Prepared for
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Dr. Frederick Kutz, Project Officer
Ms. Sandra Strassman-Sundy, Task Manager
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 816753-7600
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This document has been reviewed and approved for publication by the
Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S.
Environmental Protection Agency. Approval does not signify that the contents
necessarily reflect the views and policies of the Environmental Protection
Agency, nor does the mention of trade names or commercial products constitute
endorsement or recommendation for use.
-------
PREFACE
This final report presents the results obtained on MRI Project No.
4901-A, Task 12 "Determination of Pentachlorophenol and Hexachlorobenzene
Residues," for the Environmental Protection Agency (EPA Prime Contract No.
68-01-5915). This work was conducted through a subcontract with Gulf South
Research Institute, Ms. Wilma Subra, Task Manager. This report was prepared
by Dr. Duane B. Lakings , MRI Task Leader, and Ms. Wilma Subra.
ESEARCH INSTITUTE
Jotfn E. Going
Program Manager
Approved:
James L. Spigarelli, Director
Analytical Chemistry Department
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CONTENTS
Preface i:i.
Figures iv
Tables vi
1. Introdocution 1
2. Summary 2
3. Conclusions 4
4. Recommendations 5
5. Study Protocol 6
Sample collection 6
Sample preparation procedures 17
Analytical methods 20
Quality control procedures 21
6. Results and Discussion. . 25
Serum PCP and HCB determinations 25
Unconjugated urinary PCP determination 37
Field spike experiments for serum PCP and HCB
and urinary PCP 44
Statistical evaluaton of serum and unconjugated urinary
PCP levels 51
PCP levels in hydrolyzed urines 51
Air sample levels of PCP and HCB 59
PCP and HCB in food products 66
PCP and OCDD in wood samples. 66
Appendix I - Stenciling on Arsenal Boards from Madison County, Kentucky. 70
111
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FIGURES
Number Page
1 Location of residences sampled in Madison County, Kentucky. . . 7
2 Pentachlorophenol standard on 1.5% 0V-17/1.95% QF-1 23
3 Serum sample of individual 209A on 1.5% OV-17/1.95% QF-1. ... 30
4 Serum sample of individual 210A on 1.5% OV-17/1.95% QF-1. ... 31
5 Serum sample of individual 211A on 1.5% OV-17/1.95% QF-1. ... 32
6 Serum sample of individual 209A on 1.5% OV-1/2.4% OV-225. ... 33
7 -Serum sample of individual 210A on 1.5% OV-1/2.4% OV-225. ... 34
8 Serum sample of individual 211A on 1.5% OV-1/2.4% OV-225. ... 35
9 Mass spectrometry confirmation of serum of individuals 209A
through 212A 36
10 Urine sample (unconjugated) of individual 207A on 1.5%
OV-17/1.95% QF-1 41
11 Urine sample (unconjugated) of individual 208A on 1.5%
OV-17/1.95% QF-1 42
12 Urine sample (unconjugated) of individual 209A on 1.5%
OV-17/1.95% QF-1 43
13 Mass spectrometry confirmation of urine of individuals 206A,
207, 208A and 209A 45
14 Mass spectrometry confirmation of urine of individual 211A . . 46
15 Mass spectrometry confirmation of urine of individuals 210A,
212A, and 213A 47
16 Correlation of serum and urinary (unconjugated) concentrations
of pentachlorophenol 56
17 Correlation of serum and urinary (unconjugated) concentrations
of pentachlorophenol excluding outliers 57
IV
-------
TABLES (continued)
Number
18 Correlation of logarithms of serum and urinary (unconjugated)
concentrations of pentachlorophenol 58
19 Air sample 1007 (special case residence) on 1.5%
OV-17/1.95% QF-1 62
20 Air sample 1008 (special case residence) on 1.5%
OV-17/1.95% QF-1 63
21 Mass spectrometry confirmation of air samples 1007 and 1008. . 61
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TABLES
Number
1 Listing of Residences Sampled for Pentachlorophenol in the
Madison County Area, Kentucky
2 Individuals of Madison County, Kentucky, Sampled for Penta-
chlorophenol and Hexachlorobenzene in Their Blood and Urine . 10
3 Residences of Madison County, Kentucky Whose Air was Sampled
for Pentachlorophenol and Hexachlorobenzene 13
4 Food Products Collected from Various Residences in the Madison
County, Kentucky Area 14
5 Residences in the Madison County, Kentucky Area from Which Wood
Samples were Collected 15
6 Linearity of Pentachlorophenol and Hexachlorobenzene
Analysis by GC-EC 20
7 Levels of Pentachlorophenol and Hexachlorobenzene in the Serum
and Urine (Unconjugated) of Test Cases 26
8 Levels of Pentachlorophenol and Hexachlorobenzene in the Serum
and Urine (Unconjugated) of Controls 28
9 Duplicate Analyses of Serum Samples for Pentachlorophenol ... 38
10 Recovery of Pentachlorophenol and Hexachlorobenzene Added to
Pooled Serum Aliquots 39
11 Recovery Values for Pentachlorophenol and Hexachlorobenzene in
Serum by Two Extraction Methods 40
12 Replicate Analyses of Urine Samples for Unconjugated
Pentachlorophenol 45
13 Recovery of Pentachlorophenol Added to Pooled Urine Aliquots. . 49
14 Recovery Values for Pentachlorophenol and Hexachlorobenzene in
Field Spikes of Serum and Urine (Unconjugated) 50
15 Recovery Values for Pentachlorophenol and Hexachlorobenzene in
Simulated Field Spikes 52
16 Test Cases and Control Individuals for the Pentachlorophenol
Study in Richmond, Kentucky 54
VI
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TABLES (continued)
Number Page
17 Serum and (Unconjugated) Urinary Pentachlorophenol
Concentration (ppb) for Cases and Controls 55
18 Levels of Pentachlorophenol (Conjugated and Unconjugated)
in Hydrolyzed Test and Control Urine Samples 60
19 Levels of Pentachlorophenol and Hexachlorobenzene in Air
Samples 61
20 Recovery Values for Pentachlorophenol and Hexachlorobenzene
from Tenax 65
21 Levels of Pentachlorophenol and Hexachlorobenzene in Food
Products 67
22 Levels of Pentachlorophenol and Octachlorodibenzodioxin
in Wood Samples 68
VII
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SECTION 1
INTRODUCTION
Between 1968 and 1971, the U.S. Army Lexington Blue Grass Depot received
a large supply of wooden munition crates possibly treated with pentachloro-
phenol (PCP). A number of these crates, given or sold to residents of Madison
County, Kentucky, were used in housing construction, paneling, etc. Thus,
some area residents may have been exposed to high levels of PCP.
The Center for Disease Control (CDC), in response to requests by Congress
and local medical authorities, initiated plans to investigate potential health
problems associated with PCP exposure. A phase of the study was to determine
and compare serum and urinary (unconjugated) PCP and serum hexachlorobenzene
(HCB) levels in individuals exposed to PCP-treated ammunition crate wood in
their home and in unexposed controls and to assess the levels of PCP and HCB
in wood, air, and food product samples from the possible PCP-exposed residences
and controls. The Environmental Protection Agency (EPA) through a contract
with Midwest Research Institute (MRI) and a subcontract with Gulf South Research
Institute (GSRI) assisted in the analysis of samples selected and collected
by CDC.
The major goals of this study were:
1. Define and collect samples from a test group of approximately 30
individuals from 15 families having PCP-treated ammunition crate wood in
their homes.
2. Identify and collect samples from a control group with no PCP-
treated ammunition crate wood in the home. The control group was to be
matched with the test group in number, approximate age, sex, and race. The
residences of the control group were to be adjacent or near the homes of the
test group.
3. Samples to be collected included serum and urine from each test and
control individual and air, food products, and wood from the residences.
4. Analyze the collected samples as follows: serum - PCP and HCB;
urine - unconjugated PCP; air samples - PCP and HCB; food products - PCP and
HCB; and wood - PCP, HCB, and dioxins. The wood samples were analyzed at the
EPA laboratory in Beltsville, Maryland.
The remainder of this report presents the summary, conclusions, recom-
mendations, experimental protocol, results and discussion, and appendix.
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SECTION 2
SUMMARY
A number of individuals who have been exposed to pentachlorophenol-
treated ammunition crate wood obtained from the Blue Grass Army Depot,
Lexington, Kentucky were sampled for serum and unconjugated urinary PCP levels
and wood, air, and food product samples from selected residences were taken
for PCP level determination^" A control individual matched to each test case
in age, sex, and residence location was also sampled. In addition, control
residences were sampled to obtain background levels of PCP in wood, air, and
food products. Also, two families who live in log homes treated with "penta"
requested to be a part of the study and were designated as special cases. A
total of 45 residences were sampled and resulted in 45 test case, 7 special
case, and 45 control individual serum samples, 51 test case, 7 special case,
and 47 control individual urine specimens, 18 test case, 2 special case, and
20 control individual residence air samples, 9 test case and 7 control indivi-
dual residence food product samples, and 28 test case, 1 special case, and 21
control individual residence wood samples.
The serum, urine, air, and food product samples were analyzed for PCP at
Gulf South Research Institute. The serum, air, and food products were also
analyzed for HCB, a compound whose major metabolite is PCP. Urinary PCP
levels were determined for the unconjugated compound. The wood samples were
analyzed at the EPA Laboratory in Beltsville, Maryland.
The data for serum and unconjugated urinary PCP levels indicated that
the test cases and control individuals had similar levels. Statistical eval-
uation of these data showed no increase in the PCP levels of the test cases
and no correlation between the serum and unconjugated urinary PCP level.
However, the special cases, two familes who reside in log homes and do
not have the ammunition crate wood present, had elevated serum and unconjugated
urinary PCP levels in relation to the control individuals. The highest serum
PCP levels were in the three special case children (ages 2, 4, and 9 years)
and were 1,750, 1,680, and 910 ppb, respectively (compared to the normal control
PCP serum level average of 24 ppb). The urinary excretion of unconjugated
PCP in these three special cases was more than 20 times the average of the
normal controls.
No HCB was detected in the serum of any test or special case or control
individual.
The air samples obtained from test case and control residences had non-
detectable (< 0.005 ng/1) levels of PCP and HCB. Air samples from one log
home (special case residence) gave PCP levels of 0.2 and 0.38 ng/1. No air
sample was obtained from the other log home.
-------
Food products contained PCP levels ranging from not detectable (< 0.4
ppb) to 11.7 ppb. No correlation was made between the food products obtained
from test case and control residences due to the limited number of samples
analyzed. HCB was not detected in any food product analyzed. No food prod-
ucts were obtained from the special case residences.
The wood samples collected were analyzed for PCP and octachlorodibenzo-
dioxin (OCDD) at the EPA laboratory in Beltsville, Maryland. Seven test case
wood samples had detectable PCP (range 8.6 to 737 ppm) and eleven control wood
samples had PCP (range 4.3 to 1,452 ppm). A wood sample from one special case
log home also had PCP (836 ppm). No wood was obtained from the other special
case log home. Only one wood sample had detectable OCDD and that level was
at the detection limit of the analytical method (1 ppm). Data on the HCB levels
in these wood samples will be reported later.
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SECTION 3
CONCLUSIONS
The serum and unconjugated urinary levels of PCP in test cases and con-
trol individuals indicate that the residences with ammunition crate wood did
not increase the PCP levels in the test case individuals. However, the two
special case families, residing in log homes and not possessing ammunition
crate wood, did have high serum and unconjugated utinary PCP levels. This
increase was especially noted in the three children of the special case fam-
ilies where the serum PCP levels were 1,000 ppb or above. In an EPA report,1
serum levels of PCP above 1 ;'000 ppb were noted to cause toxic effects. Thus,
toxicity from PCP is possible in the three young special case children.
The urine from the test cases, special cases, and control individuals
was analyzed for unconjugated PCP, and no correlation between serum PCP and
unconjugated urinary PCP levels existed for the test cases and control indi-
viduals. However, when selected urines were hydrolyzed, a 2 to 7 times in-
crease in the PCP level was observed. This increase in PCP level for hydro-
lyzed urine does not affect the overall results since the serum PCP levels of
the test cases and control individuals showed similar levels. The lack of
correlation between the serum and unconjugated urinary PCP levels indicates
that unconjugated urinary analysis cannot be employed alone to assess possible
PCP exposure. However, the total urinary PCP excretion (conjugated and uncon-
jugated) over a defined time period (24 hr collection) or collection period
(early morning excretion) may provide correlation to serum PCP levels.
The results from the air sample analyses of PCP and HCB showed that the
test case individuals were not being exposed to PCP in the air. The only air
sample with detectable PCP was from a log home (special case), again indicat-
ing that the special case individuals were being subjected to PCP exposure.
The limited number of food products analyzed for PCP and HCB residues
prevented correlation between the test case and control residences.
Also, no correlation was possible from the wood samples taken from test
case and control residences and analyzed for PCP and OCDD. The one wood sam-
ple taken from a log home (special case) had a high level of PCP. Since the
treatment of the log homes with penta (PCP) may have included the total dwell-
ing, the residents of the log home may be exposed to much higher PCP levels
than the test case individuals where only a limited amount of ammunition crate
wood was present.
EPA Report No. 540-9-77-013, Recognition and Management of Pesticide
Poisoning, D. P. Morgan, 2nd edition, page 25, printed by EPA.
-------
SECTION 4
RECOMMENDATIONS
Additional studies on the PCP levels from test cases and control indi-
viduals are not required since similar PCP levels were found between these
two groups indicating that the test case individuals are not carrying a body
burden of PCP. However, the results from this study indicate that the special
cases who reside in log homes are being subjected to high PCP exposure and
additional studies on this group are recommended. These studies should be
designed to define the health effects of chronic exposure to PCP and to deter-
mine the levels at which toxic effects to PCP become apparent. These data
can be utilized to notify current log home residents of potentially adverse
health effects to PCP exposure especially with regard to children and pregnant
women.
