EPA-650/1-74-009
June 1974
Environmental Health Effects Research Series
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EPA-650/1-74-009
PESTICIDES EPIDEMIOLOGICAL
FIELD STUDIES
by
Dr. John E. Davies
University of Miami School of Medicine
1600 N. W. 10th Avenue
Miami, Florida 33152
Grant No. 802112
and
Contract No. 68-0211145
ROAP No. 21AYL
Program Element No. 1E1078
EPA Project Officer: Dr. William F. Durham
Pesticides and Toxic Substances Effects Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
June 1974
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
ii
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Abstract
Quantisation of pesticide exposure Is an essential feature of occupational health
Insofar as the safety of the pesticide worker is concerned. When accurate pesti-
cide exposure can be obtained surveillance will protect the pesticide applicator
and has the potential for evaluating human pesticide residue exposures and the
reliability of current re-entry standards. Since worker exposures are usually
multiple, the use of the.raultiresidue technique for the analyses of urinary meta-
bolites can provide the key to quantisation of mixed organophosphate and carbamate
human exposures. With this philosophy in mind, occupational studies of pilots
and loaders were measured. Aircraft loaders were found to be receiving excessive
pesticide exposure as evidenced by the occurrence of several acute pesticide intoxi-
cations, a chronic state of cholinesterase inhibition and a high turnover in this
category of work. The study of urinary di-alkyl phosphates and phenols confirmed
the excessive exposure of these two working groups and the amounts of di-ethyl
phosphate (DEP), di-ethyl thiophosphate (DETP), dl-methyl phosphate (DMP) and
di-methyl thiophosphate (DMTP) and paranltrophenol (PNP) were significantly in-
versely correlated with the red blood cell cholinesterase at the p 0.001 level.
Thus, the lower the red blood cell cholinesterase, the higher the urinary meta-
bolites.
The four di-alkyl phosphates were the derivatives constantly identified in these
occupational exposures. Following an eight hour exposure to a single organophos-
phate both the di-alkyl phosphates and the appropriate phenolic derivatives per-
sisted in the urine for thirty six hours or longer. The impression was gained that
the optimum time for urinary surveillance based on a single sample was nine hours
after the last exposure. These two groups of metabolites were also exceedingly
informative not only in the confirmation of acute pesticide poisoning but also
in the monitoring of the poisoned victim with regard to his need for antl-dotal
therapy.
Organophosphate poisoning is usually thought of as being a abbreviated episode
wherein the clinical manifestations and outcome are usually resolved within 48-
72 hours. Recently we have encountered a much more protracted illness following
acute exposure to certain halogenated organophosphates, this was especially
noticeable following intoxication of VC-13W which is a dichlorophenol di-
ethyl phosphorothioate. The presence of the halogen derivatives attached to
the phosphate moiety resulted in the delayed occurrence of acute intoxication
and a protracted clinical crisis. This was the case in the poisoning reported
herein, and emphasizes the need for a changed appraisal of human subjects in-
toxication by these fat soluble organophosphates. Contrary to past experience
VC-13'*1) and Dursban^ were regularly detected in the air sample and DDT was
conspicuously absent. Qualitatively the air samplings reinforced the greater
use of organophosphates in South Florida.
This report was submitted in fulfillment of Project Number 68X0107 Grant Number
R802112 and of Project Number AS0871 Contract Number 68-02-1145, by the Univer-
sity of Miami School of Medicine, under the sponsorship of the U.S. Environmental
Protection Agency. Work was completed as of December, 1973.
ii
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CONTENTS
Page
Abstract 11
List of Figures Iv
List of Tables v
Acknowledgements vl
Sections
I Conclusions 1
II Recommendations 3
III Introduction 4
IV Urinary Metabolite Studies 5
V Air Sampling Studies 27
VI EEC Studies 32
VII Acute Pesticide Poisoning Investigations 34
VIII References 40
IX Glossary 41
iii
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FIGURES
No. Page
1 Monthly red blood cell and plasma cholinesterase,
paranitrophenol and alkyl phosphate metabolites
observed In a helicopter crop duster (F.B.),
Belle Glade, Florida, 1973 12
2 Comparisons of cholinesterase and paranitrophenol
excretions observed in an aircraft loader (F.R.),
Belle Glade, Florida, 1973
3 Comparisons of cholinesterase and paranitrophenol
excretions observed in an aircraft loader (K.D.T.)
