EPA-650/1-75-002
March 1975
Environmental Health Effects Research Series
33
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EPA-650/1-75-002
ENVIROMMENTAL
EXPOSURE STUDY
SOUTH FLORIDA
by
Dr. John E. Davies
University of Miami School of Medicine
1600 N. W. 10th Avenue
Miami, Florida 33152
Contract No. 68-02-1277
ROAP No. 21AYL
Program Element No. 1EA078
EPA Project Officer: Dr. Thomas M. Scotti
Pesticides and Toxic Substances Effects Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
WASHINGTON, D. C. 20460
March 1975
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EPA REVIEW NOTICE
This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series. These broad
categories were established to facilitate further development and applica-
tion of environmental technology. Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields. These series are:
1. ENVIRONMENTAL HEALTH EFFECTS RESEARCH
2. ENVIRONMENTAL PROTECTION TECHNOLOGY
3. ECOLOGICAL RESEARCH
4. ENVIRONMENTAL MONITORING
5. SOC1OECONOMIC ENVIRONMENTAL STUDIES
6. SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS
9- MISCELLANEOUS
This report has been assigned to the ENVIRONMENTAL HEALTH EFFECTS
RESEARCH series. This series describes projects and studies relating
to the tolerances of man for unhealthful substances or conditions. This
work is generally assessed from a medical viewpoint, including physio-
logical or psychological studies. In addition to toxicology and other
medical specialities, study areas include biomedical instrumentation
and health research techniques utilizing animals - but always with in-
tended application to human health measures.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.
Publication No. EPA-650/1- 75-002
11
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CONTENTS
Page
Abstract 11
List of Figures Iv
List of Tables vl
Acknowledgements ix
Sections
I. Conclusions 1
II. Recommendations 3
III. Scope and Purpose, of Contract 4
IV. Urinary Metabolite Studies 5
V. Air Sampling Studies 53
•VI. EEC Studies 70
VII. Performance and Problems Encountered 73
VIII. References 75
IX. Glossary 77
X. Biblographic Data Sheet 79
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Abstract
In our Pesticide Epidemiological Field Studies in 1973 (EPA-650/1-74-009) we
showed that the alkyl phosphates were highly significantly inversely correlated
with red blood cell cholinesterase values, and this year our studies have con-
firmed that multiresidue analyses of urinary metabolites offer an effective
measurement of human exposure to the non-persistent pesticides. Besides their
epidemiologic potential, urinary metabolite information facilitated worker
surveillance and simplified the diagnosis and management of acute pesticide
poisoning.
In studies of different human exposures to parathion, DEP, the metabolite of
paraoxon, proved to be a sensitive indicator of illness and serious cholines-
terase inhibition. Thus, concentrations in excess of 0.4 ug/ml were observed
in 7 parathion poisoning cases; yet, in 71 urines from 5 pesticide exposed
workers having normal cholinesterase values, only 1 urine had concentrations
of DEP >.4 ug/ml. The ratio of DEP:DETP concentrations was also very informa-
tive. The average ratio was 4.4 in 20 urines from the hospitalized cases but
only 0.88 in the exposed workers, this difference was significant at the p <.01
level. The data suggested that in parathion exposure, if in a single urine,
DEP concentrations were twice as high as DETP, and if the former were present
in concentration of >.4 ug/ml, these were the hallmarks of over exposure. The
data suggested that the whole problem of parathion intoxication could be as-
cribed to the amount of oxon present. In the re-entry situation, danger
arises when paraoxon forms, and prevention will have to focus on the physical
and chemical factors which reduce or prevent exogenous oxon formation. In
applicator poisoning, illness appears to be the result from an over loading of
the body with endogenously produced paraoxon. These urinary metabolite data
appear to have a potential in.-.validating re-etitry times or in testing, protective
devices.
Prolonged metabolite excretion was encountered in a poisoning case which was
the result of suicidal ingestion of dichlofenthion. Cholinesterase enzymes
were 90% inhibited for 39 days and urinary metabolites were detected for 91
days. The clinical and toxicological features of this type of pesticide opens
up a whole new dimension of pesticide toxicity because of the persistence of
the effects. Expressions of low level exposures of the general population to
the non-persis'l^ni_Re&ti.c±de.3_j!itas_Br^yld.eji_bjL-urJLnar-y_me.tabo^ studies_o.f_
_38_personsA All had levels of PGP and 29% were positive for 3,5,6-TC Pyridinol,
a metabolite of Dursban.
Environmental studies were reflected by regular air monitoring of pesticides
in several different sites of South Florida. Dichlofenthion, Dursban and
Lindane were found in every urban sample, and Heptachlor and Alpha and Gamma
Lindane and Dursban were also identified. Alpha-BHC, Diazinon, Lindane and
Dursban were the pesticides most frequently identified in the Everglades.
This activity has been one of the few ongoing air monitoring studies in the
U.S. this last year and we were able to provide confirmatory evidence that as
a result of the DDT ban no traces of this insecticide were found in the ambient
air collected; the only exception being in a single sample from a pesticide
formulating plant.
iii
This report was submitted in fulfillment of Contract No. 68-02-1277 by the
University of Miami School of Medicine under the. sponsorship of the U.S. Environ-
mental Protection Agency. Work was completed as of December 31st, 1974.
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FIGURES
No. Page
L. Sequential urinary excretion rates of alkyl phosphates and
paranitrophenol in a spray man (TB) hospitalized for acute
parathion intoxication - dermal 25
2. Sequential urinary excretion rates of alkyl phosphates and
paranitrophenol in a spray man (JD) hospitalized for acute
parathion intoxication - dermal 26
3. Sequential urinary excretion of alkyl phosphates and para-
nitrophenol in a 4*5 year old white male (MP) hospitalized
after acute parathion intoxication - dermal . ^7
4. Sequential alkyl phosphate and paranitrophenol excretions
in a loader after two hours exposure to mixing and loading
6-3,ethyl methyl parathion - Dade County 1974 28
5. Sequential alkyl phosphate and paranitrophenol excretions
in a loader (WG #2) after 2% hours exposure to mixing and
loading 6-3 ethyl methyl parathion and 12 hours mixing and
loading Cygon - Dade County 1974 2^
6. Urinary alkyl phosphate and paranitrophenol excretion rates
in a helicopter pilot (FB) during and after application of
parathion mixtures Phosdrin and Cygon •*
7. Urinary alkyl phosphate and paranitrophenol excretion in a
helicopter pilot (GJ) 24 hours after occupational exposure
to parathion, Phosdrin and Cygon ^1
8. Urinary alkyl phosphate and paranitrophenol excretion rates
in a helicopter pilot (DA) 24 hours after occupational
exposure to parathion mixtures and Cygon 32
9. Sequential urinary alkyl phosphate and phenolic excretion
rates in a structural pest control sprayer (HP) during and
after 5k hours application of 2.5% Dursban and 0.75% DDVP 39
10. Sequential urinary alkyl phosphate and phenolic excretion
rates in a structural pest control sprayer (ES) during and
after 5% hours application of 2.5% Dursban and 0.75% DDVP 40
11. Urinary alkyl phosphate excretion rates in a pilot (JS)
loading and applying Phorate for 2 hours 43
12. Daily excretion of alpha naphthol (yg/ml) in two spraymen ^
applying 0.5% Sevin (carbaryl)
iv
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Figures (continued)
No. Page
13. Serum concentrations of dichlofenthion (ppb) and red blood
cell and plasma cholinesterase levels (ApH/hr) during re-
covery following oral ingestion of dichlofenthion (VC-13) ^9
lU. Urinary excretions of alkyl phosphates and phenolic meta-
bolites in a case of dichlofenthion (VC-13) poisoning.
Dade County 1971* 51
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TABLES
No.
1 List of Pesticides Discussed in This Report and Their Di-
alkyl Phosphates and Phenolic Metabolites 8
2 Mean and Ranges of Red Blood Cell and Plasma Cholinesterase
(ApH/hr) of Different Pesticide Exposure Groups, 1974 10
3 Sequential Red Cell and Plasma Cholinesterase Levels (ApH/hr)
in Different Exposure Groups, South Florida, 1974. 12
4 Exposure History and Cholinesterase Levels of Occupationally
Exposed Pesticide Workers. 14
5 Sequential Urinary Excretion Rates of Alkyl Phosphates and
Paranitrophenol in a Spray Man (T.B.) Hospitalized for Acute
Parathion Intoxication - Dermal. 15
6. Sequential.Urinary Excretion Rates of Alkyl Phosphates and
Paranitrophenol in a Spray Man (J.D.) Hospitalized for Acute
Parathion Intoxication - Dermal. 17
7. Urinary Alkyl Phosphate and Phenolic.Levels in an Acute
Intoxication of Parathion in a 4*5 Year Old White Male (M.P.) -
Dermal ia
8. Sequential Alkyl Phosphate and Paranitrophenol Excretions in
a Loader After Two Hours Exposure to Mixing and Loading 6-3
Ethyl-Methyl Parathion, Dade County, Florida 1974 (W.G. #1). 19
9. Sequential Alkyl Phosphate and Paranitrophenol Excretions in
a Loader (W.G. #2) After 2% Hours Exposure to Mixing and Load-
ing 6-3 Ethyl-Methyl Parathion and 12 Hours Mixing and Loading
Cygon and Sevin, Dade County, Florida 1974. 20
10. Urinary Alkyl Phosphate Excretions in a Helicopter Pilot (F.B.)
During and After Occupational Exposure to Parathion Mixtures,
Phosdrin and Cygon, 1974. 21
11. Urinary Alkyl Phosphate and Paranitrophenol Excretion in a
Helicopter Pilot (G.J.) 24 Hours After Occupational Exposure
to Parathion, Phosdrin and Cygon. "
12. Urinary Alkyl Phosphate and Paranitrophenol Excretion Rates
in a Helicopter Pilot (D.A.) 24 Hours After Occupational Ex-
posure to Parathion Mixtures and Cygon. 23
13. Levels of Urinary Metabolites of Ethyl Parathion in the First
Urine Samples Analyzed in Seven Cases of Parathion Poisonings. 33
vi
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Tables (Continued)
No. Page
14. Comparison of DEPrDETP Ratios with Urines From Patients With
Parathion Poisoning with Asymptomatic Occupationally Exposed
Workers, South Florida 1974. 35
15. Sequential Urinary Alkyl Phosphate and Phenolic Excretion
Rates in a Structural Pest Control Sprayer (M.P.) During and
After 5% Hours Application of 2.5% Dursban and 0.75% DDVP. 37
16. Sequential Urinary Alkyl Phosphate and Phenolic Excretion
Rates in a Structural Pest Control Sprayer (E.S.) During and
After 5% Hours Application of 2.5% Dursban and 0.75% DDVP. 38
17. Urinary Alkyl Phosphate Excretion Rates in a Pilot (J.S.) Load-
and Applying Phorate for 2 Hours. ^2
18. Alpha Naphthol Concentration in Two Dade County Parks Department
Spraymen (R.S. and E.O.) Who Had Been .Using 0.5% Sevin (carbaryl) 45
19. Cholinesterase, Pesticide Residues and Phenolic Data Following
Oral Ingestion of Dichlofenthion, Dade County 1974. /»8
20. Urinary Alkyl Phosphate Excretion Rates During Recovery Following
Oral Ingestion of Dichlofenthion, Dade County 1974. 50
21. 2,4-Dichlorophenol Concentrations in a Volunteer Sprayman (J.D.)
Using VC-13 For a Period of One Hour 40 Minutes. 52
22. Urinary Pesticide Concentrations and Rate of Excretion in the
General Population of Dade County, Florida 1974. 55
23. Frequency of Occurrence of Pesticide Urinary Metabolites (ug/ml)
in the General Population of Dade County, Florida 1974. 57
3
24. Pesticide Concentrations in Air Samples (ng/m ) from Suburban
Site, South Florida. 60
25. Pesticide Concentrations in Air Samples (ng/m ) from Everglades
Site, South Florida. 61
26. Pesticide Concentrations in Air Samples (ng/m ) from Bimini
and Selected Work Sites in South Florida. 62
o
27. Indoor Concentrations of Pesticides (ng/m ) at Two Selected
Sites in South Florida. 63
28. Mean and Ranges and Frequency of Occurrence of Pesticides in
Air (ng/ni ) at the Suburban Site, Dade County Florida 1974. 64
vii
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Tables (Continued)
No. Page
29. Mean and Ranges and Frequency of Occurrence of Pesticides
in Air (ng/nr) at the Florida Everglades Site, Dade County,
Florida, 1974 65
30. Pesticide Concentrations Collected From a Cloth Screen
(ng/Jjm2) From Two Sampling Sites in South Florida 66
31. Trapping Efficiency of Nylon Screen and MRI Impingers at
Two South Florida Sites, 1974 67
32. VC-13 Concentrations (ng/m3) in Air 10, 23 and 50 Days
After a Single Lawn Spray Application of 26 oz. of 75%
VC-13 Solution 69
33. Table of EEC Participants 71
34. Total Number of Analyses Completed During the Annual Study
Period 74
viii
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ACKNOWLEDGEMENTS
The investigators acknowledge with gratitude the cooperation and assistance
offered us to conduct these studies by Allied Helicopter Service Inc.,
Tri-State Dusting Service, South Bay Growers, U. S. Department of Agriculture,
the Dade County Housing and Urban Development Program, the Eveready Pest
Control Company, the Dade County Parks Department, Woodbury Chemical Company,
and the several volunteers representative of the general population for their
willing cooperation and participation to provide blood and urine samples for
appropriate cholinesterase and urinary metabolite studies.
In addition, the investigators at the University of Miami appreciate the
advice and guidance provided by Drs. Thomas Scotti and William Durham,
Dr. Taalat M. Shafik, Dr. John Santolucito and Mr. Frank Wiliniski.
ix
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CONCLUSIONS
The goals of these studies have been directed toward a better understanding
of different degrees of human pesticide exposure. When the pesticide worker
is over exposed and starts to develop cholinergic manifestations, convention-
ally this exposure has been related to red blood cell and plasma cholinesterase.
There are, however, several well recognized limitationswith these biological
indices and certain urinary pesticide metabolites have shown to be more sensi-
tive indices of exposure. The urinary alkyl phosphate metabolites were one
group of pesticide metabolites whose potential as biological indices of pesti-
cide exposure needed to be evaluated. In a study of these metabolites in a
group of helicopter pilots and loaders having heavy work exposure to ethyl-
methyl parathion mixtures, we found that there was excellent correlation of
these metabolites with red cell cholinesterase levels. DEP, DETP, DMP and
DMTP were all significantly inversely correlated.
Our studies this year have confirmed that both qualitative and quantitative
information was provided by the alkyl phosphate data from parathion exposures.
Concentrations of DEP were >.4 ug/ml in all the first urines in seven poison-
ings investigated. The entire urinary output during the first 48 hours of
hospitalizatioh were collected from three of the seven pesticide poisoning
cases. In each specimen voided DEP concentrations were >.4 during this period.
These were in striking contrast to the levels of DEP observed in asymptomatic
occupationally exposed workers; only one out of 71 urines had a DEP concentra-
tion of >.4 ug/ml.
The DEP:DETP ratio was also highly informative; the mean of this ratio for
these two metabolites was 4.14 in the poisoned cases compared to 0.88 in the
71 urines from the occupationally exposed group. These data clearly emphasized
the qualitative significance of DEP. DEP is the alkyl phosphate derivative
from ethyl paraoxon exposure which seems to be the only key factor in parathion
poisoning. In reviewing all of the data we concluded that if in a single urine
from a person having parathion exposure, DEP concentrations were twice as high
as DETP, and if DEP concentrations were >.4 ug/ml these were the hallmarks of
excessive exposure and were metabolite concentrations which were indicative of
overt or imminent parathion poisoning.
In our experience this year multiresidue techniques ha-, e been found to be an
excellent measure of human pesticide exposure to the biodegradable pesticides.
On most occasions urinary alkyl phosphate data were complimentary to urine
phenolic data, the combined information facilitating the identification of
specific pesticide exposures.
In metabolite studies of workers exposed to pesticides where cholinesterase
inhibition was neither observed nor anticipated, the chronicity of the meta-
bolite excretion following a short work exposure was surprising. Alpha naphthol
was detected 42 hours after a 5 hour exposure to carbaryl. Dursban metabolites
were detectable for up to 30 hours after a 4% hour exposure. Dichlofenthion
(VC-13) produced the most protracted toxic effects of all pesticides studied.
90% inhibition of cholinesterase was observed for as long as 39 days after oral
ingestion and both alkyl phosphate and phenolic metabolites could be detected
for as long as 91 days after exposure. This concept of chronicity of organo-
phosphate exposure could be attributed to the fat solubility of certain pesti-
cides and the phenomenon raises a whole new dimension of acute and chronic effects.
With compounds which are as fat soluble as dichlofenthion, if present use
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continues it is not beyond the realm of possibility that these materials
will be identified in the human adipose pesticide residue.
Both types of metabolites were also found to be of great value as measures
of incidental exposure to the non-persistent pesticides. In^ stud".of 38__
members^ of the general pQpula.tion-of—Dade—Coun£.y_jgvery urine had ti .ces
"of penjachloj3Phehpl_(LCP)_^iid_25%_w.er.e_R.o.si.tive_fQr_3.5.6-TC pyrlclinol
Ls is ametabolite of the compound_D.ur.s.b.an). Jhe concentrations of
these metabolites_in_the general pomLlatJuan_w.e£e all of a low order of~~
magnitude though PCP was as ubiquitous as DDT has been in the past.
/^ The second goal of these studies has been to measure environmental air
.pollution bv_pesticides. The air monitoring data of pesticides presented
in this report represents the only sources of pesticide concentrations_in
air in the United States last y.ear.. Significant qualitative and quantita-
'tive information was obtained. No DDT was identified in air sampljs ex-
cept in a collection from a formulating plant. _Dichlof.en.t.hion.,_D.urjiban
_and_JLindane__wer.e—found_in_ever-y—sample—f-rom-the_s.ubur.b.an_si.t.e_and in rl i e
Everglades a- BHC, diazinon, lindane and dursban were the pesticides most
frequently identified. Chlordane was identified for the first time as well
as Heptachlor. In none of the sites were sizeable concentrations of pesti-
cides detected with the exception of air levels in a formulating plant.
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RECOMMENDATIONS
Our studies to date continue to reinforce the concept that both urinary
alkyl phosphate and phenolic metabolites are excellent indices of human
pesticide exposure. In our first year of research, they were shown to
correlate with red cell cholinesterase levels, and in our studies this
year, the special significance of the di-alkyl phosphate metabolite re-
flective of oxon exposure has been identified. More and more it appears
that the presence of the oxon whether preformed exogenously on the leaves
or endogenously as the result of saturating the body's detoxification pro-
cesses is the cause of pesticide illness. It is recommended, therefore,
that the potential of DEP and DMP in occupational exposure to the more
toxic organophosphates, be further investigated through the acquisition
of more data of these metabolites in acute and occupational exposures to
parathion and Phosdrin. The relationship of these to cholinesterase in-
hibition needs to be validated.
The ratio of DEP:DETP has also been found to be very informative and the
potential of a field test kit which can measure these two metabolites
needs to be investigated. With the acquisition of data of this sort,
it should be possible to measure the safety of the work environment.
Metabolite concentrations should be expressed in micrograms per milliliter
but these values should be corrected to a standard osmolality (800).
Twelve hour urines, rather than each voided urine should be examined
under both situations. The possibility of storage of the less polar
organophosphates in fatshould be investigated. Significant prolonged
exposure effects appear to result from exposure to these more fat solu-
ble pesticides and it is recommended that every attempt be made to deter-
mine whether these are beginning to be stored in human fat. The frequency
of alkyl phosphates and phenols in the urine of the general population is
conflicting and the need to resolve this issue is urgent.
We believe that there is a need to improve the gas chromatographic and
detection systems in order to concentrate larger samples of urine including
further cleanup; this is the only way that low level exposure of the United
States population to the non-persistent pesticides can be monitored. ,In
this respect, further eaidemiological studies qf_p.entachlo.r.opheno.l_(P-CR)—
jare_4ieeded. TJiis_jnetabolite is as ubiquitous as DDT yet it has nev.er_bejen __
extensively studied epidemiologically, and Shafik has recently identified ,
residues of this pesticide in the adipose tissue of the general population.
Expanded and representative air monitoring for pesticides is another area
of monitoring where our studies seemed to have identified an unmet need.
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SECTION III
SCOPE AND PURPOSE OF THE CONTRACT
The overall goals of this program seek to measure the occupational and environ-
mental effects of pesticide exposure in South Florida. In addition to the
conventional approaches of measuring exposures to the organpphosphate and.
carbamates through cholinesterase determinations, special emphasis has been
placed upon the study of exposure to these pesticides through the study of
their urinary metabolites. The dialkyl phosphate and urinary metabolites
have been examined under varying degrees of occupational, accidental and
incidental exposure. In addition to the urinary metabolite studies possible
central nervous system effects of occupational ejCBas.ur.e_bav.e—been-exami-ned—
through the collection of elec.t.r.oejicep.halographic_trac.ings—in—workers. Environ-
mental jafia.SMrpniftnfR yf p«»g«-ifiH<» ovposure have been quantitated on the basis
of regular—mon-Jrfeering-of—ambient air samples in selected-sites in South
Florida.