Also, in future studies to assess possible exposure to PCP, or other
toxic substances, the sampling protocol should be designed for the collection
of a defined urine specimen, either a 24-hr collection or an early morning
specimen, so that the urinary excretion can be better defined. The collected
urine specimens should be analyzed for the unconjugated compounds and for pos-
sible metabolites such as the glucuronide or sulfate adduct so that the total
urinary excretion (unconjugated and conjugated) of the compound can be deter-
mined. Prior to analyzing hydrolyzed urine specimens, studies to define the
optimal hydrolysis conditions and the stability of the compound under these
conditions should be conducted. By analyzing a defined urine specimen for
total extretion of a compound and comparing the results to serum levels of
the compound, a correlation between urinary excretion and serum levels may be
obtained. This information may then be employed in other studies on the same
compound using only defined urine specimens, a non-invasive technique which
is usually more acceptable to the subjects being sampled, to determine the
possible exposure and the exposure levels to the compound.
-------
SECTION 5
STUDY PROTOCOL
The collection of human blood and urine specimens and air, wood, and food
products samples was performed from January 28, 1980 through February 7, 1980.
During that time period, the human specimens and other samples were collected
from 45 residences in the Madison County area. Table 1 presents a list of the
residences and Figure 1 indicates their location. From the 45 residences, blood
and urine specimens were collected from 97 and 105 individuals, respectively.
Blood specimens were not obtained from eight young children due to their age.
A list of the individuals by age, sex and race, their Madison County Health
Department code number, and the date of collection of the serum and urine sam-
ples are presented in Table 2. Air samples were collected from 38 residences,
listed in Table 3, in the Madison County area. Food products were collected
from five residences in the area and consisted of milk, eggs, pork, and butter.
The residences and products collected from each are presented in Table 4.
Wood samples were collected from 42 residences in the Madison County area,
and the samples sent to the U.S. EPA laboratory in Beltsville, Maryland for
analysis. Table 5 presents a list of residences, their Madison County Health
Department code numbers, the date collected, and a description of the wood
sampled. The study area was revisited between February 11 and 14, 1980 to
record the stenciled information on all ammunition boxes from the Blue Grass
Depot. All families known to have arsenal wood in their home or out-buildings,
i.e., storage sheds, barns, chicken coops, etc., were contacted, and appoint-
ments were made to visit those residences with stenciling apparent on the wood.
An appointment was not scheduled for the residences with painted wood or those
that had disposed of the wood after the initial visit of the collection team.
All visible stenciling was recorded and 35 mm photographic slides taken of the
accessible boards. The stenciling data recorded from the residences visited
are presented in the Appendix. Stenciling blurred, worn off, or covered over
by other boards are represented in the Appendix presentation as a question
mark. The 35 mm slides are on file at MRI.
SAMPLE COLLECTION
General
The screening of test case volunteers and the selection of control vol-
unteers were performed by the Center for Disease Control in cooperation with
the Madison County Health Department and Kentucky State Department of Human
Resources. The initial visit to each test and control home was made by Madison
County Health Department personnel and GSRI personnel. Collection of human
blood and urine specimens was performed by the health department personnel
while wood, food product, and air sampling was performed by GSRI personnel.
-------
TABLE 1. LISTING OF RESIDENCES SAMPLED FOR PENTACHLOROPHENOL
IN THE MADISON COUNTY AREA, KENTUCKY
Residence
number
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Residence
type
test case
control
test case
control
test case
test case
control
test case
special case
test case
test case
test case
control
test case
control
control
test case
test case
control
special case
control
control
Residence
number
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39*
40
41
42
43
44
45
Residence
type
control
control
test case
control
control
control
test case
control
test case
test case
control
control
test case
test case
test case
test case
control*
control
control
test case
control
control
control
Note: Numbers correspond to numbered locations on Madison County map
(Figure 1).
* Control changed to test case after ammunition crate wood located
in the residence.
Special cases are log home residences.
-------
00
16 (COVINGTON)
+ 43 (LEXINGTON)
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37
Figure 1. Location of residences sampled in Madison County, Kentucky.
-------
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GENERAL HIGHWAY MAP
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KENTUCKY
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KENTUCKY DEPARTMENT OF TRANSPORTATION
OFFICE OF TRANSPORTATION PLANNING
DIVISION OF FACILITIES PLANNING
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-------
TABLE 2. INDIVIDUALS OF MADISON COUNTY, KENTUCKY SAMPLED
FOR PENTACHLOROPHENOL AND HEXACHLOROBENZENE
IN THEIR BLOOD AND URINE
Madison County Health
Department number
Test cases
100A
101A
102A
103A
104A
105A
106A
107A
108A
109A
110A
111A
112A
113A
114A
115A
116A
117A
118A
119A
120A
121A
122A
123A
124A
125A
200A
201A
202A
20 3A
204A
205A
213A
214A
215A
216A
217A
218A
219A
220A
221A
Identification
age
32
62
69
11
29
47
-25
11
13
49
65
20
50
56
47
14
10
05
11
26
27
33
15
12
02
55
36
14
10
57
32
25
33
08
05
56
45
15
21
17
51
sex
female
female
male
female
female
male
female
male
male
female
female
female
female
male
female
female
male
female
male
male
female
female
female
female
male
female
female
male
female
female
female
female
female
female
female
male
female
female
male
male
male
race
white
white
white
white
white
white
unknown
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
Collection date
serum
1/28/80
1/28/80
1/28/80
1/28/80
1/28/80
1/29/80
1/29/80
a
1/29/80
1/29/80
1/29/80
1/29/80
1/29/80
1/29/80
1/29/80
1/29/80
a
a
1/29/80
1/30/80
1/30/80
2/1/80
2/1/80
2/1/80
a
2/5/80
1/28/80
1/28/80
1/28/80
1/29/80
1/29/80
1/29/80
1/31/80
a
1/31/80
1/31/80
1/31/80
1/31/80
1/31/80
1/31/80
2/1/80
urine
1/28/80
1/29/80
1/29/80
1/28/80
1/28/80
1/30/80
1/30/80
1/30/80
1/29/80
1/30/80
1/30/80
2/1/80
2/1/80
2/1/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
1/31/80
1/31/80
2/1/80
2/1/80
2/1/80
2/5/80
2/2/80
1/29/80
1/29/80
1/29/80
1/30/80
2/4/80
2/5/80
1/30/80
1/31/80
1/31/80
2/1/80
2/1/80
2/1/80
2/1/80
2/1/80
2/1/80
(continued)
10
-------
TABLE 2 (continued)
Madison County Health
Department number
222A
223A
224A
225A
226A
227A
228A
Special cases
206A
207A
208A
209A
210A
211A
212A
Control individuals
100B
101B
102B
103B
104B
105B
106B
107B
108B
109B
HOB
111B
112B
113B
114B
115B
116B,
r*
117BD
118B
119B
120B
121BD
122B
123B
124B
200B
201B
Identification
age
49
16
22
49
49
29
39
29
28
09
34
29
02
04
28
44
44
17
26
58
30
09
13
51
57
15
48
51
31
12
10
08
09
36
33
38
14
15
02
29
16
sex
female
male
male
male
female
female
male
male
female
male
male
female
female
female
female
female
male
female
female
male
female
female
male
female
female
female
female
male
female
female
female
female
female
male
female
female
female
male
female
female
female
race
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
unknown
white
white
white
white
white
white
white
white
white
black
white
white
Collection date
serum
2/1/80
2/1/80
2/1/80
2/2/80
2/2/80
2/2/80
2/2/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
2/5/80
2/2/80
2/2/80
2/5/80
2/5/80
2/1/80
2/1/80
2/1/80
2/1/80
2/1/80
2/1/80
2/2/80
2/2/80
2/2/80
1/31/80
1/31/80
1/31/80
a
2/1/80
2/6/80
2/5/80
2/4/80
2/1/80
2/4/80
a
2/1/80
2/2/80
urine
2/1/80
2/1/80
2/3/80
2/3/80
2/3/80
2/3/80
2/3/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
1/30/80
2/5/80
2/5/80
2/5/80
2/5/80
2/5/80
2/2/80
2/2/80 .
2/2/80
2/2/80
2/2/80
2/2/80
2/3/80
2/3/80
2/3/80
2/1/80
2/1/80
2/1/80
2/5/80
2/2/80
2/6/80
2/6/80
2/5/80
2/6/80
2/6/80
2/3/80
2/1/80
2/2/80
(continued)
11
-------
TABLE 2 (continued)
Madison County Health
Department number
Identification
age sex race
Collection date
serum urine
202B
203B
204B
205B
206BC
207BC
210BC
213B
214B
215B
216B
217B
218B
219B
220B
221B
222B
223B
224BD
225B
226B
227B
228B
09
49
32
32
30
33
33
28
04
06
56
55
16
32
17
65
59
23
21
54
46
29
29
male
female
female
female
male
female
female
female
male
male
male
female
male
male
male
male
female
male
female
male
female
female
male
white
white
black
white
white
white
white
white
white
white
white
white
white
black
white
white
white
white
white
white
white
white
white
2/1/80
1/30/80
2/3/80
2/4/80
2/6/80
2/5/80
2/5/80
2/5/80
a
2/5/80
2/5/80
2/5/80
2/4/80
2/3/80
2/2/80
2/5/80
2/5/80
2/5/80
2/5/80
2/2/80
2/2/80
2/5/80
2/5/80
2/1/80
1/31/80
2/3/80
2/4/80
2/6/80
2/6/80
2/5/80
2/6/80
2/5/80
2/6/80
2/5/80
2/5/80
2/2/80
2/3/80
2/5/80
2/5/80
2/5/80
2/5/80
2/5/80
2/3/80
2/3/80
2/5/80
2/6/80
a Blood specimens not obtained from these young children.
b Control individual changed to test cases after ammunition crate wood
located in their residences.
c Control individuals for special cases.
Note: None of the individuals were of hispanic origin.
12
-------
TABLE 3. RESIDENCES OF MADISON COUNTY, KENTUCKY WHOSE AIR WAS
SAMPLED FOR PENTACHLOROPHENOL AND HEXACHLOROBENZENE
Residence number Madison County Health Collection
and type Department number Date
1 -
2 -
3 -
5 -
7 -
8 -
10
11
12
13
14
15
16
17
18
19
20
22
23
24
25
26
27
28
30
31
32
33
34
35
36
39
40
41
42
43
44
45
test case
control
test case
test case
control
test case
- test case
- test case
- test case
- control
- test case
- control
- control
- test case
- test case
- control
- test case
- control
- control
- control
- test case
- control
- control
- control
- control
- test case
- test case
- control
- control
- test case
- test case
- control
- control
- control
- test case
- control
- control
- control
1004
1019
1022
H006
H007
P0007
1002
H010
H008
1025
1050
H001
1045
1003
P0001
P0002
1005
1007
1008
1021
1042
1040
1039
1014
1027
1033
1023
1031
H009
1016
1035
1015
1001
1037
1047
P0009
1006
1052
1029
P0005
1/31/80
2/1/80
2/1/80
1/29/80
1/29/80
2/5/80
1/30/80
1/30/80
1/29/80
2/2/80
2/5/80
1/29/80
2/5/80
1/30/80
2/4/80
2/5/80
1/31/80
1/31/80
1/31/80
2/1/80
2/5/80
2/5/80
2/1/80
1/31/80
2/2/80
2/2/80
2/1/80
2/2/80
1/29/80
2/1/80
2/3/80
1/31/80
1/29/80
2/4/80
2/5/80
2/5/80
1/31/80
2/6/80
2/2/80
2/4/80
Description
chicken house
dining room
second floor
basement
upstairs
study
kitchen
kitchen cabinet
under sink
--a
attic
living room
upstairs bedroom
living room
a
a
a
bedroom
first floor
second floor
dining room
bedroom
study
collected by resident
trailer
bedroom
sewing room
dining room
library
kitchen
den
kitchen
closet in middle
bedroom
basement
living room
hall pantry
utility room
stairway hall on
second floor
den
living room
~
a No description of where air sample was taken.
b Changed from control residence to test residence after ammunition crate
wood located in residence.
13
-------
TABLE A. FOOD PRODUCTS COLLECTED FROM VARIOUS RESIDENCES
IN THE MADISON COUNTY, KENTUCKY AREA
Residence number
and type
1 - test case
29 - test case
13 - control
32 - test case
40 - control
Madison County Health
Department number
G022
G021
G023
G005
G006
G007
G008
1055
1059
1060
1061
G014
GO 15
1056
1057
1058
Collection
Date
1/31/80
1/31/80
1/31/80
1/28/80
1/28/80
1/28/80
1/28/80
2/6/80
2/6/80
2/6/80
2/6/80
1/29/80
1/29/80
2/6/80
2/6/80
2/6/80
Description
egg white
egg yolk
egg shell
salted pork
milk (raw)
egg yolk
egg white
milk
(pasteurized)
egg white
egg yolk
egg shell
milk ,
butter
egg white
egg yolk
egg shell
a Chicken roost an ammunition crate.
b Chicken roost made from ammunition crate wood.
c Eggs store purchased.
d Items selected for sampling by sampling crew; no control
items obtained.