Belle- Glade, Florida, 1973 14
4 Combined alkyl phosphate excretion in an aircraft
loader (M.W.), during ethyl-methyl parathion exposure 16
5 Urinary excretion of Iso-propoxyphenol (Baygon 0.5%)
in a structural pest control operator (Max P.)
following 6 hours of exposure 21
6 Urinary excretion of Iso-propoxyphenol (Baygon 0.5%)
in a structural pest control operator (Edward S.)
following 6 hours of exposure 22
7 Comparisons of urinary 3,5,6-TC pyridinol metabolite
and alkyl phosphate metabolites observed in a structural
pest control operator (M.P.), Miami, Florida, 1973 24
8 Comparisons of urinary 3,5,6-TC pyridinol metabolite
and alkyl phosphate metabolite observed in a structural
pest control operator (E.S.), Miami, Florida 1973 25
iv
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TABLES
No. Page
1 Number of Urinary Metabolite Analyses and Blood Cholineaterase
Studies in Different Pesticide Exposed Groups in South Florida g
2 Comparisons of Urinary Alkylphosphate Concentrations in
Intermediate Exposed Workers and Controls in South Florida LQ
3 Correlation Coefficient (R) of Paranitrophenol, Red Blood Cell,
Plasma Cholinesterase With Urinary Alky 1 phosphates From Pesticide
Exposed Workers H
4 Cholinesterase and Urinary Isopropoxyphenol Levels in Baygon
(0.5%) in Structural Pest Control Operators and Assistants ^9
5 Twenty-four Hour Excretion of Isopropoxyphenol in Two Spraymen
Occupational ly Exposed for Six Hours to 0.5% Baygon Spray
Solution 20
6 Thirty- two Hour Urinary Excretions of 3,5,6-TC Pyridinol and
DMP, DEP, DETP in Two Structural Pest Control Operators 23
7 Retention of Pesticides in Ethylene Glycol (12 hr. run=Flow .82
CFM (16.4 m3) 29
8 Ethylene Glycol Trapping Efficiency (12 hr. run=Flow .82 CFM
(16.4 m3 of air) 30
3
9 Air Concentrations of Pesticides (ng/m ) from Different Sampling
Sites in South Florida 1973 31
10 Confirmed Fatal Intoxications in South Florida, December 1972 -
December 31, 1973 35
11 Confirmed Non-Fatal Intoxication in South Florida, 1973 37
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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., the
Dade County House and Urban Development Program, the Eveready Pest Control
Company. Without the enthusiastic support of the management and staff of
these institutions, these evaluations of human pesticide exposure under
normal working conditions could not have been possible.
vi
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SECTION I
CONCLUSIONS
Important conclusions were reached In three of the four areas of the research
conducted this last year. In the area of the study of urinary alkyl phosphates
and phenolic derivatives, there Is no doubt that recent multi-residue analyti-
cal techniques have provided a greater opportunity to measure human occupational
exposure to pesticides. The data facilitates the quantltatlon of mixed pesti-
cide exposures from workers involved in pesticide application, and from workers
exposed to dislodgable leaf residues in re-entry situations. Their measurement
also significantly contributed to the accurate diagnosis of acute pesticide
poisoning and in the Investigation of suspect "pesticide associated" illnesses.
They will be useful to the physician as well, for their presence is informative
during the clinical management of the poisoned victim; they provide an indica-
tion for the continued need for atropine and oxime therapy.