This annual report describes the activities of the contract in these three
areas and covers the contract period of January 1, 1974 through December 31,
1974. Much of these activities have already been reported in detail in the
three preceeding quarterly reports. In order to avoid repetition the salient
features of this year's study are described in detail, with special emphasis
being given to research and toxicological findings.
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SECTION IV
Background Information of Urinary Metabolite Studies - As a result of the
Occupational Safety and Health Act of 1970 considerable emphasis has been
focused on the introduction and enforcement of practices and standards which
are designed to improve the safety and health of the worker in industry. The
pesticide industry, and in particular the pesticide exposed worker, is an urea
of special concern. Appropriate groups in agriculture and health have responded
to these challenges and collectively have developed programs related to the
education, training, legislation and surveillance of the exposed worker.
As a result of the switch from the more persistent organochlorine to the
less persistent but more toxic organophosphate and carbamate insecticides,
the need to control and contain worker exposure to these groups of pesticides
has assumed increased importance.
From a practical point of view, worker exposure can be arbitrarily divided into
those exposures which are associated, (1) with the manufacture, formulation,
transportation and application of pesticides and (2) those exposures which
are acquired during the processes of harvesting and thinning. In the former,
the worker at some time or other, comes into contact with the concentrate;
illness which results from such an exposure can be termed "applicator poisoning".
In the latter type of exposure, sickness occurs as a result of contact with
the pesticide residue on the leaf or in the soil of the work environment.
This type of illness is sometimes referred to as "picker poisoning". The
goals of industrial health in both situations are, firstly, to prevent acute
poisoning, the symptoms and signs of which are cholinergic, and secondly,
to prevent excessive and undesirable exposures, the chief manifestation of
which is a biological effect rather than a clinical effect and is reflected
by a decline of the red cell and plasma cholinesterase. Several preventive
strategies for these two types of poisoning are currently in vogue. Picker
poisoning, or residue intoxication involves a sizeable work force so that
cholinesterase surveillance is impractical both on the grounds of worker
acceptability and also from a purely logistical point of view. The federal
government is currently in the process of developing re-entry times for this
type of occupational illness. These times are prescribed intervals between
application and picking which must lapse before agricultural workers enter
the field for harvesting—different times for different pesticides are pre-
sently under review.
In the applicator situation, surveillance of the worker has traditionally
relied upon cholinesterase testing; here however experience has shown that
there are several serious setbacks with this approach. These include the
necessity of obtaining pre-exposure levels and the absence of a definitive
cholinesterase level which is diagnostic of overt illness. For these reasons,
many workers in occupational health have explored the potential of the pesti-
cide urinary metabolite as an alternative measure of human pesticide exposure,
and as a result of new methodology significant progress has been made in the
area, which suggest that these urinary indices of exposure could become
effective expressions of worker exposure.
Metabolism studies have shown that for the biodegradable pesticides, the
phenols, phenoxy acids and the alkyl phosphates are the major metabolites.
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Before the advent of multiresidue analytical procedures, colorimetric techni-
ques were used to study some of these metabolites. Paranitrophcnol (PNP) was
one of the earliest phenolic metabolites to be investigated and several re-
searchers confirmed that PNP excretion was a more sensitive measure of parathion
than blood cholinesterase levels. Although these earlier approaches were
able to detect levels of PNP as small as 0.01' ppm, large volumes of urine
(100 ml) were required to detect these low levels and the method had additional
complications which were the result of high background interferences. The
potential for the study of low level human exposure to biodegradable pesticides
by means of the halo and nitrophenol and phenoxy acids was greatly facilitated,
by the development of the multiresidue procedures (Shafik, Sullivan and Enos).
The principle behind these new approaches were based upon the preparation of
the ethyl derivative of the phenols and acids. Similar multiresidue techniques
were developed for low level exposures to the aromatic N methyl carbamate in-
secticides. Another approach emphasized the potential of alkyl phosphate meta-
bolites during human pesticide exposure. Earlier methods relied upon the pre-
paration of the ethyl and methyl ester derivatives of the various dialkyl phos-
phates and subsequent analysis by gas chromatography employing a phosphorus
sensitive detector. ' For both of these reasons the earlier techniques did
not lend themselves to adaptation to field exposure studies on account of the
length of the analytical procedure and because at low levels of dialkyl phos-
phate excretions interference from urinary inorganic phosphates were encountered.
These earlier methods were modified by Shafik et al. in 1973, and their modi-
fied method permitted the study of the amyl derivatives of the dialkyl phos-
phates in human monitoring programs. This modified technique involved the
extraction of an acidified urine, derivitization with diazopentane, silica gel
column chromatography and flame photometric gas chromatograph. Recoveries of
the dialkyl phosphate metabolites from human urines spiked at 0.01 - 0.05 ppm
were in the range of 80 - 100%. Only four alkyl phosphates were recognized in
the non-exposed population and in a group of workers exposed to Dasanit, Thimet,
and Di-Syston; these were the dimethyl phosphate (BMP), diethyl phosphate (DEP),
dimethyl thioposhphate (DMTP), diethyl thiophosphate (DETP). Limits of
detectability were0.01 ppm for the dialkyl phosphates and 0.02 for the di-
ethyl phosphorothionates. In six samples from 6 individuals with no record
of exposure to these non-persistent pesticides, the mean concentration of
DMP was 0.012 ppm, for DEP it was 0.05 ppm, for DMTP it was 0.06 ppm and
DETP was detected in only one of the six specimens. In the 6 samples of the
occupationally exposed, the respective means for these metabolites were DMP
0.02 ppm, DEP 0.97 ppm, DMTP 0.09 ppm and DETP 0.60 ppm. Thus, DEP and DETP
concentrations were muchhigher in the exposed group than the general population.
In our project during 1973 we applied this modified method to the study of
different occupational exposure groups working in the field. These groups in-
cluded five highly exposed aircraft loaders and four intermediately exposed
pilots and three non-exposed persons. The major exposure of these workers
was to ethyl-methyl parathion (6-3) mixtures. In the highest exposed group,
the average DMP was 0.25 ppm, the average DEP was 0.48 ppm, the average DMTP
was 0.09 ppm and the average DETP was 0.49 ppm. In the intermediate group,
the averages for these respective metabolites were 0.06 ppm, 0.26 ppm, Not
Detected and 0.11 ppm respectively. None of the alkyl phosphates were detected
in the three non-exposed persons. Since these exposures were predominately
due to the more toxic pesticides severe red blood cell and plasma cholinesterase
inhibition were frequently encountered in the more exposed group. It was thus
-------
possible to correlate concentrations of these metabolites with cholinesterase
levels. DEP, DETP, and DMP were significantly inversely correlated with
red blood cell (RBC) and plasma (PL) cholinesterase (ChE) levels; positive
correlations were observed with PNP levels. All were significant at the "P"
<.C01 level. Thus, our studies confirmed that the urinary metabolites
were an excellent measurement of occupational exposure and might possibly
be used to predict cholinesterase inhibition and illness if the qualitative
and quantitative characteristics of the metabolies were known. We do not
know at what concentrations and which of the alkyl phosphates were the most
important when occupational exposures were becoming excessive. Additional
studies were clearly necessary in workers who were occupationally exposed
to the more toxic pesticides. In this area, parathion mixtures and phosdrin
are known to be the major offenders in worker sickness. The hazard from
these more toxic pesticides were the exposure situations which needed much
further study.
Apart from being probable predictors of cholinesterase inhibition and illness,
preliminary data on the excretion of the urinary metabolites were also ob-
tained following exposure to the less toxic pesticides. Here cholinesterase
inhibition was not to be expected nor was it encountered. What was observed,
however, was ah unexpectedly prolonged excretion of the alkyl phosphate and
phenolic metabolites. It soon became obvious therefore that the study of
these metabolites also had considerable epidemiologic potential.
Urinary metabolite studies following single exposure made us realized that
several of these organophosphates particularly the pesticides containing
halo phenol moieties were soluble in fat, and this was an area which certainly
needed further investigation. Another area of uncertainty was in the descrip-
tive characteristics of these metabolites under conditions of incidental ex-
posure. Very little was known of the magnitude and distribution of these
pesticides in the population at large and information was needed as to how they
were produced and how could the data be interpreted.-, n f<.
These were some of the unknowns recognized as a.jresult of our first year's
activities. In addition, grab samples oJ:_urlne had been obtained and nothing
was known about the sequential excretion of these urinary metabolites. The
studies described in this report take over from this point. In the area
of urinary metabolites we have attempted to throw some light in several
areas and have studied urinary metabolites under differing occupational
pesticide exposure situations and after exposure to several different pesticides.
The alkyl phosphate metabolites that were encountered in several pesticides
are listed in Table 1 and the material and methods, results and discussion
of the several pesticide exposure studies are presented separately with re-
ference to each of the individual pesticides studied.
Description of Phases
The studies this year were not conducted in predetermined chonological order
and the only planned exposure study was a special dichlofenthion (VC-13)
investigation. Cholinesterase determinations were made at different times
in various exposure groups; these were used to justify different exposure
categories. Sequential urinary metabolite data were collected during and
after single and multiple pesticide exposures. Additional data was collected
from the general population and from individuals hospitalized as a result of
over exposure to the pesticide under study.
-------
Table 1. LIST OF PESTICIDES DISCUSSED IN THIS REPORT AND THEIR
DIALKYL PHOSPHATE AND PHENOLIC METABOLITES
Pesticide
Metabolite
A. Dialkyl Phosphates
Ethyl parathion
Methyl parathion
VC-13
DDVP
Cygon (Dimethoate)
Phosdrin (Mevinphos)
Thimet (Phorate)
Dursban
B. Phenols
Ethyl parathion
Methyl parathion ,„.
Dichlofenthion (VC-13W
Dursban
Pentachlorophenol
2,4-D
2,4,5-T
Silvex
Ronnel
Gardona
Lindane
Sevin
DETP, DEP
DMTP, DMP
DETP, DEP
DMP
JJMTP, DMP, DMDTP
DMP
DETP, DEP, DEDTP
DETP, DEP
Paranitrophenol (PNP)
Paranitrophenol (PNP)
2,4-Dichlorophenol (2,4-DCP)
3,5,6-TC Pyridinol (3,5,6-TCP)
PCP
Free phenoxy acid
Free phenoxy acid
Free phenoxy acid
2,4,5-Trichlorophenol (2,4,5-TCP)
2,4,5-Trichlorophenol (2,4,5-TCP)
2,4,5-Trichlorophenol (2,4,5-TCP)
2,3,4,6 Tetrachlorophenol
2,3,4,5 Tetrachlorophenol
2,4,6 Trichlorophenol
2,3,5 Trichlorophenol
Alpha naphthol
-------
Phase I - Cholinesterase categorization of different exposure
groups.
Phase II - Urinary pesticide metabolite studies during and nfter
ethyl-methyl parathion exposures.
Phase III - Urinary pesticide metabolite studies during and after
work exposure to Dursban and DDVP.
Phase IV - Urinary pesticide metabolite studies during and after
phorate (Thimet) exposure.
Phase V - Urinary pesticide metabolite studies during and after
carbaryl (Sevin) exposure.
Phase VI - Urinary metabolite studies following acute and occupa-
tional exposure to dichlofenthion (VC-13).
Phase .VII - Urinary pesticide metabolite studies in the general
population.
Cholinesterase Categorization of Different Pesticide Exposure Groups
Background Information - Determination of the red blood cell and plasma Cholin-
esterase enzyme level is the traditional method of measuring relative degrees
of human exposure to the organophosphate and carbamate insecticides. Pesti-
cides workers particularly the applicator groups, tend to have lower than
average levels of both these enzymes especially if the occupational exposure
has been to the more toxic organophosphate pesticides. In our studies of
occupational effects in South Florida it was obviously necessary therefore
to categorize the different occupational work groups under study with respect
to average levels of these Cholinesterase enzymes.
9
Materials and Results - The Michel method was used in all determinations.
Table 2 presents the man and 'ranges of these enzymes in several differing work
exposure categories. As might be expected, the six hospitalized cases were
the most severely exposed group and the average RBC and plasma Cholinesterase
(ChE) in this group was 0.36 and 0.19 ApH/hr respectively. The mean of the
RBC ChE values was slightly greater than plasma ChE levels because post-PAM
bloods were included in this group and reactivation effects are being reflected
in the RBC ChE mean. The pesticide loaders, applicators (pilots) and formulators
were the next most highly exposed group and the physical nature of their work
and the opportunities for contact and exposure to parathion and Phosdrin were
the major factors in the exposure of this group. The mean RBC ChE was 0.59
ApH/hr and the mean for plasma ChE was 0.57 ApH/hr. The intermediate exposure
group consisted of agricultural and park sprayers as well as structural pest
control operators. The mean RBC ChE was 0.77 ApH/hr and the mean plasma was
0.75 ApH/hr. The average plasma Cholinesterase levels of structural pest con-
tori operators (SPCO) (0.53 ApH/hr) was lower in the two groups because of their
predominant use of Dursban. The low exposure group were made up of agricultural
inspectors and parks groundkeepers and the average levels of both enzymes from
this exposed group were no different than from the averages of the general
population.
Several individuals were subject to repeated Cholinesterase determinations,
either for reasons of surveillance and worker protection, or because of various
-------
Table 2. MEAN AND RANGES OF RED BLOOD CELL AND PLASMA CHOLINESTE''ASE
(ApH/HR) OF DIFFERENT PESTICIDE EXPOSURE GROUPS. 1974.
No. of
Group (number) Specimens
A. HIGH EXPOSED GROUP
Acute Exposure -
Hospitalized
Cases (6)
Occupational Group
Pilots (6)
Loaders (6)
Formulators (9)
Sub Total (21)
ALL HIGH EXPOSED
GROUP (27)
B. MEDIUM EXPOSED GROUP
Park Sprayers (3)
Agricultural
Sprayers (14)
Structural Pest
Control Operators (7)
ALL MEDIUM EXPOSED
GROUP (24)
C. LOW EXPOSED GROUP
6
22
8
34
64
70
6
14
' 9
29
US Dept. of Agriculture
Inspectors (26) 26
Parks Groundkeepers
(53) 74
ALL LOW EXPOSED
GROUP (69)
D. GENERAL POPULATION
(13)
100
13
RBC
mean
0.36
0.55
0.52
0.67
0.61
0.59
0.91
0.70
0.77
0.77
0.64
0.73
0.71
0.74
ChE (ApH/hr)/
ranges
0.08
0.26
0.25
0.20
0.20
0.08
0.68
0.50
0.68
0.50
0.60
0.41
0.50
0.60
- 0.55/f
- 0.75
- 0.80
- 0.90
- 0.90
- 0.90
- 1.15
- 0.90
- 0.90
- 1.15
- 1.20
- 1.30
- 0.91
- 0.89
Plasma ChE (ApH/hr)./
mean
0.19
0.67
0.56
0.56
0.60
0.57
0.78
0.87
0.53
0.75
0.81
0.88
0.84
0.83
ranges
0.07 -
0.30 -
0.30 -
0.35 -
0.30-
0.07 -
0.52 -
0.51 -
0.20 -
0.20 -
0.60 -
0.55 -
0.46 -
0.65 -
0.50//
1.02
0.90
1.09
1.09
1.09
1.05
1.44
0.77
1.44
1.20
0.91
1.30
1.10
/Michel method
//Post PAM blood
10
-------
various project activities such as electroencephalographs or urinary meta-
bolite studies. The results of these are shown in Table 3. The only serious
RBC ChE decline was seen in case #8 whose RBC ChE exhibited a progressive
decline between 2/25/74 and 5/3/74. He was taken off flying as a result of
these levels and earlier urinary metabolite studies of DEP concentraLions and
DEP:DETP ratios were diagnostic of undesirable levels of parathion exposure.
Urinary Metabolite Studies Following Acute and Occupational Exposure
to Ethyl-Methyl Parathion (6-3)
Materials and Methods - Sequential urines were collected after dermal exposures
to 6-3 ethyl methyl parathion concentrations in two occupationally exposed
workers and in one 4*5 year old child. The rate of excretion of the urinary
alkyl phosphate and paranitrophenol pesticide metabolites during the period
of recovery in these three symptomatic cases were compared to the rate of
excretion of these same metabolites in four asymptomatic pesticide workers
during and for a period of up to. 48 hours after being exposed to a 6-3 ethyl
methyl parathion mixture singly or in combination with Phosdrin, Cygon or
parathion 8E. The occupationally exposed workers included an aircraft loader
and three pilots. The loader (W.G.) first mixed and then loaded parathion
6-3 mixtures into a fixed wing aircraft. He wore a long sleeve shirt and
gloves while mixing and loading. The three pilots were helicopter aerial
applicators and were employees of Allied Helicopter Service Inc. They did
not mix or load the chemical themselves and during application each wore
coveralls, a crash helmet and respirator, gloves and rubber boots. They
were partially enclosed in a plastic bubble when flying. When not flying
they would remove their, protective clothing and spend time in the office
adjoining the helicopter hanger. The drums of the pesticide concentrate
were stored outside the hanger.
From the three symptomatic cases of acute exposure, each voided urine was
collected during the period of hospitalization by the nursing staffs of the
two hospitals involved. From the asymptomatic occupationally exposed groups
urines were collected under the supervision of the field investigator during
the day and by the volunteer himself during his time at home after receiving
proper instructions. Urines were collected from the pilots during and after
a period of 48 hours after pesticide application, during which time the pilots
were sitting around the hanger, waiting for the weather to clear and during
which time they were supposedly not occupationally exposed. Two separate
series of urines were collected from the loader one month apart; on both
occasions he was mixing and loading 6-3 ethyl methyl parathion and urines
were collected during work exposure and for a period of 48 hours after. Dur-
ing the second exposure study he also mixed and loaded Cygon and Sevin, and
in the post exposure period he was either at home or sitting around the
work site.
Sequential urine samples were collected in hexane washed jars. The volume
and time of, voiding were recorded with each specimen. The specimens were
stored in dry ice for up to four days and shipped to Miami where they were
frozen at -15 and later analyzed for phenolic and alkyl phosphate metabolites.
The Michel method was used for RBC and plasma ChE and the Shafik et al. modifi-
cation for the gas liquid chromatography analysis of alkyl phosphate metabolites
in urine.*»° The Shafik et al procedure was used for the halogen and nitrophenols
in urine and the Shafik et al procedure for alpha naphthol in urine. ^»H
. 11
-------
Table 3. SEQUENTIAL RED CELL AND PLASMA CHOLINESTERASE LEVELS (ApH/hr) IN
DIFFERENT EXPOSURE GROUPS. SOUTH FLORIDA. JANUARY - DECEMBER 1974.
Date
Occupational
Name Group
RBC
ChE
PI.
ChE
Date
Date
RBC PI.
ChE ChE
1/29/74
1. John P. Formulator 0.78 0.
2. Archie P. " 0.53 0.
3. Tommy W. " . 0.75 0.
4. Steve P. Marginally Exposed
at Formulating Pit 0.70 0.
5. Lewis T. " 0.50 0.
6. Francis B. " 0.72 0.
£ 2/25/74
7. Frank B. Helicopter Pilot
8. Danny A. " "
9. Gordon J. " "
10. Dick D. " "
11. Robert S. Parks Sprayman
12. Estan 0.
0.45 0.
0.46 0.
0.59 0.
4/22/74
0.57 0.
1/16/74
1.00
0.81
0.
1.
47
40
40
72
74
70
68
69
70
54
60
05
3/14/74
0.73 0.
0.70 0.
0.70 0.
0.50 0.
0.68 0.
3/9/74
0.50 0.
3/14/74
0.41 0.
4/22/74
0.59 0.
7/24/74
0.70 0.
3/27/74
1.06 0.
0.68 1.
35
20
45
43
50
73
68
70
50
52
03
RBC
ChE
PI.
ChE
3/29/74
0.65 0.
0.70 0.
0.70 0.
0.77 0,
0.58 0.
4/22/74
0.30 0.
0.26 0.
11/11/74
0.73 1.
0.63 0.
5/29/74
0.88
0.68
0.
0.
45
40
35
60
50
30
50
02
75
50
60
Date Date Date
Mean
RBC PI. RBC PI. RBC PI. RBC PI.
ChE ChE ChE ChE ChE ChE ChE ChE
6/7/74 10/28/74
0.85 0.60 8/14/74 0.70 0
0.60 0.54 0.82 0.45 0.76 0
0.90 0.35 0.89 0.58 0.60 0
0.72 0.90 0.72 0
0.60 0.60 0.63 0
0.45 0.78 0.80 0.80
4/27/74 11/11/74
0.30 0.30 0.69 0.65
5/3/74
0.26 0.50
6/13/74 10/3/74
1
0
.02 0.69 1.15 0.65
.80 1.15
.45 0.75 0.50
.40 0.69 0.42
.35 0.76 0.37
.60 0.72 0.53
.52 0.56 0.56
0.61 0.70
0.45 0.51
0.35 0.59
0.64 0.81
1.02 0.59
0.74 0.96
^Michel method
-------
Results - Exposure Data of Symptomatic Cases - The exposure histories of the
three persons acutely ill revealed that all were the results of excessive ex-
posure to parathion mixtures. T.B., was a 59 y/o w/m employed as a mixer in
a fixed wing aircraft company. On 10/8/74 he started working at 6:00 a.m. load-
ing an aircraft with parathion 6-3, Lannate, and a 30% methyl parathion and
Toxaphene mixture. He wore rubber gloves but was otherwise unprotected.