14
-------
TABLE 5. RESIDENCES IN THE MADISON COUNTY, KENTUCKY AREA
FROM WHICH WOOD SAMPLES WERE COLLECTED
Residence number Madison County Health Collection
and type Department number Date
] -
2 -
3 -
4 -
5 -
7 -
8 -
10
11
11
12
13
14
15
16
17
18
19
20
22
23
23
24
25
25
26
27
28
29
29
29
30
31
31
32
32
32
33
34
35
test case
control
test case
control
test case
control
test case
- test case
- test case
- test case
- test case
- control
- test case
- control
- control
- test case
- test case
- control
- special case
- control
- control
- control
- control
- test case
- test case
- control
- test case
- test case
- test case
- test case
- test case
- control
- test case
- test case
- test case
- test case
- test case
- control
- control
- test case
G024
1018
1011
1054
G001
P0008
G018
G027
G016
G017
1026
1051
1049
1046
G019
P0004
P0003
G025
1009
1020
1043
1044
1041
1012
1013
1010
1028
1034
G002
G003
G004
1024
1032
228A
G011
G012
G013
1017
1036
G026
1/31/80
2/1/80
2/1/80
2/6/80
1/28/80
2/5/80
1/30/80
1/31/80
1/30/80
1/30/80
2/2/80
2/5/80
2/5/80
2/5/80
1/30/80
2/5/80
2/4/80
1/31/80
1/30/80
2/1/80
2/5/80
2/5/80
2/5/80
2/1/80
2/1/80
1/31/80
2/2/80
2/2/80
1/28/80
1/28/80
1/28/80
2/1/80
2/2/80
2/2/80
1/29/80
1/29/80
1/29/80
2/1/80
2/2/80
1/31/80
Description
ammunition crate
chicken nest
old hoard in bnsement
closet floor
scrap hoard
beam in basement
shelf in garage
inside kitchen cabinet
inside kitchen cabinet
under sink
outbuilding
back porch
attic
studs in new room
toy box
studs in living room
toy train box in
bedroom
bookshelf in bedroom
bookshelf in study
shelf board in closet
second floor bath
outbuilding
firewood
ammunition box
firewood
outside wood
inside wood
dog house
basement
basement
hog house
cow and chicken house
meat house
old board in basement
subf loor
deck floor
ammunition box
manger
basement
workbench in basement
ammunition box
closet
(continued)
15
-------
TABLE 5 (continued)
Residence number
and type
Madison County Health
Department number
Date
Description
36 -
37 -
38 -
39 -
40 -
41 -
42 -
43 -
44 -
45 -
test case
test case
test case
a
control
control
control
test case
control
control
control
G010
G009
G020
1038
1048
P0010
G028
1053
1030
P0006
1/29/80
1/28/80
1/30/80
2/4/80
2/5/80
2/5/80
1/31/80
2/6/80
2/2/80
2/4/80
subfloor
ammunition crate
in kitchen
pantry
ammunition box
firewood
shelf
ammunition box
shelf
outside front door
outside wood
board in garage
Changed from control residence to test case residence after ammunition
crate wood located in residence.
16
-------
Blood
Blood specimens were drawn directly into red top Vacutainer collection
tubes. The blood was allowed to clot and the serum separated by centrifuga-
tion. The serum was transferred into 15 ml pre-washed (soaked in sodium hy-
droxide followed by deionized water and acetone rinses) septum vials with
pre-washed Pasture pipettes. The vials were sealed with Teflon lined septa
and frozen.
Urine
Pre-washed wide mouth 60 ml amber bottles with Teflon lined lids were
provided for the collection of urine specimens. The urine was transferred
from the amber bottles into two pre-washed 15 ml septum vials with pre-washed
Pasture pipettes. The vials were sealed with Teflon lined septa and frozen.
Air
Sampling of the air in the designated homes was performed using a Brail-
ford air pump powered by three 12-volt and two 6-volt batteries. Air was drawn
through two 500 mg portions of Tenax resin separated by glass wool and contained
in 15 cm x 1.2 cm ID glass tubes for 6 to 8 hr at a flow rate of approximately
1 liter per minute. Following sampling, the glass tubes were wrapped in heavy
duty aluminum foil and sealed in glass screw cap culture tubes with Teflon
lined lids.
Food Products
Samples of food products were collected in 60 ml pre-washed amber wide-
mouth bottles or heavy duty aluminum foil. Samples of meat and butter were
sealed in the amber bottles with a Teflon lined lid and frozen. Samples of
milk (raw or pasteurized) were transferred to pre-washed 15 ml septum vials
using pre-washed Pasture pipettes, sealed with Teflon lined septa and frozen.
Egg samples were cracked and the whites and yolks separated and collected in
pre-washed amber 60 ml wide-mouth bottles. The egg shells were also placed
in amber bottles. The bottles were sealed with Teflon lined lids and frozen.
Wood
Wood samples (10 to 20 g) were collected in pre-washed 60 ml wide-mouth
amber bottles. The bottles were sealed with Teflon lined lids and the entire
bottle wrapped in heavy duty aluminum foil and frozen. At each residence
having arsenal wood, the data stenciled on the wood was recorded and 35 mm
slides taken of accessible boards.
SAMPLE PREPARATION PROCEDURES
The procedures employed to prepare the samples for GC analysis of PCP
and HCB levels are delineated in the following paragraphs. The serum and un-
conjugated urinary levels of PCP and the serum level of HCB were determined
by the method outlined in "Analysis of Pesticide Residues in Human and Environ-
mental Samples," U.S. Environmental Protection Agency, Health Effects Research
17
-------
Laboratory, Research Triangle Park, North Carolina, revised June 1977. The
assay for hydrolyzed urine (unconjugated and conjugated PCP) was conducted
using the method of Edgerton and Moseman.2
Serum and Urine
Serum and unconjugated urinary levels of PCP and serum HCB levels were
determined by GC after extraction of the compounds from the sample matrix and
acetylation of the phenolic group of PCP. The sample preparation procedure
is as follows:
a. Quantitatively pipette 2.0 ml of serum or urine in a 15 ml culture
tube with a Teflon-lined screw cap.
b. Add two drops of concentrated sulfuric acid to the sample and mix on
a Vortex mixer for 30 sec.
c. Add 6.0 ml "nanograde" hexane (Mallinckrodt) to the sample and cap
the vial.
d. Extract the mixture for 2 hr on a mechanical rotator at approximately
30 rpm.
e. Centrifuge the sample at 2,000 rpm for 10 min to break the emulsion.
f. Pipette 3.0 ml of the hexane layer to a 15 ml septum vial.
g. Add 2.0 ml 0.1 M sodium borate and 50 [Jl acetylation reagent (2 ml
pyridine plus 0.8 ml acetic anhydride, prepared fresh daily).
h. Shake for 1 min and allow the phases to separate.
i. Transfer 1 ml of the hexane to a 1 ml autosampler vial for GC analy-
sis.
Hydrolysis of Urine
The sample preparation procedure described above for urinary PCP levels
measured the unconjugated or free levels of PC. Normally, compounds with polar
groups like the phenolic group of PCP are not excreted in the urine as the
parent compound but are first metabolized in the liver. For PCP, the metabo-
lism would most likely consist of conjugation to form the glucuronide or sulfate
adduct. The conjugated PCP would be efficiently removed from the blood by
the kidney; thus, very little of the metabolized PCP would be present in the
blood. Due to the relative nonpolarity of PCP and the ability of the kidney
to readsorb (through passive diffusion) nonpolar compounds back into the blood,
very little unconjugated PCP would be expected to be present in the urine.
2Edgerton, T. R., and R. F. Moseman, "Determination of Pentachlorophenol
in Urine: The Importance of Hydrolysis." J. Agric. Food Chem., Vol. 27,
No. 1, 197-199 (1979).
18
-------
Also, after the conjugated PCP is in the urine (bladder) or after excretion,
a limited amount of hydrolysis may occur which would be detected as unconju-
gated PCP in the urine. The kinetics of hydrolysis would vary between humans,
thus providing widely different levels of unconjugated compound in the urine.
To obtain the true rate of urinary excretion of a compound, the urine must be
analyzed for both the conjugated and unconjugated compound. If the conjugate
is the glucuronide or sulfate adduct (which are the most likely adducts for
PCP), hydrolysis to the free compound can be accomplished by enzymatic (aryl
sulfatase, fj-glucuronidase) or acid hydrolysis. The analysis of a hydrolyzed
urine provides a measure of the conjugated and unconjugated level of a com-
pound .
Analysis of the human urine specimens for unconjugated PCP was requested.
A short study was conducted to determine the total (conjugated and unconju-
gated) urinary PCP levels. Selected urine specimens were first subjected to
acid hydrolysis followed by hexane extraction. The sample preparation proce-
dure was as follows:
a. Quantitatively pipette 5.0 ml of urine into a culture tube with a
Teflon-lined screw cap.
b. Add 1.25 ml concentrated hydrochloric acid and seal the vial.
c. Heat the sample at 100°C for 1 hr with frequent shaking.
d. Cool to room temperature.
e. Adjust the pH to 11 to 12 with 1 N sodium hydroxide.
f. Add 5.0 ml "nanograde" hexane.
g. Seal the tube and extract for 1 hr on a mechanical rotator.
h. Centrifuge at 2,000 rpm for 10 min.
i. Draw off the hexane layer and discard.
j. Adjust to pH 1 with concentrated sulfuric acid.
k. Add 2 ml "nanograde" hexane, seal the tube, and extract for 1 hr on
a mechanical rotator.
1. Centrifuge at 2,000 rpm for 10 min.
m. Pipette 1.0 ml of the hexane layer to a 15 ml septum vial.
n. Derivatize the sample using the same procedure outlined for serum
and urine sample.
19
-------
Air Samples
The front and back section of a Tenax tube were emptied into a 15 ml
centrifuge tube and 5 ml of nanograde hexane added volumetrically. The tube
was sealed and extracted on a mechanical rotator for 2 hr. The contents of
the tube were centrifuged for 10 min and 1.5 ml of the hexane layer trans-
ferred to a 15 ml septum vial for derivatization. The derivatization proce-
dure was the same as described for serum and urine samples.
Food Products
Two milliliters or 2 g (ground in a mortar and pestle) of food product
were transferred to a 15 ml glass stoppered centrifuge tube. Two drops of
concentrated sulfuric acid were added to the tube and the contents mixed for
30 sec on a Vortex mixer. Six milliliters of nanograde hexane was added
volumetrically to the sample, the tube sealed, and extracted and derivatized
by the method presented for serum and urine.
Wood
The wood samples were shipped on dry ice to the U.S. EPA laboratory in
Beltsville, Maryland for analysis of PCP, HCB, and octachlorodibenzodioxin
(OCDD).
ANALYTICAL METHODS
The levels of PCP and HCB in the various samples collected from individ-
uals and their residences were determined by gas chromatography (GC) with
electron capture (EC) detection. Samples which gave a positive GC response
for PCP or HCB were subjected to gas chromatography-mass spectrometry (GC-MS)
confirmation.
Gas Chromatography
The GC conditions employed for the quantitative determination of PCP and
HCB in the various collected samples were as follows:
a. Instrument: Hewlett Packard 5840
b. Column: 1.5% OV-17/1.95% QF-1 on 100/120 mesh Supelcoport
packed in a 6 ft glass column, 2 mm ID.
c. Injector Temperature: 250°C
d. Column Temperature: 165°C
e. Detector Temperature: 325°C
f. Carrier Gas: Helium
g. Flow Rate: 30 ml/min
h. Detector: Electron capture, 63Ni.
i. Injection: 6 (Jl with an HP 7671 autosampler.
These parameters were employed for all samples analyzed. Those samples show-
ing a positive PCP or HCB response were reanalyzed on a 1.5% OV-1/2.4% OV-225
on 80/100 mesh Chromosorb W, 6 ft x 2 mm ID. If the chromatographic peaks in
the sample had the proper retention times for PCP or HCB in the two chromato-
graphic systems, partial confirmation of the peak could be made.
20
-------
Gas Chromatography-Mass Spectrometry Confirmation
The samples which had shown positive GC peaks for PCP or HCB in two
chromatographic systems were confirmed by GC-MS using selected ion monitoring
(SIM) techniques. GC-MS parameters employed to confirm PCP were as follows:
a. Instrument: Hewlett Packard 5985 GC-MS
b. Column: 1.5% OV-17/1.95% QF-1 on 100/120 mesh Supelcoport
packed in a 6 ft glass column, 2 mm ID
c. Injector Temperature: 250°C
d. Column Temperature: 165°C
e. Carrier Gas: Helium
f. Flow Rate: 30 ml/min
g. Transfer Line and Jet Separator Temperature: 275°C
h. lonization Voltage: 70 eV
i. Ions Monitored: m/e 263.8, 267.8, and 305.8
j. Injection: 5 |Jl
QUALITY CONTROL PROCEDURES
Analytical Method Validation and Method of Calculation
The EC-GC analytical method for the determination of PCP and HCB in the
various matrices was evaluated by analyzing reference solutions of PCP and
HCB. A linearity study was conducted by adding known levels of PCP and HCB
(ranging from about 4 to 2,000 ng of each) to 5 ml hexane, derivatizing, and
injecting 5 |Jl. The results of this study are given in Table 6. These data
indicate a linear response to PCP and HCB for a concentration range of 0.8
to 400 ng/ml. This range is equivalent to a concentration range in extracted
samples of 2.4 to 1,250 ppb if a 2 ml or 2 g sample is taken. The sensitivity
limit of the technique was 0.4 ng/ml for both PCP and HCB.
During sample analysis, a reference solution of PCP (13.3 ng/ml) and
HCB (12.9 ng/ml) was analyzed prior to samples and after every fifth sample.
The response factor (peak area/ng injected) was calculated for each reference
solution injected with a sample set, and the average response factor deter-
mined. This value was then employed to calculate the PCP and HCB levels in
the samples. The equations for these calculations are:
... ,. peak area total volume (ul)
1. Response factor = -*-.:-j x jr
r (Jl injected ng compound
_ ,, peak area total volume (ul)
2. ng compound/extract = -f::7 x =^r
pi injected response factor
_ , , ng compound/extract
3. ppb compound = ^. , f *-= , ..
^r r weight sample (g)
The response factors for the reference solutions analyzed during the linear-
ity study were calcualted and are shown on Table 6. A representative GC-EC
chromatogram for the determination of PCP and HCB is presented in Figure 2.
21
-------
TABLE 6. LINEARITY OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE
ANALYSIS BY GC-EC
Reference
solution
no.