In the area of occupational pesticide exposures, our preliminary data although
based upon small numbers suggested that the alkyl phosphates are significantly
inversely correlated with red blood cell cholinesterase levels. When the pesti-
cide exposures of the aircraft loaders were compared with the pilots, the ex-
cessive exposure of the former was substantiated by a) the number of acute poi-
soning episodes, b) an 88% employee turnover rate, c) very low cholinesterase
levels particularly the red blood cell values, d) high paranitrophenol averages,
and e) by DEP, DETP and DHP alkyl phosphate residues. The association of DMP
with red blood cell cholinesterase values was particularly impressive and was
an association which possibly emphasized the special toxicity problems of
Phosdrin(R)> As was the first experience of Dr. Shaflk and his colleagues,
in animal studies, OEP, DETP, DMP and DMTP were the only alkyl phosphates found
under these conditions of mixed organophosphate exposures. The monoethyl and
monomethyl phosphoric and phosphorothioic acids are not discussed herein because
Dr. Shaflk stated that they are found in acute pesticide poisonings only and
even then their sensitivity is poor, and therefore, there is no need to look
for other alkyl phosphates other than those herein described. Another signi-
ficant finding was the possible significance of DETP/DEP ratio; greater amounts
of the former were observed in workers when their exposure was Co ethyl and methyj
parathion. At this point in time, this observation must be considered as an im-
pression rather than a conclusion and it certainly warrants further study.
Since exposure to parathion was the predominant organophosphate exposure in
the applicator group this exposure promoted an evaluation of the relative
merits of the alkyl phosphate data compared to the paranitrophenol levels.
Since grab samples of urine rather than 24 hour urine outputs were studied,
firm conclusions cannot be reached on the relative merits of either type of
metabolite. During the dally studies of alkyl phosphate and paranitrophenol
levels in the urine of one loader, the Impression was gained that the former
particularly DEP plus DETP were less subject to the wide variations observed
with paranitrophenol values. One conclusion which can be made with some de-
gree of certainty is that more field research is necessary so that diurnal
variations of both types of metabolites can be studied especially following
work exposure to a single pesticide; a parathion urinary profile is the one
most urgently needed. Another important conclusion was that these metabolites
promote the study of organophosphate and carbamate exposures at levels not
necessarily producing cholinesterase inhibition. With such features, there-
fore, they are ideal for occupational surveillance and for future use as
epidemlologic Instruments.
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The special studies of Baygon and Dursban made it possible to conclude that
future surveillance programs with these pesticides, if reliance must be placed
on a single grab sample of urines, then 6 to 9 hours after exposure is the
ideal time to collect such a specimen. With regard to urinary pesticide
metabolites concentrations should be expressed in terms of micrograms per
hour rather than by correcting for urine osmolality. Pesticide residues were
much greater than expressed in this way then when corrected for an osmolar
correction factor.
From the epidemiological studies of acute pesticide poisoning, several con-
clusions were reached. The number of confirmed cases and the growing problem
of pesticide suspected Illness emphasize the future need for Pesticide
Poison Control Centers in those areas were pesticides are heavily used.
New pesticides are appearing on the scene and without a system for monitor-
Ing the acute incident it is Impossible to anticipate generalized effects in
an area before they occur. VC-13 is a case in example—the different clinical
consequences of over exposure to this fat soluble pesticide was first appreciated
as a result of the Investigation of an acute poisoning. The more halogenated
ions are in the pesticide moiety the more delayed are the effects. Our exper-
ience with VC-13 poisoning confirms that chronic organophosphate pesticide
poisoning has now become a reality.
New pesticides are now found in the South Florida ambient air such as VC-13,
Dursban and some of those identified are fat soluble and the whole picture
is changing from an incidental organochlorlne potential to an incidental
organophosphate exposure. One must conclude that an ongoing meaningful air
sampling program is essential.