Within one hour he began to develop cholinergic symptoms and was hospitalized
by 11:30 a.m. Large amounts of atropine and IV infusions of 2-PAM were ne-
cessary for his recovery, and his post-PAM blood showed an RBC and plasma
ChE level of 0.55 ApH/hr and 0.55 ApH/hr respectively.
J.D., a 17 y/o w/m was also an aircraft loader and he too developed choliner-
gic symptoms after mixing and loading ethyl-methyl parathion (6-3) and Lannate.
He was hospitalized at 7:00 p.m. on 11/17/74 and received large amounts of
2-PAM. The RBC and plasma ChE levels were 0.15 pH/hr and 0.10 pH/hr respec-
tively. M.P., the third case was a 4*s y/o w/m who at 2:00 p.m. 5/19/74 while
playing in a barn accidently spilled 1% ounces of ethyl parathion concen-
trate on his blue jeans which he wore until 6:00 p.m. By 8:30 p.m. he was
in acute cholinergic distress and was hospitalized shortly thereafter. The
post-PAM cholinesterase levels of RBC and PI. ChE were 0.55 ApH/hr and 0.18
ApH/hr respectively. Large amounts of paranitrophenol were identified in all
three cases providing confirmatory evidence of parathion exposures.
Exposure Data of Asymptomatic Pesticide Workers - The exposure histories
and cholinesterase levels of the loader and three pilots were presented in
Table 4. All were in good health during the study period.
Sequential Urinary Pesticide Data of Symptomatic Cases - Tables 5, 6 and
7 present the individual concentrations of the alkyl phosphate metabolites
and PNP levels from three individuals during their period of hospitalization
on account of cholinergic manifestations.
Sequential Urinary Pesticide Data of Asymptomatic Cases of Pesticide
Workers - Tables 8, 9, 10, 11 and 12 present similar data from the symptomatic-
ally exposed workers. Although all had occupational exposures to parathion
mixtures, the occupationally exposed workers had additional work exposures to
Phosdrin, Cygon and Sevin; the first two would add additional dimethyl alkyl
phosphate metabolites. Exposures to ethyl parathion would be reflected by
the excretion of the diethyl thiophosphates (DETP) and PNP, and the oxidation
of the intact compound to paraoxon would result in the excretion of diethyl
phosphate (DEP) and PNP. Exposure to methyl parathion would result in the
appearance.of dimethyl thiophosphate (DMTP) and PNP in the urine and the oxida-
tion of the intact compound to paraoxon would result in the excretion of di-
methyl phosphate (DMP) and PNP. In addition, Phosdrin would elicit a DMP res-
ponse and Cygon would result in DMP, DMTP, DMDTP, although the latter meta-
bolite is not encountered in occupational types of exposure. Sevin exposure
would be recognized by the excretion of alpha naphthol. Because of the mixed
exposure that some of the workers encountered, the only urinary metabolites
that were specifically reflective of exposure to ethyl-methyl parathion 6-3
were the diethyl metabolites of ethyl parathion (DETP and DEP). The excre-
tion of these metabolites therefore was especially studied in this compari-
son of 6-3 ethyl-methyl parathion exposures. Ethyl parathion metabolizes to
the oxon which is known to be far more toxic than is the parent compound so
that DEP reflects a greater potential for toxicity than does DETP.
13
-------
Table 4. 'EXPOSURE HISTORY AND CHOLINESTERASE LEVELS (ApH/hr)
' OF OCCUPATIONALLY EXPOSED ASYMPTOMATIC PESTICIDE WORKERS.
Name
W.G.
W.G.
P.B.
G.J.
D.A.
Category Date Chemical
Loader 1/26/74 Parathion
6-3
Loader 2/27/74 Parathion
. 6-3
2/28/74 Sevin
2/28/74 . Cygon
Pilot 2/24/74 Parathion
6 - .3
Parathion
6-3 and
Phosdrin
2/25/74 Parathion
6-3
Parathion
8E
Pilot 2/24/74 Phosdrin
Cygon
Parathion
6-3
Pilot 2/24/74 Parathion
6-3
Parathion
8E and
Cygon
„. Exposure time
lime
.in minutes
9:15 -
11:15 am
9:00 -
11:30 am
7:30 -
11:30 am
1:00 -
6:30 pm
4:00 -
4:10 pm
4:30 -
8:25 pm
8:45 -
9:00 am
5:25 -
7:05 pm
10:05 -
10:55 am
5:00 -
5:05 pm
6:55 -
7:35 pm
10:05 -
10:20 pm
10:30 -
11:30 am
120
150
240
330
10
235
15
100
50
5
40
15
60
Cholinesterase
RBC Plasma
0.60 0.80
0.45 0.6.8
0.59 0.70
0.46 0.69
Michel method (ApH/hr)
14
-------
Table 5. SEQUENTIAL URINARY EXCRETION RATES OF ALKYL PHOSPHATES AND PARANITROPHENOL
IN A SPRAYMAN (T.B.) HOSPITALIZED FOR ACUTE DERMAL PARATHION INTOXICATION.
Date
Hospital //
Admission 10/08/74
Initial urine
collection 10/08/74
10/08-09/74
10/09/74
10/09/74
10/10/74
10/11/74
10/11/74
10/11/74
10/11/74
10/11/74
10/11-12/74
10/12/74
10/12/74
10/12/74
10/12/74
10/12/74
10/12/74
Time
11:
5:
11:
5:
11:
5:
8:
8:
9:
10:
11:
12:
1:
2:
4:
4:
6:
35
00
00
00
00
00
00
45
15
00
30
50
30
45
15
45
15
am
pm-ll:00
pm- 5:00
am- 11: 00
am- 5:00
am- 11: 00
? 8:00
pm- 8:45
pm- 9:15
pm-10:00
pm-ll:30
pm-12:50
am- 1:30
am- 2:45
am- 4:15
am- 4:45
am- 6 : 15
am- o : 45
ml
voided
pm
am
am
pm
am
pm
pm
pm
pm
pm
am
am
am
am
am
am
am
500
315
250
800
250
210
165
165
210
330
275
400
800
200
250
400
625
DMP
ug/ ug/vol
ml voided
0.348
0.256
0.083
0.045
0.194
0.025
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
174iO
80.6
20.8
36.0
48.5
5.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ug/
hour
29.0
13.4
3.5
6.0
8.1
?
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ug/
ml
0.259
0.119
0.069
ND
0.091
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
DMTP
ug/vol
voided
129.5
37.5
17.3
ND
22.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ug/
hour
21.6
6.2
2.9
ND
3.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
/^Post-PAM cholinesterase RBC 0.55 ApH/hr and plasma 0.55 ApH/hr
Methyl parathion and ethyl parathion identified in blood at a level of 3 ppb and 14.3 ppb respectively
ND=Not detectable;
Limits of detectability: DMP 0.015, DMTP 0.026
?=Previous hour not known
-------
Table 5 (Continued)
DEP
DETP
PNP
Date
Time
ml ug/ ug/vol ug/ ug/ ug/vol ug/ ug/ ug/vol ug/
voided ml voided hour ml voided hour ml voided hour
Hospital , ,
admission" 10/08/74
Initial urine
collection 10/08/74
10/8-9/74
10/09/74
10/09/74
10/10/74
10/11/74
10/11/74
10/11/74
10/11/74
10/11/74
10/11-12/74
10/12/74
10/12/74
10/12/74
10/12/74
10/12/74
10/12/74
11:35
5:00
11:00
5:00
11:00
5:00
?
8:00
8:45
9:15
10:00
11:30
12:50
1:30
2:45
4:15
4:45
6:15
am
pm-ll:00 pm
pm- 5:00 am
am-lL 00 am
am- 5:00 pm
am-ll:00 am
- 8:00 pm
pm- 8: 45 pm
pm- 9: 15 pm
pm-10:00 pm
pm-11: 30 pm
pm-12: 50 am
am- 1:30 am
am- 2:45 am
am- 4: 15 am
am- 4:45 am
am- 6: 15 am
am- 6: 45 am
500 0.882
513 0.672
250 0.257
800 0.183
250 0.595
210 0.102
165 0.044
165 0.031
210 0.025
330 0.018
275 0.042
400 0.064
800 0.028
200 0.039
250 0.059
400 ND
625 0.056
441.0
211.7
64.3
146.4
148.8
21.4
7.3
5.1
5.3
5.9
11.6
25.6
22.4
7.8
14.75
ND
35.0
73.5
35.3
10.7
24.4
24.8
7
UC
uc
UC
4.0
8.7
UC
17.9
5.2
UC
ND
UC
0.330
0.252
0.167
ND
0.061
0.073
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
165.0
74.4
41.8
ND
15.3
15.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
17.5
13.2
7.0
ND
15.3
7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
2.14
0.880
0.630
0.204
0.590
0.186
0.064
0.030
0.048
0.048
0.064
0.052
0.078
0.64
1,070.
277.
157.
163.
147.
39.1
10.6
5.0
5.8
15.8
17.6
20.8
19.5
40.0
170.0
46.2
26.3
27.34
24.6
7
UC
UC
UC
10.6
13.2
UC
UC
UC
ND-Not detectable
Limits of detectability: DEP 0.020; DETP 0.032
?=Previous hour not known
UC=Unable to calculate less than 1 hour
-------
Table 6. SEQUENTIAL URINARY EXCRETION RATES OF ALKYL PHOSPHATES AND PARANITROPHENOL
IN A SPRAYMAN (JD) HOSPITALIZED FOR ACUTE PARATHION INTOXICATION - DERMAL EXPOSURE
A. ALKYL
Hospital
Initial
. — . — . '• — —
PHOSPHATE DATA ml DMP
Date Time void ug/ml ug/w ug/hr ug/ml
Admission1''' 11/19/74 7:00 pm
Urine 11/20/74 7:15 am-4:50 pm 276 0.372 102.7 10.7 0.038
11/20-21/74 4:50 pm-8:30 am 554 0.504 279.2 17.8 0.096
11/21/74 8:30 am-10:19 am 186 0.235 43.7 24.1 0.029
10:19 am-12:30 pm 288 0.336 96.8 42.4 0.081
12:30 pm-8: 40 pm 69 0.284 19.6 2.40.039
11/21-22/74 8:40 pm-5:30 am 358 0.388 138.9 15.7 0.057
.11/23/74 12:47 am-8:00 am 292 0.222 64.8 8.980.040
B. PHENOLIC DATA ml PHP
void ug/ml ug/w ug/hr
Initial
Urine 11/20/74 7:15 am-4:50 pm 276 1.14 314.6 32.8
11/20-21/74 4:50 pm-8:30 am 554 2.36 L307.4 83.5
11/21/74 8:30 am- 10: 19 am 186 0.88 163.7 90.1
10:19 an»-12:30 pm 288 1.4 403.2 176.6
12:30 pm-8: 40 pm 69" ' 0.6 41.4 5.1
11/21-22/74 8:40 pm-5:30 am 358 0.92 329.4 37.3
11/23/74 12:47 am-8:00 am 292 0.64 186.9 25.9
DMTP
ug/w
10.48
53.2
5.39
23.3
2.69
20.4
11.7
ug/hr
1.1
3.4
3.0
10.2
0.3
2.3
1.6
ug/ml
0.
0.
0.
0.
0.
0.
0.
992
278
824
896
79*
972
676
DEP
ug/w
273.8
711.3
153.3
258.1
54. -9
347.98
197.39
ug/hr
28.6
45.4
84.4
113.0
6.7
39.4
27.4
ug/ral
0.096
0.278
0.090
0.195
0.080
0.174
0.12
DETP
ug/w
26.5
154.0
16.7
56.2
ug/ml
2.8
9.8
9.2
24.6
. 5.52 0.64
62.3
35.0
7.1
4.9
//RBC ChE 0.15 6pH/hr and PI. ChE 0.10 ApH/hr
Methyl parathion 3.3 ppb and ethyl parathlon 14.3 ppb in blood
-------
Table
URINARY ALKYLPHOSPHATE AND PHENOLIC LEVELS IN AN ACUTE INTOXICATION OK
PARATHION IN A 4Jj YEAR OLD WHITE MALE (MATTHEW P.). DADE COUNTY. FLA.
Hospital
Date
Admission// 5/19/74
Initial
Urine
5/20/74
5/21/74
5/21-22/74
5/22/74
6/16/74
Hour
9:30 pm
7 am-1 pm
1 am- 7am
7 am-1 pm
1 pm- 7 pm
7 pm-1 am
1 am-7 am
7 am- 8 am
7:15-8:10 pm
ml
w
200
439
550
320
283
650
40
15
ug
ml
0.298
0.067
0.042
0.045
0.042
ND
ND
to
DMP
ug ug
w hr
59.6 9.9
29.4 4.9
23.1 3.9
14.4 2.4
11.9 2.
ND ND
ND ND
ND HD
ug
ml
0.342
0.342
0.304
0.351
0.364
0.649
0.577
RD
DMTP
ug
w
68.4
150.1
167.2
112.3
103.0
421.9
23.1
NO
ug
hr
11.4
25.
27.8
18.7
17.2
70.
23.1
ND
"g
ml
2.21
0.456
0.265
0.252
0.211
0.123
0.091
ND
DEP
"8
vv
442.0
200.2
145.8
80.6
59.7
80.0
3.6
ND
ug
hr
73.7
33.4
24.3
13.4
10.
13.3
3.6
ND
DKTP PNP
ug ug ug ug ug ug
ml w hr ml w hr
1.48 296.0 49.3 2.26 452.0 753
0.177 77.7 13 0.5 219.5 36.5
0.127 69.9 11.6 0.186102.3 17.1
O.1O6-34.6 5.8 0.206 65.9 10.9
0.094 26.6 4.4 0.198 56.0 9.3
0.128 83.2 133 0.134 87.1 14.5
0.101 4,0 4. 0.086 3.4 3.4
ND 'ND ND ND ND N
Q&Voat-Vam RBC ChK 0.55 ApH/hr and PI. ChE 0.18 ApH/hr
ND^Not Detectable
Limits of detectabillty; DMP 0.03; DMTP, DEP and DETP 0.04
PNP 0.009
-------
Table 8. SEQUENTIAL ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETIONS IN A LOADER AFTER TWO HOURS
EXPOSURE TO MIXING AND LOADING ETHYL METHYL PARATHION. DADE COUNTY. 1974 (W.G."#!).
Dade
1974 Hour
ml
voided
ug/
ml
DMP
ug/vol
voided
ug/ ug/
hr. ml
DMTP
ug/vol
voided
ug/ ug/
hr. ml
DEP
ug/vol
voided
ug/ ug/
hr. ml
DETP
ug/vol
voided
ug/ ug/
hr ml
PNP
ug/vol ug/
voided hr .
1/26 9:45 am
11:30 am
2:30 pm
7:15 pm
1/27 1:00 am
6:35 am
10:43 am
6:20 pm
10:00 pm
1/28 2:30 am
7:15 am
225
250
295
400
400
475
475
425
395
425
400
ND
ND
ND
ND
0.056
0.069
0.063
0.053
0.026
0.042
ND
ND
ND
ND
ND
22.4
32.8
29.9
22.5
10.3
17.9
ND
ND
ND
ND
ND
3.9
5.9
7.2
3.0
2.8
4.0
ND
0.145
0.118
0.079
0.193
0.155
0.087
0.070
0.077
0.074
0.082
0.090
32.6
29.5
23.3
77.2
62.0
41.3
33.3
32.7
29-. 2
34.9
36.0
26.1
16.9
7.8
16.3
10.8
7.4
8.0
4.3
8.0
7.8
5.3
ND
ND
ND
ND
0.058
0.058
0.061
0.062
0.029
0.047
ND
ND
ND
ND
ND
23.2
27.6
29.0
26.4
11.5
20.0
ND
ND
ND
ND
ND
4.0
4.9
7.0
3.5
3.1
4.4
ND
0.061
0.093
0.192
0.116
0.084
0.184
0.297
0.254
0.204
0.183
0.170
13.7
23.3
56.6
46.4
33.6
87.4
141.1
108.0
80.6
77.8
68.0
11.0
13.3
18.9
9.8
5.8
15.7
34.1
14.2
22.0
17.3
10.1
0.025
0.034
0.064
0.21
0.187
0.124
0.09
0.108
0.039
0.059
0.032
5.6
8.5
18.9
84.0
74.8
58.9
42.8
45.9
15.4
25.1
12.8
4.5
4.9
6.3
17.7
13.0
10.5
10.3
6.0
4.2
5.6
1.8
ND=Not detectable
Limits of detectability are:
DMP 0.02, DEP 0,02, DMTP
PNP 0.009 for phenols
0,03 and DETP 0.03 for alkyl phosphates
-------
Table 9. SEQUENTIAL ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETIONS IN A LOADER (W.G. #2) AFTER 2h HOURS
EXPOSURE TO MIXING AND LOADING 6-3 ETHYL METHYL PARATHION AND 12 HOURS MIXING AND LOADING CYGON
AND SEVIN. DADE COUNTY 1974
10
o
A. Alkyl Phosphate Data
Date
1974
2/27
2/28
3/1
Hour
11:30 am
2:00 pm
9:00 pm
11:15 pm
1:30 am
4:30 am
7:00 am
5:30 pm
6:30 pm
1:30 am
3:20 am
7:08 am
9:00 am
ml
voided
300
250
250
200
200
400
250.
175
225
250
340
340
250
ug/
ml
ND
ND
0.042
0.035
0.049
0.026
0.022
0.029
0.031
0.038
0.025
0.033
0.028
DMP
ug/vol
voided
ND
ND
10.5
7.0
9.8
10.4
5.5
5.1
7.0
9.5
8.5
11.2
7.0
ug/
hour
ND
ND
1.5
3.1
4.4
3.5
2.2
0.5
7.0
1.4
4.6
3.0
3.8
DMTP
ug/ ug/vol
ml voided
0.174 52.2
0.102 25.5
0.059 14.8
0.107 21.4
0.089 17.8
0.163 65.2
0.156 39.0
0.049 8.6
0.070 15.8
0.059 14.8
0.061 20.7
0.043 13.6
0.048 12.0
DEP
ug/ ug/ ug/vpl ug/ ug/
hour ml voided hour ml
13.10 0.044 13.2 3.3 0.065
10.20 0.039 9.8 3.9 0.123
2.10 0.071 17.8 2.5 0.141
9.50 0.052 10.4 4.6 0.080
7.90 0.078 15.6 6.9 0.067
21.70 0.042 16.8 5.6 0.071
15.60 0.034 8.5 3.4 0.074
0.82 0.061 10.7 1.0 0.097
15.80 0.072 16.2 16.2 0.070
2.10 0.055 13.8 2.0 0.130
11.30 0.051 17.3 9.5 0.109
3.60 0.058 19.7 5.2 0.155
6.40 0.056 14.0 7.5 0.102
B. Phenolic Data
Date
1974
2/27
2/28
3/1
Hour
11:30 am
2:00 pm
9:00 pm
11:15 pm
1:30 am
4:30 am
7:00 am
5:30 pm
6:30 pm
1:30 am
3:20 am
7:08 am
9:00 am
ml
voided
300
250
250
200
200
400
250
175
225
250
340
340
250
ug/
ml
0.220
0.262
0.428
0.406
0.270
0.226
0.118
0.218
0.203
0.263
0.110
0.105
0.073
PNP
ug/vol
voided
66.0
65.5
107.0
81.2
54.0
90.4
29.5
38.2
45.7
65.8
37.4
35.7
18.3
ug/
hour
1.' . 5
26.2
5.3
36.1
24.0
30.1
11.8
3.6
45.7
9.4
20.4
9.4
9.8
Alpha-Naphthol
ug/ ug/vol
ml voided
0.0073 1.83
0.0220 3.9
0.014 3.2
0.0273 6.8
0.0173 5.9
0.0155 5.3
0.0302 7.6
ug/
hour
0.73
0.40
3.2
1.0
3.2
1.4
4.1
ND=Not detectable
Limits of detectability for
are: DMP 0.02, DEP 0.02,
DETP
ug/vol
voided
19.5
30.8
35.3
16.0
13.4
28.4
18.5
17.0
15.8
32.5
37.1
52.7
25.5
alkyl
DMTP
ug/
hour
4.9
12.3
5.0
7.1
6.0
9.5
7.4
1.6
15.8
4.6
20.2
13.9
13.7
phosphates
0.03 and
A A <• 1
DETP
•
and for phenols they are: PNr u.uuy ana axpna
naphthol 0.006
'0.04
-------
Table 10. URINARY ALKYL PHOSPHATE EXCRETIONS IN A HELICOPTER PILOT (F.B.) DURING AND AFTER
OCCUPATIONAL EXPOSURE TO PARATHION MIXTURES, PHOSDRIN AND CYGON. SOUTH FLORIDA 1974
Date
1974
2/24
2/25
2/26
2/27
Hour
3:15 pm
5:20 pm
11:20 am
12:30 pm
7:20 pm
8:45 pm
6:10 am
8:30 am
9.43 am
11:00 am
4:10 pm
6:30 pm
7:30 pm
9:50 pm
6:00 am
7:30 am
9:00 am
9:50 am
10:30 am
ml
voided
325
100
175
175
175
125
175
100
200
425
150
150
150
150
325
50
125
150
250
DMP
ug/ ug/vol
ml voided
ND
0.047
0.023
0.035
ND .