1
2
3
4
5
6
7
8
9
10
ng Added
PCP
3.98
7.96
23.9
79.6
159.2
199
398
796
1,990 1
HCB
3.87
7.74
23.2
77.3
154.6
193
386
772
,930
Peak
PCP
(x
0
10.0
11.0
57.0
181.4
373.1
472.1
981.4
2,083
5,254
area
HCB
10"3)
0
12.5
22.4
80.9
249.3
488.2
591.3
1,139
2.196
5,146
Peak
area
ng injected
PCP
(x
0
2.510
1.3803
2.385
2.280
2.345
2.370
2.465
2.615
2.635
HCB
io"6)
0
3.230
2.895
3.485
3.225
3.160
3.065
2.950
2.845
2.665
Linear regression:
PCP - Y (peak area) = 2,650 x (ng) - 28,250
Correlation coefficient - 0.999
HCB - Y (peak area) = 2,670 x (ng) + 45,160
Correlation coefficient - 0.999
Response factor (peak area/ng injected)
PCP - average, 2.450 x IO6, S.D. ± 0.13 x IO6
HCB - average, 3.055 x IO6, S.D. ± 0.245 x IO6
Sensitivity limits: PCP - 0.4 ng/ml
HCB - 0.4 ng/ml
a Value not used for linearity or response factor calculations.
22
-------
URIT
STftRT
to
U)
4. 89
8.16
Figure 2. Pentachlorophenol standard on 1.5% OV-17/1.95% QF-1.
RRT (relative retention time): Pentachlorophenol - 8.16 min, 13.3 pg/yl
Hexachlorobenzene - 4.89 min, 12.9 pg/yl
-------
Sample Analysis Quality Control
The quality control for the determination of PCP and HCB in the various
samples consisted of analyzing duplicate aliquots of a sample for every 10
samples analyzed and spiking pooled samples with known levels of PCP and HCB.
For those samples with detectable PCP or HCB, the sample was reanalyzed using
a second GC column and if the retention times on the two systems agreed that
the peak detected was PCP or HCB, tentative confirmation was made. Final con-
firmation of PCP or HCB being present in a sample was made by SIM-GC-MS.
For serum specimen PCP and HCB determinations, the precision and accu-
racy of the analytical results were assessed by analyzing duplicate aliquots
of one sample and a pooled serum sample spiked with 40 ppb PCP and 39 ppb HCB
with every 10 samples analyzed. A similar protocol was employed for urinary
unconjugated PCP level precision and accuracy evaluations.
Food product samples of sufficient size were spiked with PCP and HCB to
determine recovery values for samples carried through the analytical procedure.
No duplicate food product samples were analyzed.
Analytical Procedure Quality Control
The methodology employed for the determination of PCP and HCB in human
specimens was evaluated. For serum sample analysis, the extraction procedure
was studied to determine if the recovery was higher with two 3-ml hexane ex-
tractions instead of a single 6-ml extraction. A short study was conducted
to evaluate the effects of urinary sediments on the recovery of unconjugated
PCP. Urine specimens with sediment were centrifuged, divided equally into a
clear sample and a sediment sample, extracted, derivatized, and analyzed.
Field Sampling Quality Control
The stability of PCP and HCB in samples collected in Madison County,
shipped to the analytical laboratory, and stored until assay was evaluated
by field spiking studies. Field spikes for serum and urine specimens were
prepared by adding a known level of PCP and HCB to collection vials, trans-
porting the vials to the field, and adding 5 ml serum or 10 ml urine to the
vials in the field. These spiked samples were then treated as collected spec-
imens. A simulated field spiking study was conducted in the laboratory to
confirm the results of the field spikes. For air samples, the collection tubes
were field spiked with a hexane solution containing PCP and HCB. Two tubes
were sealed immediately after spiking and two had air drawn through prior to
sealing. In addition, the same procedure was used to prepare a set of labora-
tory spiked air samples.
24
-------
SECTION 6
RESULTS AND DISCUSSION
SERUM PCP AND HCB DETERMINATIONS
Serum Analysis
The results for the GC-EC determination of PCP and HCB serum levels in
45 test case, 7 special case, and 45 control individuals are given in Tables 7
and 8. The test case individuals had an average serum PCP level of 21.0 ppb,
a standard deviation (SD) of ± 11.3, a relative standard deviation (RSD) of
54%, and a range of 2.2 to 54.6 ppb. Five test case individuals, young chil-
dren ages 2 to 11 years, could not be sampled for serum. The control individ-
uals had an average serum PCP level of 24.0 ppb, with a SD and RSD of ± 12.5
and 52%, respectively, and a range of 4.5 to 67.9 ppb. Two control individ-
uals, young children ages 2 and 4 years, did not have blood taken because they
were controls for the test case individuals who could not be sampled. No HCB
was detected in the serum of either the test cases or control individuals.
The individuals from the two special case families, who reside in log
homes, had elevated serum PCP levels. Special cases 206A and 207A reside in
a log home which they had treated with "penta," and special case 207A had a
serum PCP level of 95.8 ppb which is 4 times the average PCP serum level for
the control individuals, while special case 206A had a serum PCP level (47.6
ppb) that was 2 times the control serum PCP average level. Special case 208A,
209A, 210A, 211A, and 212A live in a commercially purchased log home. The
serum PCP level for each of these special cases and the number of times above
the control individual average were: 208A - 910 ppb (38X), 209A - 710 ppb
(SOX), 210A - 580 ppb (24X), 211A - 1,750 ppb (73X), and 212A - 1,680 ppb (70X),
respectively. Special attention is made to the fact that the highest PCP serum
levels occurred in the three children special cases (209A, 211A, and 212A).
Representative GC-EC chromatograms of special cases 209A, 210A, and 211A on
the 1.5% OV-17 and 1.95 QF-1 column are presented in(Figures 3, 4, and 5, re-
spectively. No HCB was detected in the serum of any of the special cases.
Confirmation of PCP Serum Analysis
The chromatographic peak designated as PCP on the OV-17/QF-1 column for
the special case individuals was tentatively confirmed as PCP by reanalysis
on a 1.5% OV-1 and 2.4% OV-225 column. Figures 6, 7, and 8 present chromato-
grams obtained for serum PCP confirmation for special cases 209A, 210A, and
211A on the OV-l/OV-225 .system. Final confirmation of the observed GC peak
being PCP was made by SIM-GC-MS. Figure 9 presents the GC-MS confirmation
for special cases 209A, 210A, 211A, and 212A. The areas of the three m/e ions
monitored were summed and are shown as a single peak.
25
-------
TABLE 7. LEVELS OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE
IN THE SERUM AND URINE (UNCONJUGATED) OF TEST CASES
Madison County
Health Department Identification
number
100A
101A
102A
103A
104A
105A
106A
107A
108A
109A
110A
111A
112A
113A
114A
115A
116A
117A
118A
119A
120A
121A
122A
123A
124A
125A
200A
201A
202A
203A
204A
205A
213A
214A
215A
216A
217A
218A
219A
220A
221A
222A
age
32
62
69
11
29
47
25
11
13
49
65
20
50
56
47
14
10
05
11
26
27
33
15
12
02
55
36
14
10
57
32
25
33
08
05
56
45
15
21
17
51
49
sex
female
female
male
female
female
male
female
male
male
female
female
female
female
male
female
female
male
female
male
male
female
female
female
female
male
female
female
male
female
female
female
female
female
female
female
male
female
female
male
male
male
female
race
white
white
white
white
white
white
unknown
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
white
Serum
(ppb)3
40.0
12.0
21.9
29.7
54.6
17.1
13.8
c
25.3
9.9
17.1
2.2
15.2
13.5
19.9
27.8
c
c
22.1
27.3
33.1
7.1
8.1
28.7
c
10.6
15.5
21.8
22.6
20.6
14.2
38.0
10.6
c
53.9
13.7
16.3
21.2
9.9
28.7
23.4
13.4
(ppb)3
N.D.b
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
c
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
c
c
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
c
N.D.
N.D.
N.D.
N.D.
1.0
N.D.
N.D.
N.D.
c
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
Urine PCP
(ppb)3
(unconjugated)
2.4
1.1
1.2
1.4
0.6
1.9
1.3
2.0
1.3
1.2
3.6
3.8
1.2
1.5
1.0
1.5
1.7
1.1
0.9
1.7
0.7
1.2
2.6
1.0
0.9
2.8
0.9
0.8
1.5
1.4
1.1
4.0
7.2
2.3
4.0
2.4
1.6
1.0
2.2
0.7
1.6
1.6
(continued)
26
-------
TABLE 7 (continued)
Madison County
Health Department
number
Serum
Identification
Urine PCP
(ppb)3
age sex
race (ppb) (ppb) (unconjugated)
223A
224A
225A
226A
227A
228A
117Bd
121Bd
224BQ
Number
Average
Standard
Relative
16
22
49
49
29
39
08
38
21
deviation
standard
female
male
male
female
female
male
female
female
female
deviation
white
white
white
white
white
white
white
white
white
21.1
16.5
11.0
13.6
30.5
40.6
c
16.9
22.4
45
21.0
± 11.5
54%
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
c
N.D.
N.D.
_
-
-
1
1
1
2
2
5
1
0
1
51
1
± 1
.2
.3
.5
.0
.8
.0
.5
.6
.6
.8
.2
68%
Special Cases - Log Home Residents
206A
207A
208A
209A
210A
211A
212A
29
28
09
34
29
02
04
male
female
male
male
female
female
female
white
white
white
white
white
white
white
47.6
95.8
910
710
580
1,750
1,680
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
5.1
1.7
54.7
46.8
50.8
216
51.2
a ppb - parts per billion (ng/ml), sensitivity - PCP, 0.4 ng/ml;
HCB, 0.4 ng/ml.
b N.D. - none detected, < 0.4 ppb.
c Sample not collected.
d Control subjects changed to test cases after PCP treated amunition
crate wood located in their residence.
27
-------
TABLE 8. LEVELS OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE
IN THE SERUM AND URINE (UNCONJUGATED) OF CONTROLS
Madison County
Health Department Identification
number
100B
101B
102B
103B
104B
105B
106B
107B
108B
109B
HOB
111B
112B
113B
114B
115B
116B
118B
119B
120B
122B
123B
124B
200B
201B
202B
203B
204B
205B
206B°
207B^
210B
213B
214B
215B
216B
217B
218B
219B
220B
age
28
44
44
17
26
58
30
09
13
51
57
15
48
51
31
12
10
09
36
33
14
15
02
29
16
09
49
32
32
30
33
33
28
04
06
56
55
16
32
17
sex
female
female
male
female
female
male
female
female
male
female
female
female
female
male
female
female
female
female
male
female
female
male
female
female
female
male
female
female
female
male
female
female
female
male
male
male
female
male
male
male
race
white
white
white
white
white
white
white
white
white
white
white
white
white
white
unknown
white
white
white
white
white
white
white
black
white
white
white
white
black
white
white
white
white
white
white
white
white
white
white
black
white
Serum
(ppb)3
25.0
25.8
16.9
20.5
49.8
67.9
21.0
30.8
40.0
29.4
29.0
31.6
42.2
9.5
10.0
11.7
17.6
33.5
6.3
4.4
26.2
7.4
c
23.0
35.4
35.8
13.7
24.2
19.2
11.6
20.6
22.0
38.4
c
38.1
29.3
14.6
22.8
18.4
4.5
(ppb)a
N.D.b
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
c
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
c
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
Urine PCP
(ppb)3
(uncon j ugated )
1.3
4.3
1.9
1.6
2.2
2.9
0.9
1.9
3.1
1.6
2.2
3.3
2.0
2.5
1.2
2.2
0.9
3.5
1.7
1.2
1.2
1.2
1.2
3.4
4.7
1.7
2.0
4.1
1.2
1.2
2.4
0.4
1.5
1.4
3.1
2.8
0.7
4.2
1.0
2.3
(continued)
28
-------
TABLE 8 (continued)
Madison County
Health Department
number
221B
222B
223B
225B
226B
227B
228B
Number
Average
Standard
Relative
age
65
59
23
54
46
29
29
deviation
standard
Serum
Identification
sex
male
female
male
male
female
female
male
deviation
race
white
white
white
white
white
white
white
(ppb)3
17.2
13.2
21.7
15.1
19.8
23.7
29.5
45
24.0
± 12.5
52%
(ppb)3
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
_
:
Urine PCP
(ppb)3
(unconjugated)
1.3
2.2
1.4
11.0
2.0
2.6
2.4
47
2.3
± 1.6
72%
a ppb - parts per billion (ng/ml), sensitivity - 0.4, ng/ml;
HCD, 0.4 ng/ml.
b N.D. - none detected, < 0.4 ppb.
c Sample not available.
d Control individuals for special cases.
e Number - number, average, standard deviation, and relative
standard deviation includes controls for
special cases.
29
-------
CO
o
4. 12
8.29
Figure 3. Serum sample of individual 209A on 1.5% OV-17/1.95% QF-1.
RRT: Pentachlorophenol - 8.29 min, 710 ppb
-------
DIL FflCTOR: 1..00B0 E+ S
u>
WRIT
STRRT
7,32
4. 13
0,
3 8.23
Figure 4. Serum sample of individual 210A on 1.5% OV-17/1.95% QF-1.
RRT: Pentachlorophenol 8.28 min, 580 ppb
-------
BIL FflCTOR: 1.0000 E* 0
4.94
7.25
, 88
4. 03
7'Q
Figure 5. Serum sample of individual 211A on 1.5% OV-17/1.9% QF-1.
RRT: Pentachlorophenol - 8.28 min, 1,750 ppb
-------
OJ
BIL FfiCTOR: 1 . 0S0B EH- 0
UHIT
-0.24^ @.
9.72
Figure 6. Serum sample of individual 209A on 1.5% OV-1/2.4% OV-225.
RRT: Pentachlorophenol - 9.72 min
-------
W-fl I T
OJ
-P-
1. 13
5.4;
8.34
9.7;
12.56
Figure 7. Serum sample of individual 210A on 1.5% OV-1/2.4% OV-225.