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SECTION II
RECOMMENDATIONS
The potential of the urinary pesticide metabolite needs to be further ex-
plored In the occupational environment of the pesticide applicator, in the
work situation following exposure to dlslodgable residues and as an evalua-
tory parameter of proposed field re-entry studies. In the presence of
these needs further studies on urinary metabolite excretion patterns under
normal working conditions should be conducted. Special emphasis should be
given to single pesticide exposure situations - 36 to 48 hour urinary pro-
files. Methodologic research of urine metabolites In the direction of a
simplified and accelerated method of testing is urgently needed. These
should be applicable for testing in the field, what is really needed is
a sort of dipstick test for occupational exposure. Until this is developed
grab sample urines, a system which requires knowledge of the prior voiding
time,seemsto offer the only acceptable type of specimen in a large scale
surveillance program. Based on the findings of this first year's work
the metabolites must be evaluated for as long as 48 hours after a six hour
exposure. We have no Information on the different rates of excretion of
alkyl phosphates which are the result of differences of fat solubility.
We do not know whether there are diurnal variations in the concentrations
that are excreted following a single exposure nor have we confirmed that
these metabolites are present in the general population. It is recommended
that these studies be directed to answer some of the aforementioned ques-
tions to be conducted as soon as possible if the merits of the urinary meta-
bolite is to be measured in human exposure studies.
In addition to the development of metabolite information, our emphasize
this year has been the need to establish selected pesticide poison con-
trol centers in appropriate areas where pesticides are extensively used
In the United States. Secondly, with the change of pesticide use patterns
an ongoing air monitoring program should be instituted in the areas of
high pesticide usage in the United States.
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SECTION III
INTRODUCTION
SCOPE AND PURPOSE OF THE PROJECT
This project entitled "Pesticide Field Epidemiologlc Unit" has as its primary
objective to Implement field epidemiologic studies of in-house research areas
recently developed in Che U.S. Environmental Protection Pesticides Laboratory
in Perrine, Florida. The subordinate objectives reflective of in-house research
areas which were ready for field testing included:
A. Urinary metabolite studies of pesticide workers
B. Air Monitoring studies
C. Field testing of a portable EEC apparatus
0. Pesticide poisoning investigations.
This was a new three year project, and in the first year called for the reloca-
tion and establishment of a new pesticide laboratory in the University of Miami
School of Medicine. This annual which covers pertinent findings in the first
year in these four areas of pesticide field epidemiologic investigations must
aarve as a final report since owing to budgetary cuts in projects, the second
and third years of the study were renegotiated on a contractural basis.
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SECTION IV
URINARY METABOLITE STUDIES
A. Urinary metabolite studies - Background Information. Traditionally, the
occupational health surveillance of the occupationally exposed worker has
relied upon the red cell and plasma cholinesterase changes observed under
conditions of pesticide exposure as an indication of human exposure to organo-
phosphate and carhamate insecticides. Experience has shown that there are
several serious limitations of the interpretability of these indices. These
included the wide range of normal cholinesterase values in the non-exposed
individual, the absence of a definitive cholinesterase level which is diag-
nostic of the occurrence of overt illness, and the necessity of obtaining
pre-exposure baseline data in occupationally exposed studies. Because of
this, many workers In occupational health have investigated the use of
pesticide urinary metabolites as an alternate human pesticide exposure in-
dex. Parathion, carbaryl and propoxur are examples of some of the more
commonly used pesticides in this group whose metabolites have been studied
under conditions of occupational exposure. Recently Shaflk, Enos and their
colleagues have developed a residue procedure for halogen and nitrophenols
in urine. Their preliminary data suggested that these newer techniques
lend themselves to a more specific study of pesticide exposure in man, and
may well prove to be the key to the quantltation of mixed organophosphates
and carhamate exposures.
In a preliminary study of six samples from persons having no exposure and
from occupational workers exposed to Dasanlt (Fensulfrothlon), Thimet
(Phorate) and Di-Syston (Dlsulfoton), Shafik found that DMP, DEP, DETP
and DMTP alkyl phosphate metabolites were identified. In the non-exposed
group urinary metabolite concentrations ranged from 0.005 - 0.04, from 0.003 -
0.08, from 0.02 - 0.10 and from Not Detected - 0.01 ppm respectively for
these four alkyl phosphate metabolites. The average concentrations for these
metabolites in this non-exposed group was 0.01, 0.05, 0.06 ppm and Not de-
tected respectively. Similarly from six samples of the occupationally ex-
posed, the ranges were 0.005-0.06, 0.34-2.41, 0.06-0.22, and 0.16 and
1.62 ppm respectively. Average concentrations in these six samples from
the exposed were 0.02, 0.97, 0.10, and 0.60 ppm respectively. These very
preliminary data suggested that these metabolites reflected occupational
exposure to organophosphate pesticides and were now ready for field testing.