0.030
0.090
0.080
0.042
ND
0.063
0.037
0.028
0.022
0.035
0.049
0.042
ND
ND
ND
4.7
4.03
6.13
ND
3.75
15.75
8.0
8.4
ND
9.45
5.55
4.2
3.3
11.38
2.45
5.25
ND
ND
ug/ ug/
hour ml
UC 0.287
2.26 0.195
UC 0.137
6.13 0.155
ND 0.131
2.65 0.443
UC. 0.169
3.4 0.132
6.9 0.352
ND 0.262
1.83 0.199
2.38 0.081
4.2 0.115
1.41 0.318
1.4 0.107
1.63 0.084
3.5 0.105
ND 0.059
ND 0.056
DMTP
ug/vol
voided
93.28
19.50
23.98
27.13
22.93
55.38
29.58
13.20
70.40
111.35
29.85
12.15
17.25
47.70
34.78
4.20
13.13
8.85
14.0
DEP
ug/ ug/ ug/vol
hour ml voided
UC 0.034
9.36 0.111
UC 0.030
27.13 0.078
3.36 0.086
39.1 0.088
UG 0.262
5.7 0.197
57.9 0.055
86.8 0.037
5.8 0.187
5.2 0.085
17.25 0.054
20.44 0.044
4.26 0.111
2.80 0.137
8.75 0.105
8.85 0,048
14.0 ND
11.05
11.1
5.25
13.65
15.25
11.00
45.85
19.7
11.0
15.72
28.05
12.75
8.1
6.6
36.08
6.85
13.13
7.42
ND
DETP
PNP
ug/ ug/ ug/vol ug/ ug/ ug/vol
hour ml voided hour ml voided
UC 0.098 31.85 UC 0.052
5.33 0.320 32.00 15.4 ND:
UC 0.03 5.25 UC 0.026
13.65 0.045 7.88 7.8 0.048
2.2 0.063 11.03 1.6 0.042
7.77 0.172 21.50 15.2 0.130
UC 0.441 77.16 UG 0.022
8.44 0.372 37.20 15.9 0.048
9.04 0.113 22.60 18.6 0.080
12.55 0.065 27.63 21.5 0.038
5.43 0.350 52.50 10.2 0.02
5.46 0.251 37.65 16.1 0.02
8.1 0.127 19.05 19.0 0.096
2.83 0.175 26.25 11.2 0.144
4.4 0.279 90.68 11.1 0.030
4.57 0.152 7.60 5.1 0.088
8.75 0.150 18.75 12.5 0.018
7.2 0.141 21.15 21.1 0.062
ND 0.087 21.75 21.7 0.022
16.9
ND
4.6
8.4
7.4
16.3
3.9
4.8
16.0
16.2
0.02
0.02
14.4
21.6
9.8
4.4
2.3
9.3
5.5
ug/
hour
UC
ND
UC
8.4
1.1
11.5
UG
2.1
13.2
12.6
0.02
0.02
14.4
9.3
1.2
2.9
1.5
9.3
5.5
NP«=Notdetectable
Limits of detectability: DMP 0.02, DEP 0.02,
UC=Unable to calculate previous hour not known
DETP :0.03, DMTP 0.03 and PNP 0.009
-------
Table 11. URINARY ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETION IN A HELICOPTER PILOT (G.J.) 24
HOURS AFTER OCCUPATIONAL EXPOSURE TO PARATHION, PHOSDRIN AND CYGON. 1974
ho
to
• • . . • • ;- .
Date
1974
2/25
2/26
2/27
UNot
Hour
11:45 am
3:00 pm
5:05 pm
7:50 pm
10:35 pm
5:30 am
7:05 am
8:50 am
10:34 am
1:00 pm
3:25 pm
5:25 pm
8:20 pm
2:15 am
4:50 am
7:30 am
9:00 am
detectable
ml
voided
300
108
225
525
225
275
441
320
225
225
201
358
226
215
325
225
340
Lmits of detectability:
ug/
ml
0.050
0.051
0.051
ND
0.039
0.070
ND
ND
0.039
ND
ND :
ND
ND
ND
ND
0.035
ND
DMP
PNP.
DMP DMTP
ug/vol ug/ ug/ ug/vol
voided hour ml voided
15.0 10.6 0.231 69.3
5.5 1.7 0.059 6.37
11.5 5.5 0.153 34.4
ND ND 0.119 62.5
8.78 3.2 0.151 34.0
19.3 2.8 0.120 33.0
ND ND 0.109 48.1
ND ND 0.107 34.2
8.78 5.1 0.028 6.30
ND NB. ND ND.
ND ND. ND ND
ND ND ND ND
ND ND ND ND
ND ND ND ND
ND ND ND ND
7.87 2.9 ND ND
ND ND ND ND
0.03, DEP 0.04, DMTP 0.
0.009
ug/ ug/
hour ml
48.9 0.129
2.0 0.180
16.5 0.128
22.7 0.069
12.4 0.116
4.8 0.172
30.4 "ND
19.6 ND
3.6 0.193
ND. 0.137
ND 0.106
ND 0.061
ND 0.048
ND 0.120
ND 0.069
ND 0.097
ND 0.060
03 and DETP
DEP
ug/vol
voided
38.7
19.4
49.1
36.2
26.1
47.3
. ND.
ND
43.4
30.8
21.3
21.8
10.9
30.7
22.4
21.8
20.4
0.03
ug/ ug/
hour ml
27.3 0.058
6.0 0.127
23.5 0.145
13.2 ND .
9.5 0.113
6.8 0.165
ND 0.065
ND 0.055
25.1 0.079
12.7 0.031
8.8 0.037
10.9 ND ;
3.7 ND
5.2 0.088
8.9 0.06
8.2 0.05
13.6 ND
:DETP .
ug/vol
voided
17.4
13.4
32.6
Nfl
25.4
45.4
28.7
17.6
17.8
6.97
7.43
.ND.
ND .
22.5
18.5
10.6
NB
ug/ ug/
hour ml
12.3 0.160
4.2 0.252
32.6 0.338
NB 0.096
9.3 0.274
6.6 0.336
18.1 0.060
10.1 0.032
10.3 0.336
2.9 0.168
3.0 0.190
ND 0.072
ND 0.076
3.8 0.308
7.0 0.094
3.9 0.132
ND 0.050
PNP
ug/vol
voided
48.0
27.2
76.1
50.4
61.7
92.4
26.5
10.2
75.6
37.8
38; 2
25.8
17.2
78.8
30.6
29.7
17.0
ug/
hour
33.9
8.4
36.5
18.3
22.4
13.4
16.7
5.9
43.6
15.5
15.8
12.9
5.9
13.3
11.8
11.1
11.3
-------
Table 12. URINARY ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETION RATES IN A HELICOPTER-PILOT
(DA) 24 HOURS AFTER OCCUPATIONAL EXPOSURE TO PARATHION MIXTURES AND CYGON.
Isi
U)
Date
1974
2/25
2/26
2/27
Hour
11:05 am
4:00 pm
7:30 pm
8:48 pm
7:20 am
8:55 am .
10:35 am
3:45 pm
5:25 pm
6:30 pm
7:30 am
10:25 am
DMP
ml ug/ ug/vol
Voided ml voided
160
250
150
220
60
275
350
200
160
125
75
260
0.083
0.128
0.067
0.044
0.085
0.035
0.029
0.050
0.056
0.073
0.059
0.033
13.28
32.0
10.05
9.68
5.1
9-63
10.15
10.0
8.96
9.13
4.43
8.58
DMTP
ug/ ug/ ug/vol
hour ml voided
UC 0.032
6.5 0.317
2.9 0.342
7.5 0.345
UC 0.198
6.1 0.244
6.1 0.273
1.9 0.285
5.4 0.294
8.4 0.210
UC 0.320
2.9 0.218
53.1
79.25
51.3
75.9
11.9
67.1
95.55
57.0
47.0
26.25
24.0
56.68
ug/ ug/
hour ml
UC 0.240
16.1 0.446
14.7 0.199
58.4 0.134
UC 0.395
42.4 0.169
57.3 0.081
11.0 0.211
28.2 0.246
24.2 0.343
UC 0.377
19.4 0.142
DEP
ug/vol
voided
38.4
111.5
29.85
29.48
23.7
46.48
28.35
42.2
39.36
42.88
28.28
36.92
ug/
hour
UC
22.7
8.5
22.7
UC
29.4
17.0
8.2
23.6
39.6
UC
12.7
DETP
ug/ ug/vol ug/ ug/
ml voided hour ml
0.171 27.36 UC 0.092
0.309 77.25 15.7 0.540
0.185 27.75 7.9 0.282
0.140 30.8 23.7 0.172
0.284 17.0 UC 0.470
0.146 40.15 25.4 0.112
0.127 44.45 26.7 0.046
0.220 44.0 8.5 0.236
0.249 39.84 23.9 0.340
0.284 35.5 32.8 0.364
0.214 16.1 UC 0.408
0.137 35.62 12.2 0.102
PNP
ug/vol
voided
39.6
135.0
42.3
37.8
28.2
30.8
16.1
47.2
, 54, 4
45.5
30.6
26.5
ug/
hour
UC
27.5
12.1
29.1
UC
19.5
.9.7
9.1
32.6
42.0
UC
3.. 2
UC=Unable to calculate previous hour not known
-------
The excretion levels of these several metabolites are shown in Table 5
through 12. The data are expressed in three ways, namely, micrograms
per milliliter (ug/ml), micrograms per volume voided (ug/w) and micro-
grams excreted per hour (ug/hr). We have come to realize that expressions
of data such as micrograms excreted per hour are subject to considc able
error, especially if the collections are made under field condition;. The
volumes of urines excreted at each voiding are subject to inaccuracies as
is also exact time of voiding. Too often, it has been our experience, that
participants tend to approximate to the nearest 1/2 hour rather than record
the exact time of voiding. In addition, since part of the sample collection
is during the leisure hours at home there is no certainty that the t^tal 24
hour output is being accurately collected. The micrograms of the metabolite
excreted per hour are calculated by multiplying the micrograms of the meta-
bolite per milliliter of urine by the volume of urine voided and dividing
this by the time interval between each voiding. Thus, two series of errors
.are built into the quantisation of these exposures of these metabolites when
expressed in micrograms per hour.
With this principle in mind therefore the following figures 1 through 8 com-
pare the excretion of these metabolites in the three symptomatic individuals
during their period of hospitalization with the profile observed in the
occupationally exposed group. Pesticide metabolite concentrations were
expressed in micrograms per milliliter (ug/ml) in all these samples.
It will be apparent that both quantitative and qualitative differences exist
in the alkyl phosphate and PNP excretion rates when the symptomatic groups
are compared with the asymptomatic occupational group. The first point that
is suggested by this comparison is a quantitative one. In all first urines,
concentrations of DEP were >0.4 ug/ml; concentrations of this metabolite
were at or above this level in all of the urines voided within the first 48
hours of hospitalization. In contrast, in the 71 urines analyzed from the
asymptomatic group only one sample was >0.4 ug/ml. When we reviewed four
other cases of ethyl methyl parathion intoxications not described in this
report we were able to confirm these findings, and Table 13 lists the con-
centrations of DEP, DETP and PNP in the first urines collected and cholin-
esterase levels in seven cases of parathion poisonings. It will be noted
that all had DEP concentrations of >0.4 ug/ml and all weve dermally over ex-
posed except for case //3 who ingested parathion, and v-is therefore an oral
exposure rather than a dermal exposure; highest levels of DEP were seen in
this case.
The second point that is suggested from this comparison is a qualitative one.
In all three of the parathion poisoning cases, in all the urines collected
during 48 hours of hospitalization, concentrations of DEP were always greater
than the concentrations of DETP. The same was true for the additional poison-
ing cases listed in Table 13. If the relationship of these two metabolites
to each other is expressed as a ratio, the DEPiDETP ratio was considerably
greater than unity. In the five occupational studies, the picture was re-
versed in all but two individuals (G.J. and D.A.), and DETP concentrations
we're for the most part greater than DEP concentrations. It is difficult to
explain why this was not the case .with the two exceptions but it will be
noted that the differences between DEP and DETP in these individuals were not
nearly so striking as were the differences of these two metabolites in the
24
-------
Figure 1. SEQUENTIAL URINARY EXCRETION RATES OF ALKYL PHOSPHATES AND
PARANITROPHENOL IN A SPRAYMAN (TB) HOSPITALIZED FOR ACUTE
DERMAL PARATHION EXPOSURE.
jug/ml
.40
.30
.20
.10
.8
.4
0
2.0
1.0
T.B.
V
I I
DMP
DMTP
PNP
6
PM
6
6
AM PM
10-9
6
AM
6
PM
10-10
6 6
AM PM
10-11-74
6
AM
hour
25
-------
Figure 2. SEQUENTIAL URINARY EXCRETION RATES OF ALKYL PHOSPHATES AND
PARANITROPHENOL IN A SPRAYMAN (JD) HOSPITALIZED FOR ACUTE
PARATHION INTOXICATION - DERMAL
• DMP
° DMTP
2.4 r
1.6
_L
I
6
AM
6
PM
6
AM
6
PM
11-20
11-21
666
AM PM AM
11-22
PM
11-23-74
hour
26
-------
Figure 3. SEQUENTIAL URINARY EXCRETION OF ALKYL PHOSPHATE AND PARANITRO-
PHENOL IN A 4 1/2 YEAR OLD WHITE MALE (MP) HOSPITALIZED FOR
ACUTE PARATHION INTOXICATION - DERMAL
• DMP
DMTP
2.4
1.6
.8
DEP
DETP
2.4
1.6
.8
PNP
6 6
AM PM
5-20
6 6
AM PM
5-21
/
6 6
AM PM
5-22
AM hour
6-16-74
27
-------
Figure 4. SEQUENTIAL ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETIONS IN
A LOADER AFTER TWO HOURS EXPOSURE TO MIXING AND LOADING 6-3
ETHYL METHYL PARATHION - DADE COUNTY, 1974 (WG #1)
• DMP
OMTP
.30
.20
.10
0
DEP
DETP
a .,•
.24
.16
.08
/
JL
J.
PNP
J.
JL
6 AM 6 PW
1-26-74
6 AM 6 PM
1-27-74
6AM
hour
28
-------
Figure 5. SEQUENTIAL ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETIONS IN A
LOADER (WG #2) AFTER 21/2 HOURS EXPOSURE TO MIXING AND LOADING
6-3 ETHYL METHYL PARATHION AND 12 HOURS MIXING AND LOADING CYGON
DADE COUNTY, 1974
DMP
DMTP
.15
.10
.05
0
.60
.40
.20
PNP
6 AM 6 PM
2-27-74
6 AM 6 PM
2-28-74
6AM
hour
29
-------
Figure 6.
URINARY ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETION IN A
HELICOPTER PILOT (FB) DURING AND AFTER APPLICATION OF
PARATHION MIXTURES, PHOSDRIN AND CYGON
DMP
DMTP
.15
.10
.05
PNP
b 6
M PM
2-24
6 6
AM PM
2-25
6
AM
6
PM
2-26
6
AM
2-27
6
PM
-74
hour
30
-------
Figure 7. URINARY ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETION .N A
HELICOPTER PILOT (GJ) 24 HOURS AFTER OCCUPATIONAL EXPOSURE
. TO PARATHION, PHOSDRIN AND CYGON
DMP
DMTP
o-c»—o-c» —
.32
.24
.16
.08
A A
6AM 6PM
2-25-74
6AM 6PM
2-26-74
6AM
hour
31
-------
Figure 8. URINARY ALKYL PHOSPHATE AND PARANITROPHENOL EXCRETION RATES
IN A HELICOPTER PILOT (DA) 24 HOURS AFTER OCCUPATIONAL
EXPOSURE TO PARATHION MIXTURES AND CYGON
.4
.3
.2
.1
0
D.A.
PNP
A/ly
6 AM 6 PM
2-25-74
6AM 6PM
2-26-74
6AM
hour
32
-------
Table 13. . LEVELS OF URINARY METABOLITES OF ETHYL PARATHION IN FIRST
URINE SAMPLES ANALYZED IN SEVEN CASES OF PARATHION POISONING
Case
No.
1.
2.
3.
4.
5.
6.
7.
Name
Frank R.
Maynard W.
Chris W.
Jimmy J.
Matthew P.
Tony B
James D.
DEP
ug/ml
0.46
0.44
7.84
1.47
2.21
0.88
0.99
DETP
ug/ml
0.28
0.16
0.09
0.31
1.48
0.30
0.10
PNP
ug/ml
0.44
0.70
QNS
2.26
2.26
2.14
2.14
RBC ChE
(ApH/hr)
0.21
0.37
0.30^
0.55"
O.H"
0.55"
0.15
Plasma ChE
(ApH/hr)
0.49
0.33
0.08
0.20
0.18
0.55
0.10
QNS=Quantity not sufficient
// Post-PAM blood
33
-------
symptomatic cases. Furthermore, D.A. two months later had an RBC ChE of 0.26
ApH/hr and plasma ChE of 0.50 ApH/hr and it was necessary to remove him from
further flying because his RBC ChE had dropped from 0.46 to 0.26 ApH/hr. G.J.
on the other hand continued to have satisfactory cholinesterase levels when
examined two months later (see Table 3).
These qualitative differences of DEP and DETP were compared in the two groups.
Table 14 compares the DEP:DETP ratios in 3 poisoned cases and in the occupa-
tional group. The mean ratip in the poisoning group was 4.14 (SE=0.70) and
the corresponding mean in the occupationally exposed group was 0.88 (SE=0.09).
These means are significantly different (p <.01) by any of the comparative
tests which might be used (t test, Wilcoxson Rank Score, etc.). It has al-
ready been mentioned that for the dimethyl alkyl phosphate derivatives compared
in these two groups, such a comparison is not truly valid since the comparison
in one of different ethyl methyl parathion exposures and unavoidably, the
occupationally exposed group had additional exposure to other pesticides.
Several of these had DMP of DMTP alkyl phosphate metabolites and would con-
found the interpretation of the dimethyl data. The qualitative and quantita-
tive differences of the dimethyl alkyl phosphate metabolites is not therefore
considered in this study. Paranitrophenol concentrations are almost certainly
uniquely representative of ethyl methyl parathion, since there were no exposure
to other pesticides which possess this phenolic metabolite in our studies.
The comparison of these metabolites were more variable in the two exposure
groups and the data suggested that they were less sensitive indicators of
parathion exposure, cholinergic symptoms and cholinesterase changes.
Discussion and Conclusion - The urinary metabolite data in these differing
exposures to ethyl methyl parathion mixtures suggested that the diethyl
alkyl phosphate data were the most important indicators of excessive ex-
cessive exposure to this pesticide. As predictors of cholinergic mani-
festations and severe enzyme inhibition the concentration of DEP was the
most important variable. Concentrations of DEP in excess of 0.4 ug/ml were
of the order of magnitude which were associated with symptoms and severe
degrees of cholinesterase inhibition. The respective ratio of DEP to DETP
was another important index of over exposure and ratios of DEP:DETP of 2.0
or greater were usually associated with marked degrees of enzyme inhibition
and with poisoning symptoms. Since DEP is reflective of oxon of parathion
and DETP is reflective of parathion exposure, then the data suggested that
the major contributant to severe cholinesterase inhibition and the occurrence
of overt illness in parathion exposure is the amount of paraoxon formed rather
than the amount of the original pesticide. This observation is entirely in
accord with the known relative toxicity of these two compounds.
Urinary Pesticide Metabolite Studies in Occupational Exposure to
Dursban and DDVP
Background Information - Dursban and DDVP are organophosphate insecticides
of low mammalian toxicity and to our knowledge there are no reports of human
illness and serious cholinesterase inhibition following occupational exposures
of these pesticides. Dursban is reported to inhibit plasma ChE only.
Urinary pesticide metabolite studies of work exposure to these chemicals
cannot be related to illness by cholinesterase changes but serve rather
34
-------
PEP
Table 14. COMPARISON OF DETP RATIOS WITH URINES FROM PATIENTS WITH
PARATHION POISONING WITH ASYMPTOMATIC OCCUPATIONALLY
EXPOSED WORKERS. SOUTH FLORIDA, 1974
DEP:DETP RATIO
No. of
Name Urines
A.