RRT: Pentachlorophenol - 9.73 min
-------
DIL FflCTOR: 1.0000 E+ 0
STFrrtT
CO
Figure 8, Serum sample of individual 211A on 1.5% OV-1/2,4% OV-225,
RRT: Pentachlorophenol - 9.. 72 min
-------
TRN:
1-4221
260-
350
1-4220
20-
35
-------
Quality Control - Sample Analysis, Precision and Accuracy
The precision and accuracy of the analytical data for PCP and HCB in
serum was assessed by analyzing duplicate aliquots of a sample and spiked
pooled serum aliquots. The duplicate analyses of PCP are given in Table 9.
The standard deviation of pairs (S.D.P.) and relative standard deviation of
pairs (R.S.D.P.) were ±3.6 and 15.4%, respectively; and the average percent
difference between pairs was 18.2 ± 18.9. Thus, the analytical method em-
ployed for serum PCP provided data within 20% of the actual value. Since no
serum HCB was detected, evaluation of the method was not possible. The re-
covery of PCP and HCB in pooled serum samples (Table 10) averaged 78% and 91%,
respectively, for 10 spiked samples. These data indicate that the analytical
data have the necessary accuracy.
Quality Control - Sample Preparation Procedure
The sample preparation procedure of serum PCP and HCB levels was eval-
uated by extracting spiked serum with either one 6-ml or two 3-ml hexane
aliquots. The results of this evaluation are summarized in Table 11 and show
that the single extraction employed for this study was equivalent to a double
extraction. Also, this study showed that the extraction was linear, i.e.,
similar recoveries were obtained for serum aliquots spiked with about 40 and
200 ppb of PCP and HCB.
UNCONJUGATED URINARY PCP DETERMINATION
Urine Analysis
The results for the GC-EC determination of unconjugated PCP urinary
levels in 51 test case, 7 special case, and 47 control individuals are given
in Tables 7 and 8. As was noted earlier for serum CP levels, the unconjugated
PCP urinary levels for the test cases and control individuals were similar.
The average, SD, RSD, and range for the test cases and control individuals
unconjugated urinary PCP were: 1.8 and 2.3 ppb; ±1.2 and ±2.3; 68% and 72%;
and 0.6 to 7.2 ppb and 0.4 to 11.0 ppb, respectively.
For five of the special case individuals, a substantial increase in un-
conjugated urinary PCP levels was noted. Special cases 206A and 207A had un-
conjugated urinary PCP levels of 5.1 and 1.7 ppb, respectively. While this
level is within the range of the control individuals, the serum PCP level for
these two special cases was elevated. Special cases 208A, 209A, 210A, 211A,
and 212A, members of a single family who reside in a commercially purchased
log home, all had elevated unconjugated PCP urinary levels. The levels and
the number of times above the average unconjugated urinary PCP level for con-
trol individuals were: 208A - 54.7 ppb (24X), 209A - 46.8 ppb (20X), 210A -
50.8 ppb (22X), 211A - 216 ppb (94X), and 212A - 51.2 ppb (22X). As with the
serum PCP levels for the special cases, the highest unconjugated urinary PCP
was found in a child (211A), age 2 years. Representative GC-EC chromatograms
for special cases 207A, 208A, and 209A on the OV-17/QF-1 column are shown in
Figures 10, 11, and 12, respectively.
37
-------
TABLE 9. DUPLICATE ANALYSES OF SERUM SAMPLES
FOR PENTACHLOROPHENOL
Madison County Pentachlorophenol (ppb)
Health Department Replicate Average
Number A B
100A
109A
202A
213A
219A
226A
104B
108B
111B
203B
210B
218B
36.8
11.4
22.0
9.1
9.6
13.9
49.5
40.0
27.5
16.9
21.4
29.3
Avg A and BC 23
S.D.P.e ± 3
R.S.D.P.8 15
41.1
8.6
23.3
12.0
10.2
13.4
50.1
40.1
35.7
10.5
22.5
16.2
.7
.6
4%
39.0
9.9
22.6
10.6
9.9
13.6
49.8
40.0
31.6
13.7
22.0
22.8
(A-B)
4.3
2.8
1.3
2.9
0.6
0.5
0.6
0.1
8.2
6.4
1.1
13.1
Avg f
S.D.
f
11.0
28.0
5.8
27.4
6.1
3.7
1.2
0.2
26.0
46.7
5.0
57.5
18.2
± 18.9
a ppb - parts per billion (ng/ml), sensitivity - PCP, 0.4 ng/ml.
b % - Percent difference between A and B values.
(A+B)
% = (A-B)/.
x 100
c Avg A and B - Average of all A and B values.
d Avg - Average of percent values.
e S.D.P. - Standard deviation of pairs.
S.D.P. = (I (A-B)2/2xP)1 2
P = Number of pairs
f S.D. - Standard deviation.
S.D. = (l(x-x)2/2xN)1 2
N = Number of pairs
g R.S.D.P. - Relative standard deviation of pairs.
R.S.D.P. = S.D.P./Avg A and B x 100
38
-------
TABLE 10. RECOVERY OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE
ADDED TO POOLED SERUM ALIQUOTS
Q
Pooled serum Level added (ppb )
number PCP HCB
1 40
2 40
3 40
4 40
5 40
6 40
7 40
8 40
9 40
10 40
0
39
39
39
39
39
39
39
39
39
39
0
a
Level found (ppb )
PCP HCB
55.1
51.8
54.2
46.0
53.6
50.4
51.6
52.3
53.7
47.9
20.3
37.4
33.1
31.1
32.2
37.8
36.2
38.3
35.4
38.7
35.6
N.D.C
Avg
S.D.
% Recovery
PCP HCB
87
79
85
64
83
75
78
80
84
69
78
± 7
96
85
80
83
97
93
98
91
99
91
91
± 7
a ppb - parts per billion (ng/ml), sensitivity - PCP, 0.4 ng/ml;
HCB, 0.4 ng/ml.
b 0/ _ ppb spiked - ppb unspiked ,-_
% Recovery = ** * r^3 e x 100
* ppb added
c N.D. - not detected, < 0.4 ng/ml.
39
-------
TABLE 11. RECOVERY VALUES FOR PENTACHLOROPHENOL AND HEXACHLOROBENZENE
IN SERUM BY TWO EXTRACTION METHODS
Pentachlorophenol
Sample
Level Level
spiked recovery
(ppba) (ppb)
Extraction performed with
Serum spiked
Serum spiked
Serum spiked
Serum spiked
Serum blank
Serum blank
40
40
200
200
-
-
Extraction performed with
Serum spiked
Serum spiked
Serum spiked
Serum spiked
Serum blank
Serum blank
40
40
200
200
-
one 6 -ml
50.7
46.2
185
170
16.2
16.5
two 3 -ml
52.8
50.1
178
185
19.7
18.8
Hexachlorobenzene
Level
Recovery spiked
(%) (ppb)
Level
recovery
(ppb)
Recovery
(%)
aliquot of hexane:
86
75
84
77
aliquots
84
77
79
83
38.8
38.8
194
194
-
-
of hexane:
38.8
38.8
194
194
-
34.5
35.7
155
145
N.D.
N.D.
42.3
33.6
167
168
N.D.
N.D.
86
89
78
73
106
84
84
84
ppb - parts per billion (ng/ml), sensitivity - PCP, 0.4 ng/ml;
HCB, 0.4 ng/ml.
-------
B.IL. FflCTOR: 1.0000 E-*- 8
URIT
STRRT
1. w
2.35
8.44
Figure 10. Urine sample (unconjugated) of individual 207A on 1.5% OV-17/1.95% QF-1
RRT: Pentachlorophenol 8.44 min, 1.7 ppb
-------
BIL FP.CTGR: 1 . 0800 E+
STflRT
Figure 11. Urine sample (unconjugated) of individual 208A on 1.5% OV-17/1.95% QF-1.
RRT: Pentachlorophenol 8.45 min, 54.7 ppb
-------
LI
URIT
STHRT
H ' "70
il5^
2-V^36
0 . 97
-8.44
Figure 12. Urine sample (unconjugated) of individual 209A on 1.5% OV-17/1.95% QF-1
RRT: Pentachlorophenol - 8.44 min, 46.8 ppb
-------
Confirmation of Unconjugated PGP Urinary Analysis
The unconjugated PCP in the urine specimens from the special cases was
tentatively confirmed by reanalysis on the OV-l/OV-225 column. Final confir-
mation of the detected peak being PCP was made by SIM-GC-MS. Selected ion
monitoring traces for special cases 206A through 212A and test case 213A are
shown in Figures 13, 14, and 15. The low level of PCP in special cases 206A
and 207A prevented GC-MS confirmation. The other special cases and test case
213A were confirmed as having unconjugated PCP in their urine.
Quality Control - Sample Analysis, Precision and Accuracy
The precision and accuracy of the determination of unconjugated PCP in
urine was assessed through duplicate determinations of selected samples and
the recovery of PCP added to a pooled urine sample. The results of the dupli-
cate analyses are given in Table 12; no statistical evaluation of these dupli-
cates was made because the low level of unconjugated PCP would cause large
errors for small differences between analyses. However, these data do show
that similar values for PCP were obtained for duplicate determinations. The
accuracy of the unconjugated urinary PCP levels was determined by analyzing
spiked pooled urine aliquots. The results are given in Table 13 and show an
average PCP recovery of 97% with a SD of ± 7. Thus, quantitative recovery of
PCP added to urine was obtained.
Quality Control - Sample Preparation Procedure
Selected urine specimens contained sediment which may have adsorbed un-
conjugated PCP; and thus, uniform sampling of urine may not have been possible.
A study was designed to evaluate the effect of urinary sediment on the deter-
mination of unconjugated PCP levels. Urine samples containing sediment were
centrifuged and equal aliquots taken, one with and one without the sediment.
The results are given in Table 12, relicate column 3 for the sediment contain-
ing samples and replicate column 4 for the supernatant samples. These data
show little difference between the unconjugated PCP levels in the separated
urines, thus indicating that the urinary sediment did not affect the levels
for unconjugated urinary PCP.
FIELD SPIKE EXPERIMENTS FOR SERUM PCP AND HCB AND URINARY PCP
The sampling, sample handling, storage, and shipment for serum and urine
specimens was evaluated by conducting field spiking experiments. Pre-washed
sample vials were spiked with a solution of PCP and HCB in hexane in the labo-
ratory and shipped to the field with the sample vials. In the field, 10 ml
of urine or 5 ml of serum were added to the vials, the vials sealed, and treated
as samples. The results of the field spikes of urine and serum are presented
in Table 14. Recovery values for PCP ranged from 61 to 88% in serum and 34
to 60% in urine. HCB was only detected in one serum and one urine field spike
with recovery values of 67 and 27%, respectively. Due to the lack of recovery
of HCB and the low recovery of PCP, a laboratory simulation of field spikes
was performed. The vials were spiked and stored at room temperature 6 days
prior to the addition of serum or urine. At that time, the serum and urine
samples were added to the spiked bottles, and a similar set of serum and urine
samples were added to septum bottles and these samples spiked.
44
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263-
££4
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264
SPECIAL CASE 209A
SPECIAL CASE 208A
SPECIAL CASE 207A
SPECTAI. HASE 206A
PENTACHLOfJOPHENOL STD
250 PC
TJI1E |
12345678 9101112131415
Figure 13. Mass spectrometry confirmation of urine of individuals
206A, 207A, 208A and 209A.
-------
TRN:
<'>?
W3?0
1421S
2tSO-
350
14217
2GO-
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260-
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14214
260-
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TIME
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UNI i»m ii f*" ' ^-~~f ***>*** >. j m«» SPECIAL CASE 21U
PENTACHLOROPKZNOL STD
f^
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/j
/ FtNTACHLOROPKEr«5L STD
/ SoKO
APENTACHLOROPK3NOL STD
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123-45678 91011181314151617181920
Figure 14. Mass spectrometry confirmation of urine of individual 211A.
46
-------
X
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TEST CASE 213A
SPECIAL CASE 212A
SPECIAL CASE 210A
PENTACHLOROPHZNOL STD
350 NG
T:ME
1 2 3 4 5 6 7 3 9101112131415
Figure 15. Mass spectrometry confirmation of urine of individuals
210A, 212A, and 213A.
-------
TABLE 12. REPLICATE ANALYSES OF URINE SAMPLES
FOR UNCONJUGATED PENTACHLOROPHENOL
Madison County
Health Department
number
Pentachlorophenol (ppb )
Replicate
Average
100A
101A
105A
110A
207A
225A
100B
107B
121B
200B
213B
214B
2.7
1.1
1.0
4.2
2.2
1.1
1.2
1.1
0.6
0.9
1.6
1.4
2.2
1.1
2.5
3.1
1.0
0.8
1.4
2.2
0.5
2.3
1.4
1.4
2.4
1.8
2.0
2.8
4.9
1.7
1.7
2.0
1.4
5.5
2.4
1.1
1.9
3.6
1.7
1.5
1.3
1.9
0.6
3.4
1.5
1.4
ppb - parts per billion (ng/ml), sensitivity -
PCP, 0.4 ng/ml.
Four milliliters of urine centrifuged and 2 ml of
supernatant extracted as replicate 4 and the 2 ml
of urine containing the sediment extracted as
replicate 3.