Our studies have sought to take over from this point and in a logical step-
wise progression to explore in greater detail the qualitative and quantita-
tive profile of these pesticide metabolites in several occupational groups
in South Florida. In addition, we have attempted in a preliminary way to
explore the relationship of these metabolites to cholinesterase findings.
Description of Phases - As soon as we received the grant award, we started
to prepare our study as follows:
Phase I - Making contact with the several companies in this area and
investigating what is their season, types of pesticides that
are being used and whether they would participate in our
study. It also required the specialized training of our
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chemists with Drs. Shafik and Enos in the multiple residue
and alkyl phosphate analytical procedures. Flans were also
made to equip and relocate the pesticide laboratory to the
University of Miami Medical Research Building.
Phase II - Related to the qualitative and some quantitative examina-
tions of urines from occupationally exposed pesticide workers.
Phase III - Called for the relation of these exposure indices to
cholinesterase findings.
Phase IV - Called for individual 24 to 36 hour urinary pesticide meta-
bolite profiles for each individual pesticide.
Phase V - Called for the identification of the optimal time between
and after exposure for the meaningful ongoing surveillance
of the pesticide worker.
Phase VI - The final phase called for the identification of urinary
concentrations of Individual pesticide metabolites which
were premonitory of cholinesterase decline and the occurrence
of acute symptoms. In order to systematically Implement
the above experimental design, the following studies were
conducted In a group of pesticide workers in a helicopter
spray outfit in the Belle Glade area and In selected ex-
posure studies In structural pest control operators.
Materials and Methods
The preliminary qualitative and quantitative urine studies acquired from
occupational pesticide exposure were first conducted in cooperation with
the Allied Helllcopter, Inc., In Belle Glade, Florida. This is a crop
dusting company which contracts with South Bay Growers to aerially apply
a wide variety of chemicals to the fields in the area. The individual
growers select and purchase the pesticides which they want to have applied
and the helicopter company is merely responsible for its application.
The helicopter company operates from a modern helicopter pad situated
two miles outside of Belle Glade and they have constructed a new hanger
on the site as well as adjoining administrative offices. Six multiple
rotary blade Bell helicopter aircraft are used these are fitted with twin
multiple Jet spray beams and twin loading tanks. When not in use, the
helicopters are tethered outside the hanger. Inside the hanger there is
a repair shop and a mechanic is employed full-time. Showers and changing
rooms with individual lockers are provided for the four regular pilots
and their loaders. Agricultural chemicals are stored away from the hanger
on a separate site. During the season the pilots and loaders work seven
days a week. Two sorties are made daily, the first at 6 a.m. until about
10 or 11 a.m. and the second at 2 p.m. to 6 p.m. The pilots do not mix
the chemicals themselves and wear coveralls, a crash helmet, respirator
mask, gloves and flying boots. They are partially enclosed in a plastic
bubble and each pilot works with one loader. The loader decants the agri-
cultural chemical from 55 gallon drums of the pesticide concentrate in
the airport into the drum of a large tank truck. In addition, five gallon
drums of a vide variety of pesticide concentrates are also stored and trans-
ported on tne vehicle to the various operational sites in the field. The
planes are loaded and reloaded at these sites. Water is obtained from ad-
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joining canals and after being pumped into the tank the pesticide concentrate
is added and the mixture agitated. The diluted material is then pumped through
a 50 foot hose into the twin tanks on each side of the helicpter. These are
filled and refilled three or four times an hour. The loaders are provided
with gloves, masks and rubber boots. Additionally, oceralls were provided
during the last six months of the study period. A wide variety of pesticides
are applied and the materials used last year included: parathlon 8-E, para-
thion 6-3 (ethyl-methyl mixture), parathion-toxaphene mixture, Cygon (dimetho-
ate), AAtrex (atrazine), Trithion (carbophenothion), Phosdrin (mevinphos),
Dithane,/maneb), Lannate (methomyl), DipelOO, Azodrin (monocrotophos),
Monitor W, Dlbrom (naled), Guthion (azlnophos methyl), and 2,4-DW.