TB
JD
MP
Poisonings
6
7
7
Mean
3.95
7.12
1.79
Standard
Deviation
3.24
2.58
0.69
Standard
Error
1.32
0.97
0.26
. Minimum
1.40
4.59
0.90
Maximum
9.75
10.33
2.58
Combined 20
4.14
3.21
0.70
0.90
10.33
B. Exposed Workers
WG
WG
FB
GJ
DA
if I
#2
Combined
13
11
19
16
12
71
0.
- o.
0.
1.
1.
0.
60
17
60
73
17
88+
0.
0.
0.
1.
0.
0.
24
21
40
04
29
78
0
0
0
0
0
0
.07 .
.06
.09
.08
.26
.09
0.32
0
0
0
0.64
0
1.
0.
1.
4.
1.
4.
16
69
73
42
76
42
t test - percent of significance of
differences at <0.01
35
-------
to provide descriptive information of the urinary metabolites with regard to
the magnitude and the duration of excretion of these metabolites following
known single occupational exposures. Such studies therefore are purely descrip-
tive and this was the goal of the studies undertaken herein. DEP, DETP and 3,
5,6-TC pyridinol are the major metabolites of Dursban. DMP is the major alkyl
phosphate metabolite of DDVP.
In 1973 a sequential excretion of these two metabolites was studied in two
spraymen following a single 4*5 hour exposure to 2^% Dursban and 0.75% DDVP.
Following this small isolated exposure all three metabolites were still de-
tectable in the urine for 36 hours after exposure. DETP peaked at 6-9 hours
after exposures and its concentration was always greater than DEP. 3,5,6-TC
pyridinol peaked at 8 hours in one sprayman and 32 hours in another. DEP
excretions peaked at 4*2 hours after exposure. It was decided to repeat this
study in the same sprayman but with a 5*2 hour exposure to the same insecticide.
Materials and Methods - After measuring the volume and time of voiding of the
first morning's specimen, this was discarded; thereafter, sequential urines
were collected from the same two spraymen (M.P. and E.S.) during and after
a single 5% hour exposure to Dursban 2.5% and DDVP 0.75%. Both operators
sprayed only on the day of study and had no pesticide exposure on the pre-
ceeding days. Both wore respirators and rubber gloves while working. M.P.
used a hand sprayer and E.S. used a power sprayer; they sprayed the hold of
the ship from 9:00 a.m. to 2:30 p.m. After this they washed and changed
their clothing and continued to collect the urine for 32 hours (M.P.) and
29% hours (E.S.).
Results - Tables 15 and 16 list the concentrations of DMP (DDVP), and DEP,
DETP and 3,5,6 TC pyridinol (Dursban) excreted following this single work
exposure of these two spraymen. Figures 9 and 10 described the sequential
concentration of these four metabolites in ug/ml. Red blood cell and plasma
ChE levels for M.P. were 0.76 and 0.76 ApH/hr respectively and the same
findings for E.S. were 0.69 and 0.76 ApH/hr respectively.
Discussion - All four metabolites of the pesticides being applied were identi-
fied in both spraymen. DEP concentrations ranged from 0.03 - 0.082 ug/ml
for the two men; similarly, DETP levels ranged from 0.06 to 0.18 ug/ml.
DETP concentrations were greater than DEP and 3,5,6-TC pyridinol concentra-
tions ranged from 0.014 - 0.380 ug/ml. In contrast, DEP and DETP concen-
trations did not vary much during these exposures and were of a low order
of magnitude. Both the alkyl phosphate and phenolic metabolites, however,
were detectable for as long as 30 hours after exposure. 3,5,6-TC pyridinol
peaked later than the alkyl phosphate metabolites and was maximal 17 to 27
hours after the end of the exposure in the respective spraymen. The later
maximum excretion of this phenolic metabolite was also noted in our stu-
dies conducted last year. In contrast, DMP concentrations which ranged
from N.D. - 0.3 ug/ml were maximum almost immediately at the end of the
work exposure and then declined steadily. Thus, DDVP which had the DMP
metabolite appeared to be metabolized at a fast rate than Dursban. This
observation reconfirmed the findings of last year.
Urinary Metabolite Studies During and After Early Application of
Thimet (Phorate)
Background Information - Phorate is an organophosphate insecticide with an
36
-------
Table 15. SEQUENTIAL URINARY ALKYL PHOSPHATE AND PHENOLIC EXCRETION RATES IN A STRUCTURAL PEST CONTROL
OPERATOR (M.P.) DURING AND AFTER 5 1/2 HOURS APPLICATION.OF 2.5% DURSBAN AND 0.75% DDVP
Date
1974 Hour
11/10 11:50
2:30
5:00
7:15
9:30
11:05
11/11 1:10
3:00
5:00
10:30
ml
Voided
am 250.0
pm 189.0
pm NC
pm 150.5
pm 200.0
pm 218.0
am 192.0
am 280.0
pm 134.0
pm 206.0
ug/
ml
0.036
0.120
NC
0.117
0.030
0.030
0.023
ND
0.025
ND
DMP
ug/vol
voided
9.0
22.7
NC
17.6
6.0
6.5
4.4
ND
3.4
ND
ug/
-hour
1.90
8.50
NC
7.80
2.70
4.10
2.10
ND
0.24
ND
ug/
ml
0.030
0.030
NC
0.030
ND
ND
ND
ND
0.040
ND
DEP
ug/vol
voided
7.8
5.5
NC
4.5
ND
ND
ND
ND
5.4
ND
ug/
hour
1.60
2.10
NC
2.00
ND
ND
ND
ND
0.38
ND
DETP
ug/ ug/vol ug/
ml voided hour
0.060 15.0 3.10
0.150 28.4 10.60
NC NC NC
0.050 7.5 3.40
0.090 18.0 8.00
0.100 21.8 13.80
0.08015.4 7.40
0.110 30.8 16.80
0.100 13.4 0.96
0.080 16.5 3.00
3^5^6-TC Pyridinol
ug/
ml
0.075
0.051
NC
0.045
0.023
0.019
0.041
0.014
0.114
0.063
ug/vol
voided
18.8
9.6
NC
6.7
4.6
4.2
7.8
3.9
15.3
13.0
ug/
hour
3.90
3.60
NC
3.00
2.00
2.70
3.80
2.10
1.10
2.40
RBC ChE 0.76 and Plasma ChE 0.76 pH/hr.
NC=Voided at 5:00 pm but urine not collected
ND=Not detectable
Limits of detectability are: DMP 0.03, DEP 0.04,
DETP 0.04 and 3,5,6-TC Pyridinol 0,002
-------
Table 16. SEQUENTIAL URINARY ALKYL PHOSPHATE AND PHENOLIC EXCRETION RATES IN A STRUCTURAL
PEST CONTROL OPERATOR (ES) DURING AND AFTER 5 1/2 HOURS APPLICATION OF 2.5%
DURSBAN AND 0.75% DDVP
Date
1973
11/10
w 11/11
00
ml
Hour Voided
6:21 pm
7:45 pm
11:30 pm
8:00 am
2:10 pm
4:50 pm
8:00 pm
175
80
200
175
275
360
220
ug/
ml
0.300
0.258
0.220
0.234
0.130
0.056
ND
DMP
ug/vol
voided
52.5
20.6
44.0
41.0
36.0
20.2
ND
ug/
hour
UC
14.7
11.7
4.8
5.8
7.6
ND
ug/
ml
0.068
0.082
0.070
0.100
ND
0.078
ND
DEP
ug/vol
voided
11.9
6.6
14.0
17.5
ND
28.1
ND
ug/
hour
UC
4.7
3.7
2.1
ND
10.5
ND
DETP
ug/ ug/vol ug/
ml voided hour
0.070 12.3 UC
0.170 13.6 9.7
0.170 34.0 9.1
0.180 31.5 3.7
0.170 46.8 7.6
0.160 57.6 21.6
0.150 33.0 10.4
3,5,6-TC Prydinol
ug/ ug/vol
ml voided
0.090 16.6
0.129 10.3
0.106 21.3
0.380 66.7
0.073 20.0
0.185 66.7
0.109 24.1
ug/
hour
UC
7.4
5.7
7.8
3.2
25.0
7.6
UC=Unable to calculate previous hour not known
ND=Not detectable
Limits of detectability are: DMP 0.03, DEP 0.04, DETP
0.04 and 3,5,6-TC Pyridinol 0.002
-------
Figure 9. SEQUENTIAL URINARY ALKYL PHOSPHATE AND PHENOLIC F.v(. , .T10K
RATES IN A STRUCTURAL PEST CONTROL SPRAYER (MP) D'JAING
AND AFTER 51/2 HOURS APPLICATION OF 0.75% DDVP AND 2.5%
DURSBAN
EXPOSURE
jjg/ml
.12 r
.08
.04
DMP
.15
.10
.05
0
.12
.08
.04
*
3,5,6-TCP
6 AM 6 PM 6 AM 6 PM 6 AM HOUR
11/10/73 11/11/73
39
-------
Figure 10. SEQUENTIAL URINARY ALKYL PHOSPHATE AND PHENOLIC EXCRETION
RATES IN A STRUCTURAL PEST CONTROL SPRAYER (ES) DURING
AND AFTER 5 1/2 HOURS APPLICATION OF 0.75% DDVP AND 2.5%
DURSBAN
EXPOSURE
.3
.2
DMP
u . . . . —
.2 r-
.1
n
o ' , — n- ,
( u>.
• D
'-^SA
1 1 1
• DEP
a DETP
3,5,6-TCP
6 AM 6 PM
11/10/73
6 AM 6 PM HOUR
11/11/73
-------
oral LD50 of 1.1 mg/kg and a dermal LD50 of 2.5 rag/kg; it is therefore a
highly toxic pesticide and because of this is infrequently used in agriculture
in South Florida except in a granular formulation. An opportunity was
afforded us to study the urinary excretion of the alky I. phosphates of
Phorate when a 10% granular formulation of this pesticide was aerial1 :
applied by a fixed wing aerial applicator during a two hour period. The
ordinary alkyl phosphate metabolites of Phorate are DEP, DETP, DEDTP—
the latter is present in too low concentrations to be detected under normal
occupational exposures, being recognized only in acute poisonings.
Materials and Method - A fixed wing aircraft pilot was visited on 1/19/74
and requested to participate in a pesticide urinary metabolite study. Blood
was collected and analyzed that day by the Michel method and showed that his
RBC and plasma ChE were 0.60 ApH/hr and 0.75 ApH/hr respectively. On 1/25/74
the day before the study he was working on the airfield from 8:00 a.m. to
4:00 p.m. but did no flying. On 1/26/75 he discarded his early morning speci-
men and thereafter voided into a labelled hexane washed jar and noted the
amount and time of urine voided. Sequential urines were provided from 7:00
a.m. on 1/26/74 until 10:00 p.m. 1/27/74. On the study day, he worked on
the plane at 8:30 a.m. and then between 10:00 a.m. and 12 noon he loaded
and applied 10 Ib. bags of Thimet (Phorate) granules for a two hour period.
The pilot himself opened the bags and then emptied them into the tank of
an open cockpit Stearman. He loaded and flew three times and reported that
on the third flight he developed a severe headache and felt nauseated. So
intense was his headache that it interferred with his flight and so he
showered, changed his clothes and went home. He took aspirins, the headache
improved and there were no further symptoms. Two days later a second cholin-
esterase showed that the RBC and plasma cholinesterase were 0.64 and 0.93
ApH/hr respectively.
Results - Table 17 shows the urinary concentrations of the alkyl phosphate
metabolites from the pilot during and after his application of 10% Thimet.
Figure 11 illustrates the sequential excretion of these metabolites in
ug/ml.
Discussion - The appropriate metabolites for Phorate that we should study
are DEP, DETP, DEDTP, the latter was not detected and this is not uncommon
under low level exposure situations. DEP which is reflective of oxon was
on all occasions except once less than DETP. This substantiated the negative
diagnosis of pesticide related illness. The DETP metabolites very accurately
illustrated his work exposure because concentrations of this metabolite started
at 1 and rose to 3 after two hours of aerial application of Thimet (Phorate).
DEP fluctuations were minimal. The excretion of these metabolites in this
setting suggested that there were diurnal variations with high levels found
in the morning. It will be noted that traces of DMP and DMTP were identified.
We have no explanation for the occurrence of these di-methyl metabolites and
can only postulate that these were the result of other organophosphates at
the work site and/or traces of contamination on the clothing or in the air-
craft.
Urinary Phenolic Studies in Occupational Exposure to Sevin (Carbaryl)
Background Information - Sevin (carbaryl) is not a strong cholinesterase inhibitor
and the oral and dermal LDSOs of this carbamate insecticide are 850 mg/kg and
>4000 mg/kg in male rats respectively. It is thus not a very toxic insecti-
41
-------
Table 17. URINARY ALKYL PHOSPHATE EXCRETION RATES IN A PILOT (JS) LOADING AND APPLYING PHORATE FOR TWO HOURS
ho
Date
1974
1/26
1/27
ml
Hour Voided
7:00 am
2:00 pm
4:30 pm
7:30 pm
-7:45 pm
3:30 am
8:20 am
?
5:15 ?
5:20 ?
10:00 pm
300
350
230
365
320
250
150
240
690
550
195
ug/ml
0.040
0.023
0.017
0.023
0.029
0.055
0.056
0.018
0.015
0.014
0.022
DMP
ug/vol
voided
12.0
8.1
3.9
8.4
9.3
13.8
8.4
4.3
10.4
7.7
4.3
ug/
hour
UC
1.2
1.6
UC
UC
UC
1.7
UC
UC
UC
UC
ug/ml
0.176
0.089
0.146
0.150
0.120
0.080
0.165
0.163
0.061
0.059
0.077
DMTP
ug/vol
voided
55.8
31.2
33.6
54.8
38.4
20.0
24.8
39.1
42.1
32.5
15.0
ug/
hour
UC
4.4
13.4
UC
UC
UC
5.1
UC
UC
UC
UC
ug/ml
0.082
0.033
0.074
0.045
0.042
0.146
0.154
0.027
0.023
0.026
0.048
DEP
ug/vol
voided
24.6
11.6
17.0
16.4
13.4
36.5
23.1
6.5
15.9
14.3
9.4
ug/
hour
UC
1.7
6.8
UC
UC
UC
4.8
UC
UC
UC
UC
ug/ml
0.094
0.293
0.274
0.106
0.226
0.281
0.074
0.043
0.145
0.150
0.141
DETP
ug/vol
voided
28.2
102.6
63.0
38.7
• 72.3
70.3
11.1
10.3
100.1
82.5
27.5
ug/
hour
UC
14.7
25.2
UC
UC
UC
2.3
UC
UC
UC
UC
UC=Unable to calculate micrograms per hour
?=Cannot establish correct time
-------
Figure 11. URINARY ALKYL PHOSPHATE EXCRETION RATE IN A PILOT (IS)
LOADING AND APPLYING PHORATE FOR 2 HOURS
jjg/ml
.20
.16
.12
.08
.04
0
.30
.25
.20
.15
.10
.05
• DMP
o DMTP
I i
J I I I
6 AM 6 PM
1-26-74
6 AM 6 PM
1-27-74
-------
cide and neither illness nor cholinesterase inhibition would be an expected end
point in metabolite studies following exposures to 0.5% solution of Sevin. The
purpose therefore of this investigation was purely descriptive having special
interest in determining the magnitude of alpha naphthol levels and thr post
exposure peaking and duration of excretion following the completion of work.
Alpha naphthol is the phenolic metabolite of carbaryl (Sevin).
Materials and Method - Sequential urinary excretion of alpha naphthol were
collected and analyzed from two spraymen working at the Dade County Park Depart-
ment spraying trees for Dutch Elm disease with a 0.5% solution of Sevin and
having a worker exposure period of between 3*5 to 6 hours. In addition to
spray, exposure occurred at the beginning of the day through the mixing of
30 Ibs. of water dispersable powder of 80% Sevin into a 600 gallon capacity
tank, and at the end of the day through washing and hosing down the truck.
The two spraymen alternated evenly during the spray period between driving
the truck or applying the spray. The two men wore short sleeve shirts and
wore no gloves and used no respirators. Cholinesterase activities were deter-
mined by the Michel method and alpha naphthol was analyzed by the Shafik,
Sullivan and Enos method. » 10
Results - The RBC and plasma ChE of R.S. was 1.06 ApH/hr and 0.52 ApH/hr
respectively and for E.O., 0.68 and 1.03 ApH/hr respectively. The exposure
period and the urinary excretions of alpha naphthol are shown in Table 18.
Figure 12 illustrates the daily excretion of alpha naphthol during the study
week, and during the weekend period of non-exposure in one sprayman (R.S.).
Alpha naphthol was detected in all specimens voided and concentrations ranged
from 0.2 - 3.16 ug/ml in the two spraymen. There was a gradual increase of
levels from Monday through Thursday with a decline occurring thereafter.
Alpha naphthol was still detected 42 hours after R.S.'s last exposure on
Friday, 3/29/74 until Sunday, 3/31/74. Thus, the effects of exposure were
not totally eliminated by the weekend rest. This would explain why the
first collection on Monday morning revealed small traces of alpha naphthol.
The weekend data from R.S. also suggests that the optimum time for collect-
ing a post exposure urine was 18 hours after exposure because alpha naphthol
was still being detected during the time he was not at work.
Urinary Pesticide Metabolite Studies in Acute and Chronic Exposure
of Dichlofenthion
Background Information - Dichlofenthion or VC-13 is an organophosphate which
is being used in South Florida as a nemacide and insecticide for the control
of chinch bugs. It is readily available in most horticulture and in drug
stores, and has an oral LD50 of 270 mg/kg and a dermal LD50 of 6,000 mg/kg
in rabbits. Animal studies have shown this pesticide to be soluble in fat.
We have identified VC-13 in human fat specimens in a series of five cases -.„
of human intoxication, all of which were the result of suicidal ingestion.
Such poisonings were very atypical from a clinical point of view, exhibiting
a protracted asymptomatic period following ingestion. Initial manifestations
were deceiptively mild but were followed in a period of 40-48 hours by
evolution of serious and life threatening cholinergic crises. Cholinergic
manifestations of waxing and waning in intensity lasted 5-48 days and re-
quired continuous atropine therapy and oxiines for the entire period. During
the middle of this year, we were called in-.to advise on such a poisoning
case because the patient was still exhibiting cholinesterase manifestations
on the 12th day after ingestion of VC-13; her red blood cell and plasma cholin-
44
-------
Table 18. ALPHA NAPHTHOL CONCENTRATIONS IN TWO DADE COUNTY PARKS DEPARTMENT
SPRAYMEN (R.S. AND E.O) WHO HAD BEEN USING 0.5% SEVIN (CARBARYL)
Robert S.
Alpha Naphthol
Date
1974
3/25
3/26
3/27
3/28
3/29
3/30
3/31
Exposure
history
8:00 am -
2:00 pm
8:00 am -
2:00 pm
8:00 am -
11:30 am
8:00 am -
2:00 pm
8:00 am -
1:00 pm
None
None
Hour
collected
1:00 am
4:32 am
2:50 pm
10:45 am
3:00 pm
6:20 pm
11.30 pm
5:00 am
7:00 am
10:05 am
12 noon
10:15 am
2:00 pm
6:00 pm
9:00 pm
8:00 am
10:15 am
7:30 pm
5:00 am
9:00 am
2:00 pm
5:00 pm
10:00 pm
7:00 am
ml.
voided
336
332
364
221
165
344
350
380
95
180
128
283
114
165
110
140
167
295
232
205
375
324
285
306
ug/
ml
0.80
0.60
0.60
0.60
1.20
1.20
0.60
0.70
1.40
1.00
1.00
1.50
1.80
1.00
1.50
1.20
1.00
0.40
1,60
1.0
0.60
0.80
0.80
0.20
ug/vol.
voided
268.8
199.2
218.4
132.6
198.0
412.8
210.0
266.0
133.0
180.0
128
424.5
205.2
165.0
165.0
168.0
167.0
118.0
371.20
205.0
225.0
259.2
228.0
61.2
ug/
hour
UC
56.38
UC
UC
46.59
123.84
40.65
48.36
66.50
58.40
66.78
UC
54.72
41.25
55.0
UC
74.2
12.8
UC
51.25
45.0
86.40
45.60
6.80
Hour
collected
5 : 15 pm
9:00 pm
10:45 am
10.: 45 pm
10:00 am
12 noon
3:25 pm
8:30 pm
10:45 am
5:25 pm
8:00 am
10:15 am
ml.
voided
168
160
196
142
126
60
130
129
108
150
156
134
Estanislau 0.