48
-------
TABLE 13. RECOVERY OF PENTACHLOROPHENOL ADDED TO
POOLED URINE ALIQUOTS
Pooled urine
number
1
2
3
4
5
6
7
8
9
10
a
Level added (ppb )
PCP
40
40
40
40
40
40
40
40
40
40
Level found (ppb )
PCP
35.1
42.3
37.2
35.6
39.6
41.8
42.2
38.5
38.7
42.3
% Recovery
PCP
86
104
92
88
98
103
104
95
95
104
Blank 0 0.6
Avg 97
S.D. ± 7
a ppb - parts per billion (ng/ml) , sensitivity - PCP, 0.4 ng/ml.
b % Recovery = Ppb spiked - ppb unspiked (blank)
' ppb added
49
-------
TABLE 14. RECOVERY VALUES FOR PENTACHLOROPHENOL AND HEXACHLOROBENZENE
IN FIELD SPIKES OF SERUM AND URINE (UNCONJUGATED)
Pentachlorophenol
Sample
Serum:
Field blank #1
Field blank #2
Field blank #3
220A
220A
101B
101B
HOB
HOB
106B
106B
112B
112B
200B
200B
Urine:
Field blank #1
Field blank #2
Field blank #3
108B
108B
202B
202B
Level
spiked
(ppb3)
__
--
16
16
16
80
80
80
--
__
120
120
~ *
Level
recovery
(ppb)
N.D.b
N.D.
N.D.
30.8
18.7
37.7
25.8
41.6
29.0
91.3
21.0
90.7
42.2
79.4
23.0
N.D.
N.D.
N.D.
75.0
3.1
42.3
1.7
Recovery
(%)
76
74
79
88
61
71
60
34
Hexachlorobenzene
Level
spiked
(ppb)
__
15.5
--
15.5
15.5
77.3
--
77.3
77.3
--
__
--
116
116
« _
Level
recovery
(ppb)
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
51.7
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
30.9
N.D.
N.D.
N.D.
Recovery
(%)
67
--
--
27
a ppb - parts per billion (ng/ml), sensitivity - PCP, 0.4 ng/ml;
HCB, 0.4 ng/ml.
b N.D. - none detected, < 0.4 ng/ml.
50
-------
The spiked serum and urine samples were frozen and stored for 7 days prior to
extraction. At the time of extraction, additional serum and urine samples
were spiked directly in the extraction tubes. The results of the simulated
field spikes are presented in Table 15. The recovery value of PCP increased
from spikes in the vials to spikes directly into the serum and urine samples.
The recovery of HCB in vials spiked prior to addition of the serum and urine
was non-existant. However, recovery of HCB from the field spikes which con-
sisted of spiking directly into the samples compared favorably with the ex-
traction time spikes. The vials used to store the samples were sealed with
Teflon-lined septa and the spiking volume was 10 (Jl. Thus, the loss of HCB
and the low recovery of PCP in the field spikes and laboratory simulation may
have been caused by irreversible adsorption of the compounds on the walls of
the vials or in the septum material. Another possible explanation is that
the 10 |Jl hexane evaporated leaving the dried material on the glass. When
the physiological fluid was added, the compounds may not have been dissolved
and thus were not extracted efficiently. The greater polarity of PCP compared
to HCB and the partial recovery of PCP with no recovery of HCB when the com-
pounds were added to vials prior to the physiological fluid would favor this
rationalization. Since good recovery of PCP and HCB were obtained when spiked
into the physiological fluid, the data on the serum and urinary levels should
not have been compromised.
STATISTICAL EVALUATION OF SERUM AND UNCONJUGATED URINARY PCP LEVELS
The serum and unconjugated urinary PCP levels of the control individuals
and test cases were statistically evaluated at the Center for Disease Control.
For these evaluations, the residences of the log homes (test case 206A through
212A) and their corresponding control individuals (controls 206B, 207B, and
210B) were ommitted. Also, the three control individuals (controls 117B, 121B,
and 224B) who were found to have ammunition crate wood in their residence were
changed to test cases. The breakdown of the test cases, special cases, and
control individuals by number, age, sex, and race is given in Table 16. A
total of 51 test cases and 44 control individuals were evaluated. The statis-
tical evaluation of the serum PCP levels and of the unconjugated urinary PCP
levels is presented in Table 17. These data show little or no difference in
the average serum or unconjugated urinary PCP levels of the test cases and
the control individuals.
The possible correlation between the serum and unconjugated urinary PCP
levels was evaluated by plotting the serum level versus the urinary level as
shown in Figure 16. A correlation coefficient of 0.1206 (1.000 being a per-
fect fit) indicates that the serum PCP levels do not correlate with unconju-
gated urinary level. When the outliners, i.e., those values statistically
outside the average value, were excluded as shown in Figure 17, a correlation
coefficient of 0.3025 was obtained. Likewise, when the natural logarithm of
the serum and unconjugated urinary PCP level were compared (Figure 18), no
correlation (0.0823 correlation coefficient) in the values was obtained.
PCP LEVELS IN HYDROLYZED URINES
The normal means of urinary excretion of PCP would be as a conjugate,
i.e., glucuronide or sulfate adduct, through the phenolic group.
51
-------
TABLE 15. RECOVERY VALUES FOR PENTACHLOROPHENOL AND
HEXACHLOROBENZENE IN SIMULATED FIELD SPIKES
Pent a chlo ropheno 1
Sample
Serum:
Bottle spiked
Bottle spiked
Serum spiked and
frozen
Serum spiked
Level
spiked
(ppb*)
16
.16
16
immediately before
extraction 40
Bottle spiked
Bottle spiked
Serum spiked and
frozen
Serum spiked
80
80
80
Level
recovery
(ppb)
22
22
29
59
60
58
84.3
Recovery
(%)
*e
*
*
*
*
*
*
Hexachlorobenzene
Level
spiked
(ppb)
15.5
15.5
15.5
38.8
77.3
77.3
77.3
Level
recovery
(ppb)
N.D.f
K.D.
14
36
N.D.
N.D.
70
Recovery
(%)
..
--
90
93
--
91
immediately before
. extraction
Urine:
Bottle spiked
Bottle spiked
Urine spiked and
frozen
Urine spiked and
frozen
Urine spiked
200
8
8
8
8
163
5.7
6.6
8.7
8.7
*
55
66
92
92
193
7.8
7.8
7.8
7.8
160
N.D.
N.D.
6.5
6.5
83
--
83
83
immediately before
extraction
Urine spiked
40
34
82
38.8
37
95
immediately before
extraction
Bottle spiked
Bottle spiked
Urine spiked and
frozen
Urine spiked and
frozen
Urine spiked
40
40
40
40
40
38
25
34.2
39
42
92
59
82
94
102
38.8
38.8
38.8
38.8
38.8
44
N.D.
N.D.
19.2
22
113
--
--
50
57
immediately before
extraction
200
180
89
193
153
79
(continued)
52
-------
TABLE 15 (continued)
Pentachloropheno 1
Sample
Urine spiked
immediately
extraction
Urine blank
Urine blank
Level
spiked
(ppba)
before
200
--
Level
recovery Recovery
(ppb) (%)
183 91
1.6
0.9
Hexachlorobenzene
Level
spiked
(ppb)
193
~
Level
recovery
(ppb)
153
N.D.
N.D.
Recovery
79
a ppb - parts per billion (ng/ral), sensitivity - PCP, 0.4 ng/ml;
HCB, 0.4 ng/ml.
b Spiking solutions added to glass vials with Teflon-lined septa. Six days after
spiking the bottles, urine or serum was added to the vials and the samples
frozen. Seven days after adding the samples to the vials, the samples were
extracted.
c Serum and urine samples added to clean glass bottles and the spiking solutions
added directly into the samples. The samples were frozen and extracted seven
days after the samples were spiked.
d Serum and urine samples spiked immediately prior to extraction.
e Recovery values could not be calculated due to loss of blank serum sample.
f N.D. - none detected, < 0.4 ng/ml.
53
-------
TABLE 16. TEST CASES AND CONTROL INDIVIDUALS FOR THE
PENTACHLOROPHENOL STUDY IN RICHMOND, KENTUCKY
Age
0-9
10-19
20-29
30-39
40-49
50-59
60+
Sex
Male
Female
Race
White, not hispanic
Black, not hispanic
Unknown
Cases
5
13
10
7
7
6
3
18
33
50
0
1
Controls
6
10
7
7
5
8
1
17
27
40
3
1
Special
Cases
3
-
3
1
3
4
7
Special
Case
Control
-
-
-
3
1
2
3
Total
14
23
20
18
12
14
4
39
66
100
3
2
Total
51
44
105
54
-------
TABLE 17. SERUM AND UNCONJUGATED URINARY PENTACHLOROPHENOL
CONCENTRATION (ppb) FOR CASES AND CONTROLS
Test Cases
a
Controls
Serum:
Number
Range
Median
Arithmetic mean
Standard deviation (S.D.)
Geometric mean
Median log concentration
Mean log concentration
S.D. log concentration
Urinary (Unconjugated):
45
2.20 - 54.6
18.7
20.99 .
11.27
18.19
2.929
2.901
0.572
42
4.32 - 67.9
23.35
24.19
12.79
20.70
3.150
3.030
0.610
Number
Range
Median
Arithmetic mean
Standard deviation (S.D.)
Geometric mean
Median log concentration
Mean log concentration
S.D. log concentration
51
0.6 - 6.6
1.5
1.83
1.23
1.56
0.405
0.446
0.541
44
0.7 - 11.0
2.0
2.34
1.67
2.00
0.693
0.693C
0.534
Cases - does not include seven special cases; does include three control
individuals later changed to test cases when ammunition crate wood was
located in their residences.
b Controls - does not include three controls for the seven special cases.
c p < 0.05 2-tailed unpaired t-test (t = 2.24, df = 93).
55
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60
50
40
20
10
Correlation Coefficient R = 0.1206
R2 = O.OU5
1
1
1
1
1
1
1
1
2 4 6 8 10
Unconjugated Urinary Concentration of Pentachlorophenol (PCP)
in Parts per Billion (ppb)
12
Figure 16. Correlation of serum and urinary (unconjugated)
concentrations of pentachlorophenol.
56
-------
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The urinary PCP levels for this study were determined on the unconjugated
compound, and all data evaluations described earlier were conducted on these
values. A short study to determine the level of total (conjugated and uncon-
jugated) PCP in the urine was conducted and the results are given in Table
18. The urines of one test case, three special cases, and four control in-
dividuals were acid hydrolyzed by the procedure presented in the Experimental
Protocol. Each of the urines had a higher PCP level after hydrolysis, and
the ratio of hydrolyzed to unhydrolyzed PCP levels ranged from 1.7 to 7.0.
The average PCP levels in the hydrolyzed urines for the four control individ-
uals was 12.5 ppb while the geometric mean for PCP in hydrolyzed urine from
the HANES II study was < 5 ppb. The PCP level in the hydrolyzed urine of test
case 122A was in the normal range. The three special cases had increased PCP
levels in their hydrolyzed urines. Compared to the average control individual
hydrolyzed urine PCP level, the special cases had increased levels of 3.1 (206A),
7.0 (209A) and 8.8 (210A) times the control average. While this increase is
not as high as the unconjugated PCP level increase for special cases 209A
and 210A, special case 206A had an unconjugated urinary PCP level that was
not increased in relation to the unconjugated urinary PCP average for the con-
trol individuals and the hydrolyzed urine for special case 206A was 3.1 times
the average for hydrolyzed control individual urinary PCP. The optimal hydrol-
ysis conditions were not evaluated. Thus, the possibility of incomplete hydrol-
ysis exists and higher levels of PCP may be present in the urine. An evaluation
of the stability of PCP to the hydrolysis conditions was conducted, and excellent
recovery of PCP was obtained for samples spiked and then hydrolyzed (Table
18). These data indicates that PCP is stable under the hydrolysis conditions.
AIR SAMPLE LEVELS OF PCP AND HCB
Pentachlorophenol and Hexachlorobenzene in Air Samples
The results of the GC analysis of the 40 air samples are presented in
Table 19. Detectable levels of PCP were found only in samples 1007 and 1008,
collected in the commercial log home. HCB was not detected in any of the 40
samples. The minimum detectable level of PCP and HCB in the air samples was
0.005 nanograms per liter.
Representative chromatograms of air samples 1007 and 1008 are presented
in Figures 19 and 20. The mass spectrometric confirmation of the two samples
are presented in Figure 21. Sample 1008 did not contain sufficient PCP to be
detected by the GC-MS system.
Field Spike Quality Control for PCP and HCB in Air Samples
The recovery of PCP and HCB in collection tubes spiked in the laboratory
and carried to the field is presented in Table 20. Recovery values were same
for the field spikes with and without air being pulled through for HCB but
were higher for PCP for the tubes with air pulled through. Even though quan-
titative recovery for PCP, i.e., > 80%, was not obtained, the sensitivity of
the method (0.005 ng/liter detection limit) indicates that PCP was not pres-
ence or at very low levels.
59
-------
TABLE 18. LEVELS OF PENTACHLOROPHENOL (CONJUGATED AND UNCONJUGATED)
IN HYDROLYZED TEST AND CONTROL URINE SAMPLES
Madison County Ratio
Health Dept. Pentachlorophenol (ppb) Hydrolyzed
number Hydrolyzed urine Non-hydrolyzed urine Non-hydrolyzed
122A - test case 4.5 2.6 1.7
206A - special case 38.8 5.1 7.6
209A - special case 87.6 46.8 2.0
210A - special case 110 50.8 2.2
104B - control 15.5 2.2 7.0
118B - control 6.8 3.5 1.9
204B - control 18.3 4.1 4.5
222B - control 9.4 2.2 4.3
HANES IIC < 5
RECOVERY VALUES FOR PENTACHLOROPHENOL IN HYDROLYZED URINE
Sample
Urine blank
Urine spiked
Urine spiked
Urine blank
Urine blank
Urine spiked
Level
spiked
(ppb3)
-_
80
80
--
80
80
Level
recovery
(ppb)
5.6
82
72
7.3
83
82
Recovery
(%)
93
83
95
94
a ppb - parts per billion (ng/ml), sensitivity - PCP, 0.4 ng/ml.
b Values from Tables 7 and 8.
c Preliminary data based on the analysis of 4,480 - 4,580 samples collected
from the general population via the Health and Nutrition Examination
Survey II (HANES II); 81% of the urines showed a positive PCP response
with 11.6% having a trace level; the highest value was 2,670 ppb and
the geometric mean was < 5.