After obtaining a signed consent form from sixteen employees of the Company
a study was conducted on four pilots, five loaders and three controls.
Periodic blood chollnesterase and urine samples were obtained from this
occupatlonally exposed group. Ten cc. of blood were collected in a heparinzed
vacutainer tubes, transported over 100 miles in an icebox to the University of
Miami Pesticides Laboratory were they were analyzed 24 hours after collection.
Periodic grab sample urines were collected in labelled hexane washed jars
stored in dry ice for up to four days and then shipped to Miami where they
were frozen at -15 C and at a later date analyzed both for phenolic deriva-
tives and alkyl phosphate metabolites.
The Michel method was used for red blood cell and plasma chollnesterase deter-
minations, and the Shaflk, Bradway, Enos & Yobs modification for the gas ,
liquid chromatography analyses of alkyl phosphate metabolites in urine. '
The Shaflk, Sullivan and Enos procdure was used for the analyses of halo and
nitrophenols In urines and the Shaflk, Sullivan and Enos procedure for 1-
Napthol In urine was adapted to measure Iso-propoxyphenol (IPP). 5 Grab
sample urines were corrected to an osmolality of 800 ml/Osm/1 prior to
analysis.
Urine and blood studies were conducted in two groups of structural pest con-
trol operators exposed to a single organophosphate or a single carbamate
insecticide. Blood and grab urine samples were obtained from six structural
pest control operators (SPCO) working for the Dade County Housing and Urban
Development program who had sprayed tenement building eight hours a day with
a 2% solution of Dursban and a 1.5% Baygon (propoxur); search was made for
3,5,6-TC pryldinol and IPP during these exposures. Continuous urinary meta-
bolite excretion profiles over a 36 hour period were obtained from two SPCOs
of the Eveready Pest Control Company selectively exposed to 0.5% Baygon, 2%
Dursban and 0.75% DDVP.
Results
Table 1 lists the total number of urinary metabolite analyses and Cholin-
esterase studies in the several occupational groups. Cholinesterase studies
were not always obtained on every urine specimen collected. In addition,
118 chollnesterases were analyzed from pesticide exposure groups including
agricultural inspectors from the U.S. Department of Agriculture, sprayers
from the Dade County Department of Parks, etc. Clinical surveillance of
and pesticide metabolite data from the helicopter group of workers revealed
that pesticide exposure in this group of workers, particularly the aircraft
loaders, was extensive. Three episdoes of acute pesticide intoxications, all
in pesticide loaders, occurred in the study period; 34% of 54 red blood cell
Cholinesterase determinations in this group gave a delta pH per hour of 0.40
or less. A high turnover rate was observed during this study period; 88%
of the loaders and 28% of the pilots changed their jobs during a period of
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Table 1. NUMBER OF URINARY METABOLITE ANALYSES AND BLOOD CHOLINESTERASE
STUDIES IN DIFFERENT PESTICIDE EXPOSED GROUPS IN SOUTH FLORIDA
Analyses
Urinary Phenols
Urinary Alkylphosphates
Blood Chollnesterase
(red blood cell and plasma]
Aircraft Applicators
(n=21)
87
39
54
SPCO
HUD (n=6)
13
11
SPCO
Eveready (n=2)
32
19
6
Others
118
Total
132
58
189
00
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12 months and were lost to follow-up. To the observer it was obvious that signi-
ficant loader exposure occurred during the refilling of the aircraft with pesti-
cides; an effect which was due to the down draft produced by the rotary wings
causing an aerosol exposure from pesticide spillage on the ground. This spillage
could be avoided if an automatic nozzle cutoff valve were a mandatory requirement
in all aircraft spray booms, a suggestion which was reported to the Project Officer.