Alpha Naphthol
ug/
ml
1.35
1.60
1.55
3.87
1.35
0.86
1.70
2.72
3.16
2.05
1.15
1.00
ug/vol
voided
227.14
255.36
303.41
549.54
169.60
51.24
221.0
350.75
341.28
307 . 50
179.40
134.0
ug/
hour
56.8
68.1
52.8
274.8
44.2
25.6
64.7
69.0
68.3
90.0
59.8
59.6
UC=Unable to calculate previous hour not known
•H RBC ChE 1.06 ApH/hr, PI. ChE 0.52 ApH/hr (R.S.) and F..O. RBC ChE 0.68 ApH/hr and PI. C'.hK I..03 ApH/hr
-------
Figure 12. DAILY EXCRETION OF ALPHA NAPHTHOL (ug/ml) IN TWO SPRAVMEN
APPLYING 0,5% SEVIN (CARBARYL)
2.00
1.60
1.20
.80
40
EXPOSURE TIME
CASE1
O
| 3.0
<
< 2.0
1.0
CASE 2
F I I—
A
12PM PM PM PM PM PM
3-25 3-26 3-27 3-28 3-29 3-30-74
46
-------
esterase were almost 100% inhibited. Pesticide residues and urinary metabolite
studies were collected in this patient and our involvement in this case pro-
vided an excellent opportunity to study the delayed excretions of the urinary
metabolite of this less polar organophosphate. The data that follows describes
the pesticide residue studies in this extraordinary case, and also presents uri-
nary phenolic metabolite data of a volunteer sprayman (J.D.) who applied VC-13
to his 1/2 acre lawn. The persistence of this organophosphate in air is dis-
cussed later in the section under "Air Monitoring". The urinary metabolites
for dichlofenthion (VC-13) are DETP and DEP, and 2,4-Dicblorophenol (2,4-DCP).
Materials and Methods - Sequential urines and blood samples were collected
from the pesticide poisoning case during the period of her recovery. The
intact pesticide was measured in the blood and also in one fat biopsy collected
on the 39th day. RBC and plasma ChE determinations were also performed dur-
ing and after hospitalization and urine was analyzed for the urinary alkyl , ..-.
phosphates by the Shafik et al. method and 2,4-DCP by the Shafik et al method. '
In the field studies, 26 ounces of a 75% solution of VC-13 was applied to a
1/2 acre lawn over 100 minute time period pre, during and post exposure urines
were analyzed. Gas chromatographic problems prevented simultaneous analysis
of alkyl phosphates. No protective clothing was used and the volunteer sprayed
his lawn in a short sleeve shirt, long pants and canvas shoes. Immediately
after spraying he showered and changed his clothes.
Results - Tables 19 and 20, and Figures 13 and 14 present the cholinesterase
pesticide, residue data, phenolic excretion of 2,4-DCP and the urinary alkyl
phosphate levels after oral ingestion of VC-13 and during the recovery period.
This pesticide was identified in a fat biopsy in a concentration of 34 ppm
and the intact pesticide was detectable in the serum for 75 days after ex-
posure. The concentrations of the phenolic metabolite (2,4-DCP) ranged
from 35.97 - 0.019 ug/ml. Concentrations of DEP ranged from 5.25 - N.D.
ug/ml and for DETP from 15.3 - <0.04 ug/ml. DMP and DMTP traces which pro-
bably reflected contamination of dichlofenthion ranged from 0.258 - N.D.
ug/ml and from 0.38 - <0.04 ug/ml respectively.
Discussion - The chronicity of the intoxication in this case was its most
striking feature. The patient required 2 hourly infusions of atropine IM
for 40 days to adequately control ChE symptoms and the alkyl phosphate and
phenolic metabolites were detected for a period of up to 75 days and when
reexamined on the 129th day levels of all five urinary metabolites had fallen
below the limits of detectability.
Table 21 presents the urinary excretion of 2,4-DCP during and after applica-
tion of VC-13 to a 1/2 acre lawn.
Discussion - Dichlofenthion or VC-13 is one of a group of pesticides being
used with increasing frequency in many parts of the world. Some of these
are halogenated and include such compounds as Ronnel and Leptophos (Phosvel).
In studies elsewhere the partition coefficient for the four organophosphate
pesticides were studied: dichlofenthion, Ronnel, Leptophos and parathion.
Dichlofenthion had a much higher partition coefficient (1.372 x 10^) than
the trichloro substitute compound Ronnel (7.5 x 10^) and the partition co-
efficient of dichlofenthion was 20 times greater than parathion. Leptophos
was even more fat soluble than dichlofenthion having a partition coefficient of
47
-------
Table 19. CHOL1NESTERASE, PESTICIDE RESIDUES AND PHENOLIC DATA FOLLOWING ORAL INGESTION
OF DICHLOFENTHION (VC-13). DADE COUNTY 1974
2 , 4-Dichlorophenol
Date
3/2/741*
3/14/74
3/15/74
3/18/74
3/28/74
3/29/74
3/30/74
3/31/74
£ 4/2/74
4/10/74
4/11/74
4/12/74
4/25/74
5/6/74
5/16/74
5/30/74
7/9/74
RBC ,
Hour ChE f
5:45 pm 0.08
0.08
0.08
0.08
0.25
0.40
0.40
0.65
Plasma VC-13 PI.
ChE f (ppb)
0.07 173
0.07 141
0.07 86
0.07 68
11.5
0.25 7.6
0.45 2.2
0.50 ND
0.88
VC-13 Fat
(ppm) Hour
5:45 pm
6:55 pm
7:45 pm
8:30 am
2:50 pm
1:10 ?
3:20
36
4:10 am
9:20 pm
2:45 pm
10:25 pm
2:45 pm
10:40 pm
8:55 am
1:05 pm
3:30 pm
4:20 pm
ml
Voided
310
90
180
495
450
?
650
500
360
300
290
360
290
170
197
186
380
ug/
ml
7.71
7.02
3.27
35.97
6.1
5.9
1.16
3.9
5.42
2.82
2.92
1.72
2.88
1.04
1.29
0.37
0.19
ug/vol
voided
2,390.1
631.8
588.6
17,805.2
2,745.0
?
754.0
1,950.0
1,951.2
846.0
846.8
619.2
835.2
176.8
253.3
69.2
73.7
ug/
hour
UC
541.5
588.6
1,396.5
986.8
?
UC
531.8
477.9
253.8
267.4
256.2
238.6
96.4
121.6
46.1
73.7
7
-------
Figure 13. SERUM CONCENTRATIONS OF DICHLOFENTHJON (ppb) AND RED CELL
AND PLASMA CHOLINESTERASE LEVELS (ApH/hr) DURING RECOVERY
FOLLOWING ORAL INGESTION OF DICHLOFENTHION (VC-13)
• PLASMA ChE
RBC ChE
• VC 13 IN SERUM
20
40 60 80 100
DAYS POST POISONING
49
-------
Table 20. URINARY ALKYL PHOSPHATE DURING RECOVERY FOLLOWING ORAL INGESTION OF DICHLOFENTHION. 1974.
Date
3/14
3/15
3/18
3/29
4/2
4/11
4/12
5/6
7/9
Hour
5:45 pro
6:55 pm
7:45 pm
8:30 am
2:50 pm
1:10 ?
3:20 ?
4:10 am
9:20 pm
2:45 pm
10:25 pm
2:45 pm
10:40 pm
8:55 am
1:05 pm
4:20 pm
12:02 pm
ml
Voided
310
90
180
495
450
?
650
500
360
300
290
360
290
315
197
380
314 .
ug/ml
0.044
0.088
0.061
0.258
0.076
0.023
0.021
0.068
0.053
0.057
0.060
0.044
0.072
0.103
0.072
0.038
ND
DMP
ug/w
13.6
7.9
10.98
127.7
34.2
?
13.7
34.0
19.1
17.1
17.4
15.8
20.9
17.5
28.4
13.4
ND
ug/hr
UC
6.8
10.98
10.02
12.1
?
UC
9.3
4.7
5.1
5.5
6.6
6.0
9.6
13.6
8.9
ND
ug/ml
0.134
0.151
0.152
0.212
0.300
0.104
0.078
0.264
0.276
0.278
0.254
0.229
0.382
0.217
0.188
0.324
ND
DMTP
ug/w
41.5
13.6
27.4
104.9
135.0
7
50.7
132.0
99.4
83.4
73.7
82.4
110.8
36.9
37.0
60.3
ND
ug/hr
UC
11.7
27.4
8.2
47.7
?
UC
36.0
24.3
25.0
23.3
34.0
31.7
20.1
17.8
40.2
ND
ug/ml
1.53
2.60
1.22
5.24 2,
2.28 1,
0.80
1.12
1.41
1.76
1.44
1.57
1.10
1.44
0.76
1.00
0.37
ND
DEP
ug/vv
473.3
233.8
219.2
593.8
026.0
?
728.0
705.0
633.6
432.0
455.3
396.0
417.6
128.5
197.4
68.8
ND
ug/hr
UC
200.4
219.2
203.4
362.1
?
UC
192.3
155.2
129.6
143.8
163.9
119.3
70.1
94.8
45.9
ND
ug/hr
4.99
8.48
1.88
15.1
6.58
3.58
0.87
2.97
2.24
1.34
1.25
0.71
0.90
0.20
0.21
0.10
ND
DETP
ug/w
1,545.7
762.8
338.4
7,456.7
2,960.1
7
564.2
1,485.0
807.8
403.2
363.7
255.6
261.0
33.3
41.2
17.7
ND
ug/hr
UC
653.8
338.4
584.8
1,044.7
?
UC
405.0
197.8
130.0
114.8
105.7
74.6
18.2
19.7
11.8
ND
UC=Previous hour not known; unable to calculate
?=Hour and amount of voiding not available
ND=Not detectable
Limits of detectability are: DEP 0.02, DMP 0.02, DMTP
0.04 and DETP 0.04
-------
Figure 1A. URINARY EXCRETIONS OF ALKYL PHOSPHATES AND PHENOLIC METABOLITES
OF DICHLOFENTHION (VC-13) POISONING. BADE COUNTY 1974
DMP
DMTP
30
20
10
0
DEP
DETP
2,4-DCP
20 40 60 80 100
day
51
-------
Table 21. 2,4-DICHLOROPHENOL CONCENTRATIONS IN A VOLUNTEER SPRAYMAN
(J.D.) USING VC-13 FOR A PERIOD OF 1 HOUR 40 MINUTES
2 , 4-Dichlorophenol
Previous
Date hour
7/15/74 7:05 am
7/16/74
7/17/74 11:26 pm
7/18/74
7/19/74
7/20/74 10:05 am
Hour of
collection
8:45 am
10:53 am
3:14 pm
11:40 pm
6:50 am
10:43 am
2:00 pm
6:27 pm
7:22 am
8:34 am
1:47 pm
11:43 pm
7:25 am
10:45 am
7:10 am
11:25 am
5:20 pm
ml.
Voided
98
236
292
282
309
221
286
164
234
82
325
373
398
410
372
422
440
ug/
ml
ND*
ND
0.054
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ug/vol
voided
ND
ND
15.77
ND
ND
ND
ND
ND
ND
ND
ND
ND
.•ND
ND
ND
ND
ND
up,/
hour
ND
ND
3.6
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND=Not detectable
Limit of detectability
0.02
52
-------
(2.02 x 10 ). Based on the partition coefficient data it is our hypothesis
that VC-13 is readily absorbed by the fat (possible storage) and through
slow mobilization the compound is being released over a period of time, back
to the circulatory system where the metabolism changes it to the more toxic
oxon and it is this mechanism which we believe accounts for the prolonged
symptomatology after exposure.
As is discussed later in the section on "air monitoring", dichlofenthion has
been identified in all air samples in the urban environment of Dade County.
In view of the fat solubility of this material, if present use patterns
continue, it is highly probable that trace amounts of this organophosphate
might be detectable in the human adipose pesticide residue profile, especially
if lower limits of detectability can be developed.
Pesticide Urinary Metabolite Studies in the General Population
Background Information - Little is known of the magnitude of incidental ex-
posure of the general population of the United States to the non-persistent
pesticides. In a presentation at the 167th meeting of the American Chemical
Society .in Los Angeles, California in 1974, Shafik and Bradway reviewed the
very limited data that was available on this topic. Their report included
results of earlier studies by Shafik of 14 urines from non-exposed individuals.
DETP was not identified and DEP concentrations ranged from 0.04-0.12 ppm.
At the low levels of detectability, Shafik and his colleagues were able to
detect DEP which was identified in all samples tested. DMP and DMTP were
also found in all 14 samples and the range of DMP levels were 0.005-0.04
ppm and this project in 1973 from three non-exposed members of the general
population in which none of the alkyl phosphates were identified. He pre-
sented limited information from Mrs. Sarah Borthwick of Colorado—S.ta£e_U.aiyAr-
sity, Fort Collins, Colorado, in her studies from 47 urines from non-exposed
Colorado males where the mean levels for DMP and DETP were 0.01 ppm and 0.01
for DEP and DMTP. The percentage frequency of occurrence of both alkyl phos-
phate and phenolic metabolites from data collected from Aim Yobs of the State
Services Program Office of Pes_tic.ides..—EPA in the human monitoring survey
was also discussed. lLappeared that from 267 samples 90.3% were pnsif-ivp ,
J:or DMTPr 70.8% were positive for DEJJL 76.7% were positive for DMP and 94%
were_p.Q5jLtJLveJEor DjSP± In the phenol studies, j?6.3% were positive for penta-
chlorophenol (PCPU 10.9% were positive for alpha naphthol and 6.7% were posi-
tive for PNP. The reviewers did not state the lower limits of detectability
for the laboratories involved in these studies. In this year's study we planned
to conduct additional studies in the general population group but were in part
held up in the analysis of the alkyl phosphates because of impurities in the
reagents used for preparing the derivatives during the latter part of this year.
The data presented hereinafter, therefore, provides more information of phenol
prevalence in the general population than alkyl phosphate data.
Materials and Methods - Urines were collected for a variety of subjects having
no known occupational exposure to pesticides. Volunteers were asked to note
the 'time and volume of the first morning?s specimen and then to discard it.
The second voiding was collected in toto in labelled hexane washed jars and
time of voiding recorded. Urinary alkyl phosphates were analyzed bv the
Shafik et al method and the phenols by the Shafik et al method. '
53
-------
Results - The results were expressed in micrograms per milliliter, -micrograms
per volume voided and micrograms per hour. The lower limits of detectability
for DMP and DEP in our laboratory were 0.03 ppm and 0.04 ppm for DETP and DMTP.
For the phenols', it was 0.028 ppm for 2,4-DCP, 0.002 ppm for 3,5,6-TC prydinol,
0.001 for 2,4,5-TCP, 0.001 for PGP, 0.009 for PNP, 0.021 for 2,4-D, 0.003 for
Silvex, 0.005 for 2,4,5-T, 0.015 for IPP and 0.006 ppm for alpha naphthol.
Table 22a presents the urinary concentrations of the phenols of 38 members of
the general population of Dade County, Florida, in 1974. Table 22b presents
the urinary concentrations of the alkyl phosphates from seven members of the
general population. .Table 23 presents the frequency of the urinary metabolites
of the general population of Dade County, Florida in 1974.
Discussion - Although this was a small sample and by no means representative
of the total general population of Dade County and although concentrations
of all of the urinary metabolites identified were uniformly very low, several
pesticide metabolites were1 found in high frequencies. Thus, PGP was found-
in all 38 samples analyzed and DMTP in all 7 urines tested. PCP apjieared
to be as ubiquitous as was DDT yet this widespread contamination has received
none 6~f"~fhe~no-feor-i-ety"'that DDT has. 3,5,6-TC Pyridinol was the second most
commonly found, this urinary phenol being identified in 11 of 38 samples or
29%. This phenol is a urinary metabolite of Dursban which is one of the in-
secticides commonly used in the homes in Dade County for the control of roaches.
54
-------
Table 22a. URINARY PESTICIDE CONCENTRATIONS AND RATE OF EXCRETION IK THE GENERAL POPULATION OF DADE COUNTY 1974
Shafik Sullivan Method
Age,
Kace
Name & Sex
CM
AB
JD
KF
OF
CR
LR
JT
PT
MB
LR
CR
AR
LP
PL
AL
AM
CM
RK
FA
SK
LW
MT
JG
CH
FR
ER
MC
AC
IW
JP
JU
AC
38 W/F
49 W/F
53 W/M
W/F
W/M
32 W/F
69 W/F
23 W/M
23 W/F
74 W/F
28 W/F
4 W/M
35 W/M
46 W/M
10 W/M
42 W/F
39 B/M
48 B/F
36 W/M
29 B/M
32 W/F
40 W/M
24 B/F
21 W/M
55 W/M
51 W/M
33 B/M
26 B/M
21 B/F
19 B/F
48 B/M
16 B/M
21 B/M
Hr.
(min)
60
120
207
128
172
105
193
120
480
480
480
390
570
450
440
60
112
85
90
295
60
240
360
110
140
240
240
135
135
80
150
ml
Void.
56
118
278
34
262
120
160
144
60
110
304
108
306
152
158
38.5
101
56.8
56
434
61
129
409
266
328
158
97
61
109
27
56
2,4-
DCP
-/•
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
3,5,6-TC Pyrdinol
ug/ ug/v'ol ug/
ml voided hour
0.008 0.45 0.45
ND
ND
ND
ND
0.006 0.240 0.095
ND
ND
ND
0.006 0.864 0.432
ND
ND
ND
ND
ND
0.008 1.22 0.162
0.008 1.26 0.17
0.024 0.92 0.92
0.006 0.61 0.32
0.006 0.34 0.24
ND
ND
ND
0.032 4.13 1.03
ND
ND
ND
ND
ND
ND
ND
ND
0.008 0.45 0.18
' 2.4,
5-T
NC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
PCP
, ug/ ug/vol
ml voided
0.016
0.014
0.008
0.012
O.OL8
0.016
0.002
0.004
0.002
0.004
0.020
0.016
0.022
0.016
0.004
0.006
0.010
0.010
0.012
0.006
0.010
0.002
0.008
0.006
0.004
0.006
0.001
0.012
0.010
0.006
0.006
0.020
0.006
0.89
1.65
2.22
1.4
2.2
0.54
0.32
0.48
0.32
0.57
1.2
1.76
1.73
1.22
0.91
1.58
0.39
1.21
0.34
0.56
0.87
0.49
0.77
1.64
1.60
0.46
1.89
0.97
0.36
0.65
0.54
2.34
ug/
hour
0.89
0.83
0.65
0.27
0.24
0.25
0.18
2.27
0.09
0.38
0.15
0.22
0.83
0.26
0.13
0.12
0.22
0.39
0.65
0.24
0.37
0.18
0.49
0.19
0.27
0.87
0.19
0.47
0.24
0.16
0.29
0.41
0.34
2,4,5-TCP
ug/ ug/vol
ml voided
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.10 1.52
ND
ND
ND
ND
ND
0.014 6.08
ND
ND
ND
ND
ND
0.004 0.63
ND
ND
ND
0.004 0. I 1.
ND
ug/
hour PNP
m
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.20 ND
ND
ND
ND
ND
ND
1.24 ND
ND
ND
ND
ND
ND
0.16 ND
ND
ND
ND
0.08 ND
ND
2,4
-D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Chloroacetic
Anhydride Method
Sil- alpha Occupa-
vex 1PP Napthol tion
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SD
SD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
SD
ND
SD
ND
ND
*
*
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
•ND
ND
ND
ND
ND
ND
ND
ND
Chemist
Chemist
Physician
Lab Tech
Lab Tech
Cashier
Housewife
Lab Tech
Secretary
Housewife
Housewife
Hairdresser
Draftsman
Student
Seamstress
PhD Director
'Counselor
Manager
Lab Tech
Secretary
Lab Superv.
Lab Tech
Mail Clk.
Mail Superv.
Univ. Prof.
Lab Tech
Airline Mech
Secretary
Secretary
Unemployed
Unemployed
Lab Tech
-------
Table 22 . ( Continued)
Table 22b.
Ln
Name
R.P.
R.C.
J.T.
M.H.
A.J.
Age.
Race Hr
Sex (mln)
59 B/F 245
36 B/M 140
45 B/M 295
23 B/F 220
B/F 300
ml
void
211
211
66
106
92
2,4
DCP
ND
ND
ND
ND
ND
3,5.6-TCP
PCP 2.4,5-TCP
ug/ ug/ ug/ 2,4,
ml w hr
ND ND ND
ND ND ND
ND ND ND
ND ND ND
ND ND ND
5-T
ND
ND
ND
ND
ND
ug/ ug/ ug/ ug/ ug/
ml w hr ml w
0.002 a 38 0.09 ND
0.002 0.380.16 ND
0.006 0.380.08 0.024 1.
0.023 2.480.68 ND
0.002 0.180.04 ND
ug/
hr
2,4- Sil-
PNP D
ND ND
ND ND
610.33 ND ND
ND ND
ND ND
vex
ND
ND
ND
ND
ND
IPP
ND
ND
ND
ND
ND
a Naph-
thol Occupation
ND Reg. Nurse
ND Reg. Nurse
ND Plasterer
NO Fkg. Clerk
ND Housewife
B. ALKYL PHOSPHATE DATA
Name
C.M.
A.B.
J.E.D.
J.D.
J.A.
M.P.
A.S.
•fC.H.
*A.H.
?«IInahl
Age,
Race Hr
Sex (min)
38 W/F 60
49 W/F 120
53 W/M 190
50 W/M 217
72 W/M ?
4»s W/M 60
51 W/F
0.67 ug/ml, 37.
0.13 ug/ml, 1.5
ml
void
56
118
154
278
7
15
.314
ug/
ml
ND
ND
ND
ND
ND
ND
ND
5 ug/w and
ug/vv and 0
DMP
ug/ ug/
w hr.