60
-------
TABLE 19. LEVELS OF PENTACHLOROPHENOL AND HEXACHLOROBENZENE IN AIR SAMPLES
Madison County Volume of
Health Department Residence number air sampled Pentachlorophenol
number and type liters (ng/1)
H001
H006
H007
H008
H009
HO 10
1001
1002
1003
1004
1005
1006
1007
1008
1014
1015
1016
1019
1021
1022
1023
1025
1027
1029
1031
1033
1035
1037
1039
1040
1042
1045
1047
1050
1052
P0001
P0002
P0005
P0007
P0009
14 -
5 -
5 -
11 -
32 -
10 -
36 -
8 -
16 -
1 -
19 -
42 -
20 -
20 -
26 -
35 -
33 -
2 -
22 -
3 -
30 -
12 -
27 -
44 -
31 -
28 -
34 -
39 -
25 -
24 -
23 -
15 -
40 -
13 -
43 -
17 -
18 -
45 -
7 -
41 -
test case
test case
test case
test case
test case
test case
test case
test case
control
test case
control
test case
special case
special case
control
test case
control
control
control
test case
control
test case
control
control
test case
control
control
control
test case
control
control
control
control
control
control
test case
test case
control
control
control
499
426
426
408
287
403
394
705
454
413
475
418
480
480
349
468
498
718
484
449
387
644
396
490
572
515
448
446
525
432
493
449
275
360
364
472
765
605
256
368
N.D.b
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
0.20=
0.38°
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
Hexachlorobenzene
(ng/l)a
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
a ng/1 - nanograms of compound per liter of air.
b ND - not detected.
c 0.14 ng/1 in the front half of the air collection tube
and 0.06 ng/1 in the back half.
d 0.37 ng/1 in the front half of the air collection tube
and 0.01 ng/1 in the back half.
e Control residence changed to test case after ammunition crate wood
located in residence.
61
-------
8.51
B. 17
1149B
i R j 1
1 . 243
DIL FRCTOR: 1.S8S3 E+ 0
1 . 57
o _-i ..1
z:m
Figure 19. Air sample 1007 (special case residence) on 1.5% OV-17/1.95% QF-1.
RRT: Pentachlorophenol - 8.17 min, 0.20 ppt
-------
2 4. 89
IHL FfiCTOR: 1.BBSS"E+ 3
o . ^ o t.' tit t -*- i
3.860S E-s- 1
y. t.^^'5 E 5
8.9187 E- 5
Figure 20. Air sample 1008 (special case residence) on 1.5% OV-17/1.95% QF-1.
RRT: Pentachlorophenol 8.16 min, 0.20 ppt
-------
rpN:
1-£30
1-J233
£63-
264
£63-
TIIIS:
X - .13 V - 1.00
«
1 IJJJLJEJJV lfc3sTii!7?S? SAMPLE 1008, SPECIAL CASE RESIDENCE
BF.y-i'yii.'ifHT'tf jfufT
1
, . J I!f fO L ?.'"-Mii'i4'S'^i;k-iiBll SAMPLE 1007, SPECIAL CASE RESIDENCE
^|£y"- "fSfTl/T 1 | j --* -
r
/^
^3=Rte« A / pgNTftCHLOROPPHENOL STD
r^ ^ta-^.^ ,J V=^ S50 FG
^-^y^TSy
12345678 9101112131415
Figure 21. Mass spectrometry confirmation of air samples 1007 and 1008.
64
-------
TABLE 20. RECOVERY VALUES FOR PENTACHLOROPHENOL
AND HEXACHLOROBENZENE FROM TENAX
Pentachlorophenol
Sample
Field blank #1
Field blank #2
Field blank #3
Field blank #1
Field blank #2
Field blank #3
Field blank #4
Lab spike
Level Level
spiked recovery
(ng) (ng)
--
--
200
200
- 293
200
- 126
200
80
N.D.3
N.D.
N.D.
106
113
liters of air
147
liters of air
141
27.6
Hexachlorobenzene
Level
Recovery spiked
(%) (ng)
h
53b
57b
drawn through
74B
drawn through
71
35
--
194
194
194
194
78
Level
recovery
(ng)
N.D.
N.D.
N.D.
172
160
163
168
58.2
Recovery
(%)
b
89b
82D
V.
84b
87b
75
a N.D. - none detected.
b Compound detected only in the front portion of the Tenax tubes.
-------
PCP AND HCB IN FOOD PRODUCTS
A total of 16 food samples from selected residences were analyzed for
PCP and HCB levels and the results are presented in Table 21. HCB was not
detectable in any of the products. PCP levels ranged from not detectable to
11.7 ppb in an egg shell sample. Selected samples were spiked with PCP and
HCB, and excellent recovery was obtained indicating the validity of the re-
sults. No conclusions were made as to possible elevated levels of PCP on this
limited number of samples. No food products were obtained from either of the
special case families.
PCP AND OCDD IN WOOD SAMPLES
Fifty wood samples were sent to the EPA laboratory in Beltsville, Maryland,
for analysis of PCP, HCB, and OCDD levels. The results for PCP and OCDD levels
in the wood samples are presented in Table 22; the data for HCB levels is not
yet available. Nineteen of the wood samples had detectable (> 5 ppm) levels
of PCP. Of the 28 test case wood samples, seven had detectable PCP ranging
from 8.6 to 737 ppm. Eleven of the 21 control wood samples had detectable
PCP ranging from 4.3 to 1,452 ppm. These data indicate that the PCP levels
in known ammunition crate wood is not present in higher levels than in wood
from the control residues. The possibility exists that some of the control
residence wood was from the ammunition crates and that the residents were not
aware of this wood. The one special case wood sample did contain PCP (836
ppm). No wood sample was available from the other special case family. Only
one wood sample (residence 38-test case) had detectable OCDD and that was at
the detection limit (1 ppm) of the analytical method.
66
-------
TABLE 21. LEVELS OF PENTACHLOHOPHENOL AND UEXACHLOROBENZENE IN FOOD PRODUCTS
Madison County
Health Department Residence number
number and type
G006
CO III
1055
G015
COOS
GOO 7
G008
G022
G021
6023
1056
1057
1058
1059
1060
1061
29 -
32 -
13 -
32 -
29 -
29 -
29 -
1 -
1 -
1 -
40 -
40 -
40 -
13 -
13 -
13 -
test case
test case
control
test case
test case
test case
test case
test case
test case
test case
control
control
control
control
control
control
Sample spiked with
Pentachlorophenol
Sample (ppb)
milk (raw)
milk
milk (pasteurized)
butter
meatc d
egg yolk .
egg shell"
egg white
egg yolke
egg shell*
egg white
egg yolk ,
egg shell'
egg white
egg yolk f
egg shell
N.D."
0.9
1.4
N.D.
4.2
< 0.9
11.7
0.9
< 0.9
2.2
< 0.9
N.D.
1.3
N.D.
N.D.
5.6
Hexachlorobenzene
(ppb)a
N.
N.
N.
N.
N.
N.
N.
N.
N.
N.
N.
N,
N.
N
N.
D.
D.
D.
D.
D.
D.
.0.
D.
D.
D.
.D.
.0.
.D.
.0.
.D.
pentachlorophenol
(40 ppb)
41.
40.
38.
--
29.
--
35.
19.
35.
13.
33.
20.
7
2
1
1
4
2
1
2
9
7
hexachlorobenzene % Recovery
(39 ppb) PCP HCB
39.9
41.7
38.1
--
30
36.0
51
38
31.8
36
67.8
104
98
92
--
73
86
48
86
33
--
85
52
102
107
98
--
77
--
92
131
--
97
82
--
92
100
N.D.
a ppb - paits per billion (ng/ml or ng/g), sensitivity - PCP, 0.4 ng/ml; HCB, 0.4 ng/ml.
b N.D. - none detected, < 0.4 ng/ml.
c Items selected for sampling by sampling crew; no control items obtained.
d Eggs obtained from chicken roost made from ammunition crate wood.
e Eggs obtained from an ammunition crate chicken roost.
f Eggs store purchased.
-------
TABLE 22. LEVELS OF PENTACHLOROPHENOL AND OCTACHLORODIOXIN
IN WOOD SAMPLES
Residence
number
and type
Madison County
Health Dept.
number
Description
PCP
(ppm)
OCDD
(ppm)
1 - test case
G024
3
5
8
10
11
11
12
14
17
18
25
25
27
28
29
29
29
31
31
32
32
33
35
36
37
38
42
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
- test case
1011
G001
G018
G027
G016
G017
1026
1049
P0004
P0003
1012
1013
1028
1034
G002
G003
G004
1032
228A
G011
G012
GO 13
G026
G010
G009
G020
G028
20 - special case
2
4
7
13
15
16
control
control
control
control
control
control
1009
1018
1054
P0008
1051
1046
GO 19
ammunition crate
chicken nest
closet floor
beam in basement
inside kitchen cabinet
inside kitchen cabinet
under sink
outbuilding
back porch
attic
toy box
bookshelf in bedroom
bookshelf in study
outside wood
inside wood
basement
basement
hog house
cow and chicken house
meat house
subfloor
deck floor
ammunition box
manger
basement
closet
subfloor
ammunition crate shelf
in kitchen
pantry
ammunition box
second floor bath
old board in basement
scrap board
shelf in garage
studs in new room
studs in living room
toy train box in
bedroom
134
N.D.
30.8
51.9
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
10.8
8.6
N.D.
N.D.
N.D.
N.D.
N.D.
62.1
73.7
N.D.
836
57.7
7.2
N.D.
N.D.
50.0
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
1.0
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
(continued)
68
-------
TABLE 22 (continued)
Residence
number
and type
19 -
22 -
23 -
23 -
24 -
26 -
30 -
33 -
34 -
39 -
40 -
41 -
43 -
44 -
45 -
control
control
control
control
control
control
control
control
control
control
control
control
control
control
control
Madison County
Health Dept.
number
G025
1020
1043
1044
1041
1010
1024
1017
1036
1038
1048
P0010
1053
1030
P0006
Description
shelf board in
closet
outbuilding
firewood
ammunition box
firewood
dog house
old board in basement
workbench in basement
ammunition box
ammunition box
firewood
shelf
outside front door
outside wood
board in garage
PCP
(ppm)
1,452
24.4
N.D.
N.D.
8.6
4.3
N.D.
79.8
N.D.
253
N.D.
11.8
116.6
N.D.
N.D.
OCDD
(ppm)
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
Sensitivity levels:
pentachlorophenol - N.D. = < 5 ppm
octachlorodioxin - N.D. = < 1 ppm
Positives for pentachlorophenol:
test cases - 7, range 8.6 to 737 ppm
special case - 1, 836 ppm
controls - 11, range 4.3 to 1,452 ppm
69
-------
APPENDIX
STENCILING ON ARSENAL BOARDS FROM MADISON COUNTY. KENTUCKY
70
-------
Residence No. 1 - Test Case
Feb. 13, 1980
At this residence there were two boxes both of which were used as
chicken nests in an outbuilding for the chickens. Nothing was legible on
one box and on the other only the manufacturer's name was apparent and is
presented below.
Slide //I
Marvel Box Co.
Homer, Louisiana
June ?
Residence No. 3 - Test Case «
Feb. 13, 1980
There were no boards accessible with stenciling apparent at this
residence. All boards were subfloor covered with linoleum or a painted
ceiling on the front porch.
Residence No. 5 - Test Case
Feb. 12, 1980
Only accessible boards were floor joists in the basement with no
stenciling apparent or as wall boards under paneling.
Residence No. 6 - Test Case
This was an elderly female in a Covington, Kentucky Hospital with
terminal cancer. Her residence was never visited. Only blood and urine
were sampled.
Residence No. 8 - Test Case
Feb. 13, 1980
There were several boards used in making kitchen cabinets. Seven
boards had stenciling and these are indicated below.
Wt. 81 Ibs. 2 ROS-SHELL with FUZE, 3 INCH GUNS
Cu. 1.89 MK2A M ? M5 & M7
Loaded? T & S.Q M ?
LOT PA ?
Two boards with the above embossing.
71
-------
Slides #2 & 3.
MFC Picatinny Arsenal
Dover, N.J.
11-44
Four boards with above.
RIK
Residence No. 9 - Test Case
This residence was an untreated log cabin .purchased and at a later
date treated by the Capo's with one part penta and nine parts kerosene.
They possess no arsenal wood.
Residence.No. 10 - Test Case
Feb. 12,:1980
At this residence were many boards used throughout the house. Those
presented below were kitchen cabinets and subfloor.
Kitchen cabinets: Slide #4
52 8374-C505
N for CANNON
) Projectile
1315 752 8374 C505
Miller Box Co.
Tuscaloosa, Ala. -
August 1962 DWG 8835039 REV. E
Subfloor: - Slide #5 & 6
Wt. 140
Cu. 3.2
Loaded
Ibs.
11-6?
1315 75
2
7
7
?
342-C507
RIDGES 105MM TP-T
For GUN M68
LOT MA-61-4
M393A1
72
-------
A Projectiles APERS - [, ? 46
W/0 FUZE ?
For HOWITZER M2A2. ,MI ? & M137
Slide #7
Wt. 140 Ibs
Cu. 3.2
Loaded 2-62
1315-753-1842
2 Cartridges
For
9
9
?
705
105MM TP-T M393EI
M68
LOT MA-60-5
1315 728 0704-C518
2 Cartridges 105MM HEP-T M393A1E1
LOT MA ?
? 53-1842-C507
Slide #8
Wt. 148 Ibs.
Cu. 3.3
Loaded 10-66
13 ? 5-0713-C511
? 2 CARTRIDGES 105MM TP-T M490
? For GUN M68
Lot MA 97- ?
Wt. 140
Cu. 3.2
Loaded 11-62
1315 753 1842 C507
2 Cartridges 105 MM TP-T M393A1
Lot MA-6- ?
Wt. 154
Cu. 2.8
Loaded 12-53
2 CARTRIDGES HE M223W ?
73
-------
Residence No. 11 - Test. Case
Feb. 13, 1980
All boards were located in a single outbuildinggarage and adjoining
storage shed.