Sequential data was available on twelve subjects, these were 5 loaders, 4 pilots
and 3 controls. The mean and ranges of the red blood cell chollnesterase, the
urinary alkyl phosphate and paranitrophenol concentrations of these subjects
are shown in Table 2. These subjects during the study period are typical of
high, intermediate and non-organophosphate exposures. Both the RBC and urinary
pesticide metabolite data emphasized the excessive exposure of the loaders. The
four di-alkyl phosphates (DEP, DETP, DMP and DMTP) were the only ones tested in
these samples. Except for DMTP all were found in each of the 27 urines analyzed
in the loaders; some of these specimens included pre-exposure 6:00 a.m. voidings.
Paranitrophenol (PNP) was likewise found in every specimen in this occupational
category. DMTP was not found in 14 of the 27 urines from the loaders, a de-
ficiency which probably reflected early analytical problems of separation of
the metabolite and which was subsequently cleared up. In the pilots, these
biological indices predominately of ethyl and methyl parathion exposure was
considerably less and on four occasions DMP was not Identified. DEP was Identi-
fied on every occasion as was also PNP. The correlation coefficients of PNP,
RBC and PI. ChE with these urinary metabolites are shown in Table 3. Signi-
ficant exposure to organophosphates resulted in the lowering of the RBC and
PI. cholinesterases and also exposure to parathion as high levels in PNP were
found. Thus, If urinary alkyl phosphates were equally good measures of occupa-
tional exposure to anti-cholinesterase, one would expect significant inverse
correlation of them with RBC and PI. ChE and a highly significant correlation
with PNP. Conventionally excessive exposure to organophosphates is reflected
by the red blood cell and plasma cholinesterase inhibition. If the organo-
phosphate exposure is from parathion, urinary paranitrophenol levels is' an
additional index of pesticide exposure and high levels of these metabolites
are found. This Indeed was the case and DEP, DETP and DMP were significantly
correlated with these known biological Indices of pesticide exposure at the
highly significant level of p<£ 0.001. The only exception was in the correlation
of DMTP data which almost certainly reflected initial analytical difficulties
with this specific metabolite. The Inverse correlation of red blood cell
cholinesterase with paranitrophenol on the basis of 15 samples from ten sub-
jects in this study group was -.76. Although the occupational exposure to
this group were to a wide variety of pesticides, ethyl and methyl parathion
(6-3 mixture) were the preparations most frequently used. The highly signi-
ficant correlations herein shown strongly support the potential of these
metabolites in occupational studies of organophosphate expsores, although
the smallness of sample size should^be emphasized. The highly significant
inverse correlations of DMP with RBC ChE is especially noteworthy. It is
possible that Phosdrin^ ' exposure which is known to be highly toxic and
which would give DMP urine metabolites only might be contributory to the signi-
ficance of this association.
Figure 1 illustrates the monthly levels of urinary metabolites obtained on a
grab sample basis from a pilot who was studied over a three month period of
excessive spraying. Monthly red bloqd cell and plasma cholinesterase are
also depicted. Figures 2 and 3 are first expressed with urinary di-alkyl
phosphate and phenolic data detected in these helicopter pilots and swampers
on a grab sample basis. Corresponding red blood cell and plasma cholinesterases
were not obtained on every occasion that the urine samples were collected.
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Table 2. COMPARISONS OF URINARY ALKYLPHOSPHATE CONCENTRATIONS IN HIGH,
INTERMEDIATE EXPOSED WORKERS AND CONTROLS IN SOUTH FLORIDA.