ND ND
ND ND
NO ND
ND ND
7 7
NO ND,
ND ND
ug/
ml
ND
ND
ND
0.16
NO
ND
•m
37.5 ug/hr of 2.4-DCP
.8 ug/hr and J.D. 0.14
DMTP DEP
ug/ ug/ ug/ ug/
w hr. ml w
ND ND ND ND
ND ND ND ND
ND HO ND ND
15.2 9.1 ND ND
J » TO t-
ND. ND ND ND
NO RD NB ND
ug/ml and 3.9 ug/w and
ug/
hr.
ND
ND
ND
ND
?
ND
ND
1.13
ug/
ml
ND
ND
0.073
0.05
ND
ND
ND
ug/hr of
DETP
ug/
w
ND
ND
11.2
4.9
7
ND
ND
ug/
hr.
NT)
ND
3.7
2.9
7-
ND
ND
Occupation
Chemist
Chemist
Physician
Investigator
Retired
Child
Housewife
a naphthol
ND-Not detectable
Limits .of detectability are: DMP 0.03,. DMTP 0.04, DEP
0.04 and DETP 0.04 for alkyl phosphates
l'^Vn «;?28; 3>5~6 TC pyrldlno1 °-002: 2,4,5-TCP 0.001; PCP 0.001; PNP 0.009;
2,4-D 0.021; Silvex 0.003; 2,4,5-T 0.005; IPP 0.015; and alpha naphthol 0.006
tor phenols
-------
Table 23. FREQUENCY OF OCCURRENCE OF PESTICIDE URINARY METABOLITES
(ug/ml) IN THE GENERAL POPULATION OF DADE COUNTY, FLORIDA.
Metabolites
A. PHENOLS
Pentachlorophenol
3,5,6-rTC Pyridinol
2,4,5-TCP
a napthol
2 , 4-Dichlorophenol
2,4,5-Ti
Paranitrophenol
2,4-D •
Si 1 vex
Isopropoxyphenol
B.. ALKYL PHOSPHATES
Dimethyl phosphate.
Dimethyl thiophosphate
Diethyl phosphate
Diethyl thiophosphate
No. of persons
tested
38
38
38
38
38
38
38
38
38
38
. 7
7
7
7
No.
positive
38
11
6
2
1
0
0
0
0
0
3
7
4
6
Per cent
positive
100
29
16
5
3
43
100
57
86
Ranges
0.001-0
<0. 002-0
0.002-0
0.13-0.
<0.03
<0.04 -
<0.03
<0.04 -
.02
.03
.02
14
0.16
0.3
57
-------
SECTION V
Background Information - This is a continuation of air monitoring activities
conducted in 1973 in the South Florida area. The dat.i last year indicated
a changing profile of the ambient air in South Florida. Minimal traces of
brganophosphates were identified, in contrast to the usual presence of
organochlorine pesticides. DDT was not identified in any of the samples
although p,p'-DDE was found in trace amounts. The three sample sites last
year were a suburban site, Everglades National Park and Miami International
Aiport. It was decided to continue these activities in 1974 in eight differ-
ent sites and in addition to obtain a qualitative assessment of the pesticide
profile in the ambient air by experimenting with the use of an ethylene
glycol impregnated nylon organdy screen 0.5 M^. These activities have
assumed increased importance since we have been informed that these are
one of the few ongoing pesticide monitoring studies of air being conducted
at present in the United States.
Description of Phases
Phase I - Continuation of sampling sites as in 1973.
Phase II - Relocation of work sites.
Phase III - Pesticide studies of air concentrations of VC-13.
Phase IV - Nylon cloth screen experimental studies.
Materials and Methods - A double impinger system was used in each sampler
and 100 ml of ethylene glycol placed in each impinger. During the first
12 hour period air was drawn through the double impinger system and at
the completion of this 12 hour period, a second sample of air was drawn
through the second impinger system. The vacumn pump was run at all full
capacity during the 24 hour period. The 24 hour volume collection of air
was recorded as was the wind direction and velocity. This 24 hour sample
was then transferred to the University for analysis. The analytical method
used to measure the air samples was the Sherma and Shafik method.-" A
slight modification was made in the second and third fractions by the addi-
tion of 5 and 10 drops of keeper, thi.s prevented the loss of the organo-
phosphate compounds. For the testing of the nylon organdy screen the Tesari
and Spencer method was used. ^ The cloth screen was washed with methylene
chloride and then with hexane. It was then cut into 1/2 square meters
and impregnated with a 10% ethylene glycol in acetone. Three screens were
treated in this way. The first screen was placed in a frame 6 feet from
the ground in a vertical position facing east which was the direction of
the wind at the time of the study, then left for 24 hours and placed in a
hexane washed jar and transferred to our laboratory for analysis. The
cloth screens were analyzed by the Sherma and Shafik method.^ Analysis
of the screen was seriously complicated by the identification of numerous
interfering peaks due to background impurities in the material, therefore,
a third screen was spiked with 11 pesticides and the-percentage recovery
of these were as follows:
I Fraction II Fraction III Fraction
Heptachlor 107% Lindane 83% Diazinon 103%
Aldrin 90% Hep. Epox. 90% Malathion 108%
p,p'-DDE 106% Dieldrin 96%
p,p'-DDD 94% E. Parathion 95%
p,p'-DDT 95%
58^
-------
Results - Tables 24 and 25 list the concentrations of pesticides in air
from 14 collections from the suburban site in downtown Miami in 1974 and
from the Everglades National Park. Table 26 lists the pesticide concentra-
tions from the Bimini control sampling site and from selected pesticide work
sites in South Florida where occupational studies of workers were being con-
ducted during this contract year. Highest serial concentrations of pesti-
cides in all of the air samples were obtained inside a formulating plant.
Table 27 compares levels from inside a formulating plant and from a storage
shed where packaged pesticides are stored.
The mean and ranges of pesticide concentrations in air and frequency of
occurrence of all the pesticides tested are in the suburban site and the
Everglades are shown in Tables 28 and 29 respectively. The concentrations
of pesticides when measured by the cloth screen are shown in Table 30. Com-
parisons of these residue collections by the MRI double impinger air
sampler and the cloth screen are shown in Table 31.
The persistence of VC-13 in air was studied by repeated sampling by
air above the lawn site where 26 ounces of a 75% VC-13 solution has been applied.
The air concentrations of the pesticide 10, 27 and 50 days after application
are shown in Table 32.
Discussion - From a qualitative point of view, traces of a variety of pesti-
cides were found with regular frequency in both downtown Miami and the Ever-
glades. At the former site VC-13, Dursban and Lindane were found in all
samples collected. Heptachlor, Diazinon and Dieldrinwere the pesticides
next most commonly found in the urban site. Parathion, DDT and its metabolites
were never found at either site. Alpha and gamma chlordane and Ronnel were
identified for the first time in the ambient air of South Florida. In the
Everglades, alpha-BHC, Diazinon, Lindane and Dursban were the pesticides most
frequently identified. The detection of Malathion in both areas was seasonal
and coincided with the use of this insecticide for mosquito control during the
hot and humid months: Pesticides were identified more frequently in the air
of the suburban environment of Miami than in the Everglades.
The concentrations of pesticides in air were not high except in the areas
close to pesticide formulating plants or areas where pesticides are mixed
for aerial application. In the formulating plant, very high concentrations
of a wide variety of pesticides were identified, a finding which emphasized
the importance of wearing protective clothing and respirators. The air con-
centrations in the plant were strikingly different than those seen in a pesti-
cide storage shed where the compounds were sealed and where there was no pre-
paration of formulated products. The air profile of the pesticides in the
formulating plant is not only illustrative of the chemicals in greatest
demand in the area, but the data also illustrate the opportunity for cross
contamination of products during the formulating process. In contrast to
these urban and industrial sites, the island of Bimini in the Bahamas was
almost totally free from aerial contamination by pesticides.
The data from the cloth screen was really qualitative rather than quantita-
tive. If the pesticides trapped by the screen are compared to those identified
59
-------
- /<""'
, x
1
-------
Table 24. PESTICIDE CONCENTRATIONS IN AIR SAMPLES (ng/m°) FROM SUBURBAN SITE IN SOUTH FLORIDA. 1973-74.
Pesticide
VC-13
Dursban
Diazinon
Malathion
a BHC
Heptachlor
Aldrin
Lindane
Dieldrin
Ronnel
a Chlordane
Y Chlordane
3
m Total
Air Volume
S #3
0.6
1.8
ND
ND
0.2
ND
ND
0.2
ND
ND
51
S #4
0.8
4.4
1.2
ND
1.4
1.8
ND
2.5
0.5
ND
51
s #7
0.8
3.7
1.7
ND
1.8
2.2
ND
1.7
ND
ND
49
S #11
0.6
3.3
1.1
ND
0.4
1.2
ND
1.5
0.5
0.6
54
S #13
0.6
1.4
3.3
ND
0.5
1.8
1.1
0.4
0.4
ND
51
S #17
1.0
2.5
2.3
ND
0.5
0.9
ND
0.3
0.5
ND
49
S #19
1.0
2. it
1.0
4.3
0.2
0.7
ND
0.2
0.3
ND
53
S #21
0.5
2.3
1.2
28.1
0.3
1.0
1.1
0.3
0.9
ND
ND
ND
51
S #24
65.0
2.0
2.2
18.2
0.5
1.5
ND
0.3
0.6
ND
ND
ND
51
S #27
5.0
2.8
0.5
ND
0.4
0.9
ND
0.3
0.3
ND
ND
ND
52
S #29
1.3
1.5
1.7
ND
0.6
1.5
ND
0.3
0.7
ND
ND
ND
50
S #32
0.7
1.4
1.0
ND
0.5
1.2
ND
0.5
1.0
ND
ND
ND
49
S #36
0.7
1.9
2.1
ND
0.8
0.6
ND
0.3
0.3
ND
ND
ND
54
S #38
0.4
2.2
2.1
2.0
0.6
1.4
ND
0.3
0.6
ND
0.9
!•*
50
Date Collected
(24 hrs)
Wind-Start
Finish
12/2/73
NE-N
SE
2/7/74
E-SE
E-SE
2/26
N-NW
N-NW
3/22
E-SE
SW
4/30
SE
SE-E
5/28
S-SW
Calm
6/25
S-SW
S
7/8
E-NE
E
7/26
E-SE
E-SE
8/7
Calm
E-SE
9/3
S
SE
9/17
E
E
10/14
SE
SE
11/5
E-SE
S=Sample
ND=Not detectable
All the following pesticides were not detected (ND) in the 14 samples: p,p'-DDE, p,p'-DDT, o,p'-DDE, g-BHC,
HCB, Endrin, Trithion, Ethion, Methyl Parathion, Ethyl Parathion, Phorate,
Methyl Bromophos, Fenthion, Chlorobenside, Methyoxychlor and Toxaphene.
-------
Table 25. PESTICIDE CONCENTRATIONS IN AIR SAMPLES (ng/m ) FROM EVERGLADES SITE IN SOUTH FLORIDA. 1973-74
Pesticide
Dursban
Diazinon
Malathion
a BHC
Heptachlor
Aldrin
Lindane
Dieldrin
Ronnel
a Chlordane
Y Chlordane
3
m Total
Air Volume
Date Collected
Wind - Start
Finish
S #1 S #2
2.0
1.1
ND
0.4
ND
ND
0.2
ND
ND
ND
ND
36
11/4/73
N-NE
SW
2.6
ND
ND
0.5
ND
ND
0.3
ND
ND
ND
ND
28
12/2
N-NE
NE
S #5 S
ND
ND
ND
0.2
ND
ND
0.1
ND
ND
ND
ND
45
2/7/74
E-SE
E-SE
#8
ND
1.3
ND
0.2
ND
ND
0.2
ND
ND
ND
ND
43
2/26
N-NW
N
S #10
1.1
0.8
ND
0.1
ND
ND
0.2
0.3
ND
ND
ND
47
3/22
E
W
S #14
0.5
ND
ND
0.4
ND
0.5
0.5
0.2
ND
ND
ND
43
4/30
E-SE
NW
S #16
0.5
0.5
ND
0.3
ND
ND
ND
ND
ND
ND
ND
43
5/28
S-SE
S-SW
S #18
0.3
0.2
ND
0.2
ND
ND
ND
ND
ND
ND
ND
41
6/25
S-SE
S-SW
S #20
0.3
0.2
38.1
0.3
ND
ND
0.2
ND
0.9
ND
ND
41
7/8
N-NE
SE
S #26
ND
ND
ND
0.3
0.1
ND
0.1
ND
ND
ND
ND
41
8/7
SE-E
E
S #30 .
1.0
0.3
ND
0.9
1.7
ND
0.3
0.5
ND
ND
ND
38
9/3
SE
SE
S #35
1.1
1.9
ND
0.6
0.3
ND
ND
ND
ND
ND
ND
37
10/7
W-NW
N
S #39
ND
1.1
ND
0.4
0.4
ND
0.1
0.3
ND
0.3
0.5
38
11/5
E
SE
S #41
ND
1.5
ND
0.5
0.2
ND
ND
ND
ND
ND
ND
38
12/9
N-NW
N-NE
S=Sample
ND=Not detectable
All the following pesticides were not detected (ND) in the 14 samples: VC-13, p,p'-DDE, p,p'-DDT, o,p'-DDE,
B-BHC, RGB, Endrin, Trithion, Ethion, Ethyl Parathion, Methyl Parathion,
Phorate, Methyl Bromophos, Fenthion, Chlorobenside, Phosdrin, M^rhoxychlor
and Toxaphene
-------
Table 26. PESTICIDE CONCENTRATION IN AIR SAMPLES (ng/m ) FROM BIMINI CONTROL SAMPLING SITE
AND FROM SELECTED PESTICIDE WORK SITES IN SOUTH FLORIDA. 1974
Pesticides
VC-13
Dursban
Diazinon
Malathion
a BHC
Heptachlor
Lindane
Dieldrin
Endrin
Ethion
Ethyl
Parathion
Methyl
Parathion
Phorate
Phosdrin
a Chlordane
Y Chlordane
Toxaphene
Total air
collected m
Date Collected
Wind-Start
Finish
Bimini
S #6
ND
ND
ND
ND
0.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
51
2/11
N-NE
NE
S #9
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
53
Mar.
NA
NA
S #12
ND
0.8
0.4
ND
0.1
ND
ND
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
49 .
3/22
S
NA
S #15
ND
0.5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
53
5/24
S-SE
S-SE
Allied Hel.
S #22
ND
0.5
48.7
ND
1.1
ND
0.4
ND
ND
ND
135.7
59.1
0.8
ND
ND
ND
ND
39
7/12
Calm
E-SE
S #33
ND
1.6
37.6
ND
0.8
I
0.3
ND
ND
ND
196.0
21.0
0.3
ND
ND
ND
P
40
9/23
E
NE
Tri-State
S #23
0.6
ND
0.5
ND
1.1
0.4
19.8
1.6
2.3
ND
12.1
4.1
ND
ND
ND
ND
ND
36
7/26
Calm
E-SE
S #31
ND
0.8
0.8
ND
1.0
1.5
1.2
2.2
1.0
17.5
5.9
ND
0.3
ND
7.6
6.6
ND
39
9/16
E
E
Miami
S #25
0.6
2.0
0.9
ND
0.3
0.8
0.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
43
8/5
SE
E-SE
Airport
S #37
ND
12.9
1.0
ND
0.8
0.3
0.7
0.4
ND
ND
ND
ND
ND
ND
ND
ND
ND
52
10/29
E-SE
E-NE
Shed
S #40
ND
ND
27.3
1.6
2.5
I
1.1
33.2
5.6
ND
48.9
4.9
0.2
1.3
ND
ND
P
52
11/13
Calm
Calm
S=Sample
ND=Not detectable
NA=Not available
I=Interference
P=Present
All the following pesticides were not detected (ND) in the 11 samples:
Aldrin, p,p'-DDE, p,p'-DDT, o,p'-DDE, B-BHC, HCB, Trithion, Ronnel,
Methyl Bromophos, Fenthion, Chlorobenside, Methoxychlor
-------
Table 27. INDOOR CONCENTRATIONS OF PESTICIDES (ng/m ) AT TWO SELECTED
SITES IN SOUTH FLORIDA, 1974.
Pesticides
Storage Shed
South Bay
S #40
Formulating Plant
Goulds
S #28
VC-13
Dursban
Diazinon
Malathion
a BHC
Heptachlor
Aldrin
Lindane
Dieldrin
Endrin '
Trithion
Ethion
Ronnel
Ethyl Parathion
Methyl Parathion
Phorate
Methyl Bromophos
Phosdrin
Methoxychlor
a Chlordane
Y Chlordane
p,p'-DDT
Toxaphene
Total air collected
Date collected
ND
ND
27.3
.1.6
2.5
I
ND
1.1
33.2
5.6
ND
ND
ND
48.9
4.9
0.2
ND
1.3
ND
ND
ND
ND
P
m3 52
11/12/74
10.3
1,417.0
2,078.0
7,305.0
1,913.0
22,171.0
437.0
2,082.0
418.0
107.0
3.5
4.0
10.2
557.0
30.7
0.6
1,544.0
ND
254.0
1,535.0
2,303.0
278.0
ND
28
8/15/74
(2ft hrs.)
S=Sample
ND=Not detectable
I=lnterference
P=Present
All the following pesticides were not detected (ND) in the two samples:
p/p'-DDE, o,pf-DDE, B-BHC, HCB, Fenthion, Chlorobenside
63
-------
Table 28. MEAN, RANGES AND FREQUENCY OF OCCURRENCE OF PESTICIDES
IN 14 AIR SAMPLES (ng/m ) AT SUBURBAN SITE. 1973-74.
Pesticide
Mean
Range
Frequency of Occurrence
VC-13
Dursban
Diazinon
Malathion
a BHC
Heptachlor
Aldrin
Lindane
Dieldrin
Ronnel
a Chlordane
Y Chlordane
0.7
2.4
1.5
3.8
0.6
1.2
0.2
0.7
0.5
0.04
0.1
0.1
0.4
1.4
ND
ND
0.2
ND
ND
0.2
ND
ND
ND
ND
- 1.0
- 4.4
- 3.3
- 28.1
- 1.8
- 2.2
- 1.1
- 2.5
- 1.0
- 0.6
- 0.9
- 1.4
11/11*
14/14
13/14
4/14
14/14
13/14
2/14
14/14
12/14
1/14
1/14
1/14
ND=Not detectable
*Three VC-13 samples were excluded because they were collected just after
application of this pesticide.
All the following pesticides were not detected (ND) in the 14 samples:
p.p'-DDE, p,p'-DDT, o.p'-DDE, &-BHC, HCB, Endrin, Trithion, Ethion,
Ethyl Parathion, Methyl Parathion, Phorate, Methyl Bromophos, Fenthion,
Chlorobenside, Methoxychlor, and Toxaphene.
64
-------
Table 29. MEAN, RANGES AND FREQUENCY OF OCCURRENCE OF PESTICIDES
IN 14 AIR SAMPLES (ng/m ) AT THE EVERGLADES SITE. 1973-74
Pesticides
Mean
Range
Frequency of Occurrence
Dursban
Diazinon
Malathion
a BHC
Heptachlor
Aldrin
Lindane
Dieldrin
Ronnel
a Chlordane
Y Chlordane
0.67
0.64
2.22
0.38
0.19
0.04
0.16
0.09
0.64
0.02
0.04
ND -
ND -
ND -
0.1 -
ND -
ND -
ND -
ND -
ND -
ND -
ND -
2.6
1.9
38.1
0.9
1.7
0.5
0.5
0.5
0.9
0.3
0.5
9/14
10/14
1/14
14/14
5/14
1/14
10/14
4/14
1/14
1/14
1/14
ND=Not detectable
All the following pesticides were not detected (ND) in the 14 samples:
VC-13, p,p'-DDE, p,p'-DDT, o.p'-DDE, &-BHC, HCB, Endrin, Trithion, Ethion,
Ethyl Parathion, Methyl Parathion, Phorate, Methyl Bromophos, Fenthion,
Chlorobenside, Phosdrin, Methoxychlor, and Toxaphene.
65
-------
Table 30. PESTICIDE CONCENTRATIONS COLLECTED FROM A CLOTH SCREEN
(ng/%m ) FROM TWO SAMPLING SITES IN SOUTH FLORIDA. • 1974
Pesticides
Cloth #1
Sites
Date of
Collection
Suburban
9/18
Cloth //2
Suburban
9/18-9/23*
Cloth //3
VC-13
Dursban
Diazinon
a BHC
Heptachlor
Lindane
Dieldrin
Ethyl Parathion
Methyl Parathion
Toxaphene
9.8
I
62.3
I
51.3
22.2
31.8
ND
ND
ND
11.5
I
33.5
5.1
4.7
20.4
ND
ND
ND
ND
ND
I
184.0
3.4
I
18.1
ND
2,190.0
325.0
P
Allied Helicopter
9/23
ND=Not detectable
I=Interference
P=Present
*Five day collection sample
All the following pesticides were not detected (ND) in the 3 cloth samples:
Malathion, Aldrin, p,p'-DDE, p.p'-DDT, o,p'-DDE, 3- BHC, Endrin, Trithion,
Ethion, Ronnel, Phorate, Methyl Bromophos, Fenthion, Chlorbbenside, Phosdrin,
Methoxychlor, aChlordane, Y Chlordane.