Slide #9
SPIR No. 2 938 SPA
Slide #10
CONT NEL F/PRINT OVEN
Slides #11 & 12
D.E.R.
Packing
Dehydrating
Do Not Open
Until Ready
Slides
P/0 1940
Paint Suppl
Assorted
A/A
Wt. 1485
L 10 FT
W 5 FT
Residence No. 12 - Test Case
Feb. 13, 1980
Boards at this residence were in the house as ceiling joists and roof
and as'subfloor. They, were also located in an outhouse and barn/garage.
74
-------
At this location was found the oldest boards dating from 1944. The gentle-
man had obtained boards from the arsenal through the early 1970s at which
time the army refused to supply him.
Slide #14
2 SHELL SEMIFIXED HE COMP Mi Dualgram
Wt. 120.0 W Suppl Chg + FUZE PD M51A5 0.05 Sec Delay
Cu. 2.02 105 MM Howitzers COMP B
Loaded 3-53
RAPBA
Lot LS-100-1Z
Slide //15
Boxes Inc.
Medora, Ind.
7-53
DR WG No. 76-1-1389
Slide //16
R C Bennett Box ?
AHOSKIE, N.C.
Apr. 53
ORG No. 16-1-13 ?
Slides //17 & 18
Drawing No. P-82477
Date MFC 5-52
Gideon Anderson Lumber Co.
Gideon, Missouri
Slide #19
MFC by Chapman and Dewey LBR Co.
Memphis, Tenn 6-52
DWG No. P-82477
75
-------
Slide #20
P5QEA
LOT KOP
38-7
Slide #20a
LOT IOP-2-7-X
B-2
Slide #21
RADMA Ammunition for
LOT KOP Cannon w Solid
Projectiles
Slide #22
Ammunition for Cannon with Solid Projectiles
P5QES
Slide #23
RADMA
LOT KOP-47-4
Slide #24
P5QDS
Lot KOP
15-4-X
Slide #25
2 Rounds Complet (without fuses)
ROCKET HE 4.5 Inch MBA 1
Wt. 102 Ibs
Cuff 2.02 LOT GOP 1-29
Loaded 4-44
76
-------
Slide #26
Goodyear Yellow Pine
Picayune, Miss.
August 1944
Slide #27
RIQSA
LOT IL-
5-15-
Residence No. 14 - Test Case
Wood consisted of a single box used by son to store electric train
in his room.
Box top:
Ammunition for Cannon w Explosive Projectiles
RASBA
LOT IOP-3-15
Box backside:
Slide //28
2 CARTRIDGES HF M323 w/Suppl Chg & Fuze
Wt. 154 PD M51A5 0.05 Sec Delay
Cu. 2.8 105 MM Rifle COMP B
Loaded 5-53
LOT IOP 3-15
RASBA
Box front - Blank, nothing
Box Bottom:
Manufactured by
? ? Weaver LM Co.
Nov, 1951
Box ends:
Slide //29
LOT IOP 3-15
RASBA
77
-------
Residence No. 17 - Test Case
Feb. 13, 1980
No stenciling apparent any longer on finished boards.
Residence No. 18 - Test Case
Feb. 13, 1980 -
Wood used to make book shelves in house and to store firewood on
outside porch. Book shelves have been painted.
Box top: . . . Slide #30
Box
Box
Box
BOJ
ROCKET FINS ?
S9NKA
LOT DMFC-5-6
backside: Slide #31
1 340-028-
6100-J450
24 RDS
frontside: . Slide #32
S9NKA
Wt. 70 4 Modification Kits
Cu. 5.9 ROCKET AIRCRAFT 5 INCH M34
Loaded ?
(54 possibly) LOT DMFC-5-6
: ends: Slides #33 & 34
S9NKA
LOT DMFC-5-6
i bottom: Slide //35
ROCK MGF Co.
Stoughton,. Mass.
June, 1952
Residence No. 20 - Test Case
The residence was a log cabin commercially treated by the manufacturer.
78
-------
Residence No. 25 - Test Case
Feb. 13, 1980
At this residence there were approximately 120 boxes stacked in the
yard and were used as firewood.
Slides #36,
37, & 38
Two Cartridges HE M323 w/Suppl Chg
and fuze PD M51A5 0.05 Sec Delay
Wt. 154 105 MM Rifle Comp B
Cu. 2.8
Loaded 5-53 LOT IOP 3-16
Approximately 40 boxes with above data.
Slide //39
1315 926 1928 C601
2 Cartridges 90MM Canister Apers M377.
For Guns M36 & M41
Wt. 18 ?
Cu- 2-5 LOT IOP 2-16
Loaded 12-67
Approximately 80 boxes with above data. If these are preserved, they were
in no better condition than the 1953 boxes.
Residence No. 29 - Test Case
Feb. 13, 1980
There was no wood within the house, however, there were four out-
buildings in which the wood was used. Two buildings were for pigs, one
was for hogs and chickens, and a fourth was a smokehouse. In the chicken-
house a box was used as chicken nests. In the smoke house was a large
boards on which exposed salted meat was laid for storage and later use.
There was no wood with any stenciling.
Residence No. 31 - Test Case
Feb, 12, 1980
Wood used as subfloor throughout house.
79
-------
Slide #40
RINTB
LOT CA ? 7-17
Slide /Ml
RINBT
LOT JA 7-17
Slide #42
LOT IOP 5-8
B-2
Slide #43
LOT
IOP 5-10
B6
LOT IOP
5-7
LOT 5-10
B-2
Slides #44 & 45
83 Ibs
Wt- 7.2 4-52 2 Cartridges ? TP M09A1 w/Fuze
Cu. 1.64 PD M51A5 ? 0.5 Sec Delay
Loaded ? 75 MM ? Rifle
LOT J " 7-17 .
RINTB
80
-------
Slides #46 f, 47
Wt. 7.2
Cu. 1.64
Loaded 6-54
83 Ibs
4-52
2 Cartridges
PD M51A5
75 MM
Lot 5-10
TP M09A1 w/Fuze
0.5 Sec Delay
Rifle
7-17
RINTB
Slides #48 & 49
Wt. 7.2
Cu. 1.64
Loaded ?
80 Ibs
4-52
2 Cartridges
PD M51A5
Lot 7-17
TP M09A1 w/Fuze
0.5 Sec Delay
Rifle
7-17
RINTB
Residence No. 34 - Control
Feb. 13, 1980
Boards were used as subfloor and as a storage box in basement.
Box top - Nothing legible
Bottom - Nothing
Backside:
Slide #50
Blue
Streak
Project Code
t
Right left ends:
Slide #51
R40FA
LOT IOP:
4-82
81
-------
Front:
Slide #52
R40FA
Wt. 79
Cu. 1.49
Loaded 8-53
2 SHELL HE ?
& Fuze PD M ?
Residence No. 32 - Test Case
Feb. 12, 1980
There are about 150-200 boxes stored in an old barn.
to have same stenciling except for LOT Nos.
Top:
Most all appear
4
Slide #53
Bac
Box
Ammunition for Cannon w
Explosive Projectiles
RITUS
LOT LOP-9-28-X
kside:
2 Shell Fixed HE COMP B M42A1
Wt. 73.50 Smokeless w/Fuze PD M51A5 0.05
Cu. 1.34
Loaded 7-54 76 MM GUNS COMP B
RITUS
Lot LOP 9-2 8-x
ends:
Slide #54
Sec Delay
Slide #55
RITUS
LOT LOP 9-2 8-x
Other boxes (Slide #56) have the same information with either the dates
Loaded being 7-54 or 9-54 with Lot Nos. such as:
LOP 9-36-x
LOP 9-27-x
LOP 9-25-x
LOP 9-34-x
etc.
82
-------
Residence No. 35 - Test Case
Feb. 12, 1980
Boards used in walls and ceilings with no stenciling apparent
Residence No. 36 - Test Case
Feb. 13, 1980
Boards used as subfloor with most stenciling visible from the basement.
Slides //57,
58, & 59
Wt. 118
Cu. 2.69
Loaded 2-5A
2 Cartridges HE-T ?
W/Fuze PD M51A5 0.5 Sec Delay
90MM Gun
LOT ? .A
RADGA
? 19
23-9
TNT
(seven of above)
Wt. 118
Cu. 2.69
Loaded 2-54
2 Cartridges HE-T ?
W/Fuze PD M51A5 0.5 Sec Delay
90MM Gun ? 19
LOT ? A-23-6
TNT
RADGA
(five of above)
Wt. 118
Cu. 2.69
Loaded 2-54
2 Cartridges HE-T ?
W/Fuze PD M51A5 0.5 Sec Delay
90MM Gun ? 19"
LOT ? A-23-11
TNT
RADGA
(only one of above)
83
-------
Wt.
Cu.
118
2.69
Loaded 2-54
2 Cartridges HE-T ?
W/Fuze PD M51A5 0.5
90MM Gun ? 19
LOT ? A 23-1
RADGA
Sec Delay
TNT
(five of above)
Slide #60
Wt. 118
Cu. 2.69
Loaded 2-54
2 Cartridges HE-T ?
W/Fuze PD M51A5 0.5 Sec Delay
90MM Gun ? 19
LOT ? A-23-14
TNT
RADGA
(five of above)
Slide #61
J & S Mfg. Co.
Little Rock, Ark.
December 1953
Slide #62
R C Bennett Box Co.
AHOSKIE, N.C.
Nov. 1953
(eight of above)
Slide #63
Wt. 118
Cu. 2.69
Loaded 11-53
2 Cartridges HE- ? T 91
W/Fuze PD M51A5 ? 0.5 Sec Delay
90 MM Gun ? T 119
L ? RVA-20-19
TNT RADGA
84
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Slides #64 & 65
Wt. 118
Cu. 2.69
Loaded 11-53
2 Cartridges HE-
W/Fuze PD M51A5
90 MM Gun ? T 119
L ? RVA-20-29
TNT RADGA
? T 91
? 0.5 Sec Delay
Slide //66
Wt. 131
Cu. 2.69
Loaded ?
HE COMP B
W/0 Fuze
Guns
LOT
Flashless P50TA
Comp B
A
Slide //67
Edwards & McGehee
Auburn, Ala
Dec. 1953
(five of above)
Slide #68
Newman Const.
LaGrange, Ga.
1-54
(four of above)
Slide #69
Ammunition for Cannon with
Explosive Projectiles
? Lumber Co.
? Ala
June 1953
85
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Slides #70 & 71
2 Shell fixed HE COMP B M71
SMKLS-FLHLS P50M ?
Wt. ? W Suppl. Chg. W/Fuze PD M51A5
Cu. 2.68 0.05 Sec Delay
Loaded ? 90MM Guns Ml M2 M3 & T8
LOT RVA
Other short residence slides include Slides #72, 73, 74, and 75.
. *
Residence No. 37 - Test Case
Feb. 12, 1980
All boards in a kitchen storage shelf are painted. Other boxes stored
outside were disposed of.
Residence No. 38 - Test Case
Feb. 13, 1980
All wood has been used in house and all is painted.
Residence No. 39 - Control
Only one box once used as a toy box but subsequently stored away in
attic.
Top:
Ammunition for Cannon w Explosive Projectiles
R1TUS
LOT LOP 9-21-x
Backside: Nothing
Front: Slide #76
2 Shell Fixed HE MA2A1 Normal Charge
Wt. 735.0 Comp B
Cu. 1.34 Smokeless w Fuze, PD M51A5 0.05
Loaded 5-54 Sec Delay,
76MM GUN LOT LOP 9-21-x
RITUS
86
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Bottom:
Slide #77
R C Bennett Box Go.
Herlong, Calif
Feb. 1951
Ends:
Slide #78
RITUS
LOT LOP ?
Residence No. 42 - Test Case
Feb. 12, 1980
Boxes used as shelves and all have been painted.
Note: ? - Stenciling blurred, worn off or covered over by other boards.
87
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 560/13-80-030
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
DETERMINATION OF PENTACHLOROPHENOL AND
HEXACHLOROBENZENE RESIDUES
5. REPORT DATE
June 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Duane B. Lakings,1 Wilma Subra,2 John Going1
8. PERFORMING ORGANIZATION REPORT NO.
4901-A12
9. PERFORMING ORGANIZATION NAME AND ADDRESS
1. Midwest Research Institute
425 Volker Boulevard, Kansas City, MO 64110
2. Gulf South Research Institute
P.O. Box 26518, New Orleans, LA 70186
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-5915 Task 12
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, SW, Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 1/80 - 7/80
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
An evaluation of possible exposure to pentachlorophenol (PCP) by residents in
Madison County, Kentucky, who had obtained ammunition crate wood treated with PCP from
the Blue Grass Army Depot was conducted. Serum and unconjugated urine levels of PCP
were determined in 51 test cases and 47 control individual and in 7 special cases
(residents of log homes treated with PCP). In addition, air, food product, and wood
samples collected at the residences were analyzed for PCP residues.
The results showed similar PCP levels in the serum and urine of the test cases
and control individuals. No PCP was detected in the air collected from these groups'
residences; and the levels of PCP found in the food products and wood samples from the
test case and control residences were similar. Thus, the test case individuals were
not being subjected to PCP exposure from the ammunition crate wood.
However, high PCP levels were found in the serum and urine of the special cases,
particularly three young children who had PCP serum levels above 1,000 ppb (40 times
the control individual average). Air arid wood samples from a special case residence
also contained PCP. Thus, the special cases were being subjected to PCP exposure and
additional studies on log home residences are recommended to define the exposure level
and the possible adverse health effects. No hexachlorobenzene was found in any samples.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI l-'ield/Group
Pentachlorophenol
Hexachlorobenzene
Serum levels
Unconjugated urinary levels
Ammunition crate wood
Log homes
Air
Wood
Food products
18. DISTRIBUTION STATEMEN1
Release to public.
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
95
20. SECURITY CLASS
lURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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