66
-------
Table 31. TRAPPING EFFICIENCY OF NYLON SCREEN AND MRI IMPINGERS
AT TWO SOUTH FLORIDA SITES. 1974
Suburban
S #32
MRI Air
Sampler
(24 h^s)
Pesticide ng/m
VC-13 0.7
Dursban 1.4
a BHC 0.5
Heptachlor 1.2
Lindane 0.5
Dieldrin 1.0
Ethyl
Parathion ND
Methyl
Parathion ND
Phorate ND
Toxaphene ND
Cloth
#1
(24 hjjs)
ng/Jjm
9.8
I
I
51.3
22.2
31.8
ND
ND
ND
ND
Cloth
#2
ng/Jjm
11.5
I
5.1
4.7
20.4
ND
ND
ND
ND
ND
Allied Helicopter
S #33
MRI Air
Sampler
(24 h^s)
ng/m
ND
1.6
0.8
I
0.3
ND
196.0
21.0
0.3
P
Cloth
#3
(24 hjs)
ng/Jgm
ND
I
3.4
I
18.1
I
2,190.0
325.0
ND
P
m
Volume
49
40
Date
Collected
9/18
9/18
9/18-9/23
9/23
9/23
ND=Not detectable
I=Interference
S=Sample
P=Present
All the following pesticides were not detected (ND) in the two MRIs and the
three cloth samples: Malathion, Aldrin, p,pVDDE, p,p'-DDT, o,p'-DDE,
3-BHC, HCB, Endrin, Trithion, Ethion, Ronnel, Methyl Bromophos, Fenthion,
Chlorobenside, Phosdrin, Methoxychlor, a Chlordane, and Y Chlordane.
67
-------
by the M.R.I, impinger, there was good qualitative concordance. Of parti-
cular interest to us was the ethyl parathion trapped by the screen when
placed in the local environment of the helicopter site. As has been mentioned
in the discussion of the urinary metabolite studies in this setting, we were
surprised to see continuous excretion of parathion metabolites in the urine
long after the completion of an occupational exposure as defined by pesticide
application. The findings of pesticides in the ambient air could well be
the reason why the metabolites were identified when there was no obvious
work exposure.
For obvious reasons, the human and environmental aspects of dichlofenthion
has been of special interest this last year. It was the regular identification
of this pesticide in the air that prompted us to measure this pesticide after
a single application. As will be seen from Table 32, the air concentrations
were 0.54' ng/m3 a week before the application, yet 10 days after application
the air concentrations at the experimental site was 64.60 ng/m3, and it was
4.95 ng/m-* 23 days later and 1.3 ng/m3 50 days after application! The environ-
mental and human characteristics of this organophosphate pesticide identified
during the last year certainly qualified this chemical as being persistent
in both senses of the word.
68
-------
Table 32. VC-13 CONCENTRATIONS (ng/m ) IN AIR 10, 23 AND 50 DAYS
AFTER A SINGLE LAWN SPRAY APPLICATION OF 26 OZ. OF
75% VC-13 SOLUTION
AIR CONCENTRATIONS
10 Days 23 Days 50 Days
Pre-Application Post Application Post Application Post Application
0.54 64.60 4.95 1.30
69
-------
SECTION VI
EEC STUDIES
EEC Studies - Background Information - Changes in the electroencephalo'.jraph
following human pesticide exposure are dependent upon the type of pesticides
involved and the nature of the exposure. In acute poisoning, the duration of
cerebral anoxia has been shown to produce EEC changes. Hypothalamic spikes
were noted.by Holmes which persisted three years after parathion exposure.
Brown reported persistent EEC changes similar to those seen in temporal lobe
epilepsy following mild acute organophosphate exposure.^ Metcalf and Holmes
reported unusual EEC changes in organophosphate exposures. " Hunter and
Robinson conducted EEC studies in three groups of volunteers fed 0.01, 0.05
and 0.211 mg of dieldrin per man per day, no abnormal EEC changes were noted
with this amount of dieldrin intake.^
Animal studies recently conducted in the U.S. Environmental Protection Agency,
Perrine Primate Laboratory by Dr. John Santolucito and others in the Pharma-
cologogical Branch have compared chronic and low level exposure effects of
Carbaryl on the EEC of monkeys. Similar abnormalities have been noted follow-
ing parathion, dieldrin and DDT exposure. Using a portable EEC machine suit-
able for battery operation in the field it was planned to conduct EEC studies
in human volunteers who were occupationally exposed to pesticides.
Description - With the approval of the Human Experimentation Committee for the
use of the portable EEC Unit whose only additional requirements were for an
extra safety fuse within the circuitry to prevent any possible current over-
load. After a final electronic check, the field trials were initiated.
Field studies in pesticide exposed workers were conducted and volunteer accept-
ability was first observed. Thereafter EEC studies were conducted in the follow-
ing categories: (1) multiple pesticide exposures, (2) single pesticide exposures,
Tracings were collected in relation to the amount and degree of exposure to a
variety of pesticide applications and those personnel involved in single-pesti-
cide exposure.
EEC tracings were collected from a single exposure to different chemicals. A
tracing was obtained during a Baygon (Propoxur) application and upon completion
when the applicator switched to Dursban, a second tracing was collected. EEC
tracings were obtained during and after a VC-13 application. In addition, trac-
ings were obtain after an acute intoxication with this pesticide.
After numerous consultations with Dr. John Santolucito, transference from
the needle electrode to surface electrodes was adapted and EEC tracing were
taken on one volunteer by the surface electrode first and immediately thereafter
by the needle electrode technique.
Results - Tables 33a and 33b lists t.he demographic and exposure category of the
31 participants.
Problems Encountered - Volunteer acceptability was greatly enhanced with the
switch to surface electrodes. Toward the end of the year reports were received
of trouble with the playback unit in Research Triangle Park. Several corrective
measures were taken but apparently with limited success. Until these in-house
difficulties were resolved, Dr. Santolucito advised against further collection.
70
-------
Table 33a . TABLE OF EEC PARTICIPANTS.
Identi-
fication
J.S.
R.S.
E.G.
R.S.
E.O.
A.S.
C.L.
R.J.
J.P.
S.P.
F.B.
A. P.
L.T.
A.S.
J.D.
J.P.
S.P.
F.B.
Afle
39
55
45
55
45
54
45
42
50
22
.59
38
21
54
50
50
22
59
Sex
M
M
M
M
M
F
M
M
M
M
M
M
M
F
M
M
M
M
Occupation
Pilot
Applicator
Ground
Applicator
Ground
Applicator
Ground
Applicator
Ground
Applicator
Housewi fe
Housing Unit
Applicator
Housing Unit
Applicator
Formulating
Plant Supvr.
Form. Plant
Dispatcher
Form. Plant
Loader
Formulator
Assistant
Formulator
Housewi fe
Researcher
Formulating
Plant Supvr.
Form. Plant
Dispatcher
Loader
Classification
of Pesticide
Exposure
Chronic
Chronic
Chronic
Chronic
Chronic
Ingestion
Chronic
Chronic
Chronic
Chronic
Chronic
Chronic
Ch roni c
Ingestion
Occasional
Chronic
Chronic
Chronic
.Categorical
Type of
Pesticide
Agricul-
tural
Parks and
Recreation
Parks and
Recreation
Parks and
Recreation
Parks and
Recreation
VC-13
Concentra-
ted Dursban
Dursban
Multiple
Exposure
Multiple
Exp os ure
Multiple
Exp os .ure
Multiple
Exp os ure
Multiple
Exposure
VC-13
Purpose of
Recording
Base Line
Base Line
Base Line
Exp os ure
to Sevin
Exposure
to Sevin
Sympto-
matic
Base Line
Base Line
Base Line
Base Line
Base Line
Base Line
Base Line
Asymptomatic
Follow-up
Volunteer Pre- Study
Study VC-13
Multiple
Compound
Multiple
Coup ound
Multiple
Low- Level
Form. Activity
Coordinated
W/Air Sampler
Coordinated
Type of
Electrode
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Needle
Compound W/Air Sampler
71
-------
Table 33b. TABLE OF EEC PARTICIPANTS.
Identi-
fication Age
A. P.
L.T.
J.D.
J.D.
R.D.
R.S.
G.J.
B.I.
A.C.
L.S.
T.J.
R.S.
T.W.
38
21
50
50
28
27
53
23
42
! 22
24
54
19
Sex
M
M
M
M
M
M
M
M
M
M
M
M
M
Occupation
Formulator
Assistant
Formulator
Researcher
Researcher
Agri-App..
Pilot
Agri-App.
Pilot
Agri-App .
Pilot
Agri-App .
Mechanic
Agri-App .
Pilot
Agri-App .
Mixer
Agri-App .
Mixer
Ground App.
Parks
Assistant
Formulator
Classification Categorical
of Pesticide Type of
Exposure Pesticide
Chronic
Chronic
Occasional
Occasional
Chronic
Chronic
Chronic
Chronic
Chronic
Chronic
Chronic
Chronic
Chronic
Multiple
Compound
Multiple
Compound
VC-13
Study
VC-13
Study
Multiple
Compound
Multiple
Compound
Multiple
Compound
New
Emp loyee
Multiple
Comp ound
Multiple
Compound
Multiple
Compound
Multiple
Compound
Multiple
Compound
Purpose of Type of
Recording Electrode
Coordinated
W/Air Sampler
Coordinated
W/Air Sampler
Post VC-13
Study
Post VC-13
Study
Seasonal Work
Activity
Seasonal Work
Activity
Seasonal Work
Activity
Control
Seasonal Work
Activity
Seasonal Work
Activity
Seasonal Work
Activity
Azodrin
Coordinated
W/Air Sampler
Needle
Needle
Needle )
Surface )
Surface
Surface
Surface
Surface
Surface
Surface
Surface
Needle
Needle
72
-------
SECTION VII
PERFORMANCE AND PROBLEMS ENCOUNTERED
Performance - Table 34 lists the number of chemical and biochemical ana-
lyses conducted during the study period and number of EEC tracings collected.
Problems Encountered - After injecting 144 samples of urine to determine
the alkyl phosphates using the Shafik et al. method it was noticed at the
end of August that the first fraction of the silica gel column chromato-
graphy which contains DMTP and DETP when concentrated to one milliliter
and injecting five micrograms, negative peaks and sometimes ghost peaks
appeared on the gas chromatograph using the flame photometric detector.
The negative peaks interfered with the quantitation of these alkyl phos-
phates ,:-.t ppb levels. The instrument was turned off and the inlet port,
transfer line, head and base were subjected to ultra-sonic cleaning using
different solvents. New columns were packed "and after these had been
cured and treated with carbowax and installed^and in working condition,
the problem still persisted.
These problems were discussed with Dr. T. M. Shafik in Research Triangle
Park and he,after making some additional recommendations, agreed to investi-
gate the problem in his own laboratory. He found that the original N-amyl
N'-nitro-N-nitrosoguanidine precursor supplied by Aldrich Chemical Company
had been packaged in glass containers. Their second production had been
packaged in plastic containers which questioned the purity of the reagent
and contained certain impurities. Aldrich Chemical Company was contacted
and requested to investigate the reagent. At the time of the preparation
of this report it appears that the problem has been resolved but we were unable
to completely fulfill the alkyl phosphate requirements of .the contract.
73
-------
Table 34. TOTAL NUMBER OF ANALYSES COMPLETED DURING THE ANNUAL STUDY PERIOD.
Type of Analyses
Urinary Alkyl Phosphates
Urinary Phenols
Blood Cholinesterases
Air Samples
Cloth Sample
EEC Collected
Month and Number of Tests
Jan.
Feb.
Mar.
Jan.
Feb.
Mar.
Jan.
Feb.
Mar.
Jan.
Feb.
Mar.
Jan.
Feb.
Mar.
- 16
- 31
- 24
- 23
- 12
- 39
- 71
- 4
- 24
- 3
- 3
- 3
- 1
- 2
- 2
Apr. -
May -
June -
Apr. -
May -
June -
Apr. -
May -
June -
Apr. -
May -
June -
Apr. -
May -
June -
32
23
18
13
64
11
14
9
51
3
3
3
1
2
5
July -
Aug. -
Sept. -
July -
Aug. -
Sept. -
July -
Aug. -
Sept. -
July -
Aug. -
Sept. -
Sept. -
July -
Aug. -
Sept. -
0
0
14
12
33
0
8
22
4
5
5
5
1
2
7
7
Oct.
Nov.
Dec.
Oct.
Nov.
Dec.
Oct.
Nov.
Dec.
Oct.
Nov.
Dec.
Oct.
Nov.
Dec.
- 8
- 0
- 0
- 22
- 28
- 50
- 18
- 25
- 0
- 3
- 3
- 2
- 3
- 1
- 0
Total Number
164
307
250
41 + 12 blanks
1+1 spiked
cloth + 1 blank
33
-------
REFERENCES
1. Aterberry, J.D., Durham, W.F., Elliott, J.W. et al. Exposure to
Parathion: Measurement of Blood Cholinesterase Level and Urinary
p-Nitrophenol Excretion. Arch, of Environ. Health 3:^76-1*85, 196l.
2. Davies, J.E., Davis, J.H., Frazier, D.E. et al. Urinary p-Nitrophenol
Concentrations in Acute and Chronic Parathion Poisoning. Advances in
Chemistry Series, Washington, D.C., American Chemical Society, 1966,
Vol 60, pp 67-78.
3. Elliott, J.W., Walker, K.C., Penick, A.E. et al. Insecticide Exposure:
A Sensitive Procedure to Parathion. J. Agr. Food Chem. 8:111-113, I960.
1*. Shafik, T.M., Sullivan, H., Enos, H. Method for Determination of Low
Levels of Exposure of 2,U-D and 2,U,5-T. Intern. J. Environ. Anlal.
. Chem. 1:23, 1971.
.5. Askew, J., Ruzicka, J.H., Wheals, B.B. Organophosphorus Pesticide: A Gas
Chromatographic Screening Technique Based on the Detection of Methylated
Hydrolysis Products. J. Chrom. Ul:l80, 1969.
6. Shafik, T.M., Bradvay, D., Biros, F., Enos, H. Characterization of
Alkylation of Diethyl Phosphorothionate. J. Agr. Fd. Chem. l8:1171*, 1970.
7. St. John, L.E.Jr., Lisk, D.J. Determination of Hydrolytic Metabolism
of Organophosphorus Insecticide in Cow Urine Using an Improved Thermionic.
J. Agr. Fd. Chem. l6:U8, 1968.
3. Shafik, T.M., Bradway, D., Enos, H., Yobs, A. Human Exposure to Organo-
phosphorus Pesticides: A Modified Procedure for Gas Liquid Chromato-
graphic Analysis of Alkyl Phosphate Metabolites in Urine. J. Agr. Fd.
Chem. 21:625, 1973.
9. Michel, H. An Electrometric Method for the Determination of Red Blood
Cell and Plasma Cholinesterase Activity. J. Lab. Clin. Med. 34:1564.
10! Shafik, T.M., Sullivan,. H.C., Enos, H.F. A Multiresidue Procedure for
Halo and Nitrophenols-Measurement of Exposure to Biodegradable Pesticides
Yielding These Compounds as Metabolites. J. Agr. Fd. Chem. 21:295, 1973.
11. Shafik, T.M., Sullivan, H.C. and Enos, H.F. A Method for the Determination
of 1-Napthol in Urine. Bull. Environ. Contain. & Toxicol. 6:34, 1971.
12; Shafik, T.M. The Determination of Urinary Metabolites—An Index of Human
and Animal Exposure to Non-Persistent Pesticides. Presented at the 167th
ACS Natl. Mtg., Los Angeles, California, April 1-5, 1974.
13.' Sherma, J. and Shafik, T.M. A Multiclass, Multiresidue Analytical Method
for Determining Pesticide Residues in Air. Arch. Environ. Contarn. &
Toxicol. 3: 55, 1975
75
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14. Tc-ssari, J.D. and Spencer, D.L. Air Sampling for Pesticides in the Ijum.-m
Environment. JOAC 54:1376, 1971.
15. Brown, H.W. Electroencephalographic Changes and Disturbance of Brain
Function Following Human Organophosphate Exposure. Northwest Mcd 70:
856, 1971.
16. Metcalf, D.R. and Holmes J.H. EEC, Psychological and Neurological
Alterations in Humans with Organophosphorus Exposure. Ann. N.Y. Acad.
of Sci. 16:357, 1969.
17. Hunter, C.G., Robinson, J., Roberts, M. Pharacodynamics of Dieldrin
(HEOD) Part II: Ingestion by Human Subjects for 18-24 Months and Post
Exposure for 8 Months. Arch Environ. Health 18:12-21, 1969.
18. Shafik, T.M. The Determination of PGP and HCP in Human Adipose Tissues.
Bull, of Environ. & Toxicol. 10:57, 1973.
76
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GLOSSARY
EEC - Electroencephalograph
N.D. - Non-detectable
ppm . - Parts per million
ml/mOSM/1 - MLlliliter per ndlliosmols per liter
PI. - Plasma
ChE - Cholinesterase
n - Number of persons
HUD -Housing and Urban Development (Dade County)
Tr - Trace
yg/ml - Micrograms per mi Hi liter
ng - Nanograms
CFM - Cubic feet per raLnute
o
mj - Cubic meter
PAM - Protopam Chloride
RBC - Bed blood cells
ppb - Parts per billion
w - Volume voided
DMP - (),(>-Dimethyl phosphate
DEP - J),0-Diethyl phosphate
DETP - J),J) Diethyl phosphorothionate thiophosphoric acid
DMTP - C),j>-Di methyl phosphorothionate thiophosphoric acid
Propoxur - 2-Isopropoxyphenyl N-methycarbamate
TJ
Cygon - 0,0-Dimethyl S-(N-me thy lace tamLde) phosphorodithioate-(Dimethoate)
Phosdrin^ - 0,0-Dimethyl 2 methoxycarbony 1-1-methyl vinyl phosphate
Dursban - 0,0-Diethyl 0-(3,5,6,-trichloro-2-pyridyl) phosphorodithioate
IPP - 2-Iso-propoxyphenol
77
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GLOSSARY
Baygon^
DDVPR
RonnelR
VC-13
oBHC
BBHC
- Aprocarb 2Tisopropoxypheniy-N-roethyl carbamate
- Dichlorvos 2,2-dichlorvinyl dimethyl phosphate
- Fenchlorphos 0,0-Dimethyl (2,4,5-trichlorphenol
phosphorothioate
- Dichlofenthion (0-(2,4-dichlorophenyl) 0,0-clietyl
phosphorothionate)
- Alpha isoner of 1,2,3,4,5,6-hexacloro-cylcohexane
- LLndane gamma is oner of 1,2,3,4,5,6-hexachloro-
cyclo-hexane of 99+% purity
78
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
2.
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUB! ITLE
"OCCUPATIONAL & ENVIRONMENTAL PESTICIDE EXPOSURE STUDY
IN SOUTH FLORIDA"
6. PERFORMING ORGANIZATION CODE
5. REPORT DATE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO
John E. Davies, M.D.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Department of Epidemiology & Public Health
University of Miami School of Medicine
P.O. Box 520875
Miami, Florida 33152
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
Contract No. 68-02-1277
12. SPONSORING AGENCY NAME AND ADDRESS
U. S. Environmental Protection Agency
Pesticides and Toxic Substances Effects Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Annual 1/1/74-12/31/74
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT Multiresidue anaiysis of urinary pesticide metabolites offer an effective
means of measurements of human exposure to the non-persistent pesticides. In studies
of different degrees of human exposure to parathion DEP, a metabolite of paraoxon, was
the most sensitive indicator of serious exposure. Concentrations in cases of>0.4 ug/ml
were observed in first urines collected in 7 cases of poisoning with serious enzyme in-
hibition. In contrast, from 71 sequential urines in parathion exposed workers only 1
urine exceeded these concentration. The DEPrDETP ratio was equally informative; the
mean ratio being 4.14 in 20 urines from the poison cases and 0.88 in urines of exposed
workers, a difference which was significant at the <.01 level. Excretion of metabolite
for 91 days after ingesting of Dichlofenthion was observed, emphasizing the significanc
of exposures to the less polar organophosphates in both acute and chronic effects. Lou
level exposures of 38 members of the general population showed that 29% were positive
for Dursban exposure and 100% were positive for PCP, a frequency which suggested tha:
this pesticide was as ubiquitous as DDT in man. A variety of pesticides were identi-
fied in a regular air monitoring program for pesticides in South Florida.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
1. Urinary metabolite surveillance of the
occupational pesticide worker
2. Special significance of DEP the oxon
metabolite in parathion exposure
3. Chronicity of human health effects of
the less polar organophosphates.
4. Low level exposure to general population
_ of non-persis.tentr. -*-*•*--
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
89
20. SECURITY CLASS (Thispage)
22. PRICE
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