Exposure
groups
High-
Loaders
(n=5)***
Intermediate-
pilots
(n=4)
Controls
(n=3)
Cholinesterase*
RBC
No. mean,
tests ranee
15
9
3
0.3
:09-.72)
0.7
(.5-. 8)
0.8
(.80-. 82)
Alkylphosphates (ppm)**
DEP DETP DMP DMTP
No. mean, mean, mean, mean,
tests
27
11
3
ranee ranee ranee .range
0.48
(.10-1.37)
0.26
(.07-. 66)
0
0.49
(.11-1.7)
0.11
(.001-. 3)
0
0.25
(.005-. 62]
0.06
(0-.26)
0
0.09
(0-.36)
ND
0
0
Paranitrophenol (ppm)**
No. Mean,
tests ranee
61
11
3
0.8
(.04-4.36)
0.3
(.04-. 74)
0
* pH/hr
**corrected to 800 mOsm/1
***includes 3 acute Illnesses
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Tfcble 3. ODREBLAXIflH OOEPFICIEIR (R) OP PAPAT"*OF"™»ff t »F» W-QQn CELL, PLASMA. GBOUH-
ESTRASB. HUH URINARY ALKfLPBQSPHAXES FROM PESTICIDE EXPOSED
Biological Alkylphosphates (ppm)
indices n PEP DBTP BMP MtTP PEP 4- DETP 1BIP + PMTP PEP. DETP. BHP. BMTP
PHP 39 .75 .75 .5 .54 .80 .66 .79
(pp.)
RBC ChE
15 -.72 -.64 -.89 -.11 -.72 -.86 -.78
Plasma ChE 15 -.52 -.48 -.75 .04 -.53 -.68 -.58
-------
Figure 1. Monthly red blood cell and plasma cholinesterase, paranitrophenol
and alkylphosphate metabolites observed In a helicopter crop
duster (F.B.), Belle Glade, Florida 1973
PPM
A pH/hour
1.00 r
075
0.50
0.25
6
FEB.
PLASMA Che
28
DATE
29
MARCH
j
30
APRIL
12
-------
Figure 2. Comparisons of cholinesterase and paranltrophenol excretions
observed in an aircraft loader
-------
Figure 3. Comparisons of cholinesterase and paranltrophenol excretions
observed in an aircraft loader (K.D.T.), Belle Glade, Florida 1973
PPM
A pH/hour
2.00 r
1.50
1.00
0.75
0.50
0.25
RBC——
6 28 11 12 13 14 15 16 17 22 23 24 26 28 28 29 30
=EB. MARCH APRIL
DATE
-------
These figures are presented merely to indicate the interpretative complexities
that were first encountered when urines were obtained from persons whose pesti-
cide exposures were multiple and where the data was from Individuals who re-
ceived pesticide exposure dally. In addition they illustrated the need first
to obtain baseline information on the magnitude and duration of the urinary
metabolite excretion following a single exposure to a single pesticide so that
information could be obtained of the duration of excretion of the metabolite
and the nature of the diurnal fluctuations.
In order to better understand some of these, dally urines were collected from
an aircraft loader (Maynard W.). This man had overt symptoms of anticholines-
terase intoxication which had developed from occupational exposure to parathion.
He was hospitalized and given atropine (this point is shown in Figure 4). His
chollnesterase levels at that point in time were RBC ChE 0.09 and PI. ChE was
0.13ApH/hr; during the next month he mixed and loaded parathion 8E and ethyl-
methyl parathion 6-3 mixtures on the following days:
March 13th, 18th, 19th, 20th, 21st, 23rd, 24th, 27th and 28th
He was unable to give us his pesticide exposure on the other days during this
month. Figure 4 illustrates that based upon the combined di-ethyl and di-
methyl alkyl phosphate levels in dally grab samples there was Indeed signi-
ficant pesticide exposure to ethyl methyl yet at the end of the study period
a repeated cholinesterase showed that the red cell had risen from 0.09 to 0.35
pH/hr and the plasma had risen from 0.13 to 0.32ApH/hr.
One observation which may prove significant in future studies concern the
ratio of DETP to DEP, as already mentioned, we have noted that the loaders
were more exposed than the pilots and since the predominant organophosphate
exposure was to ethyl-methyl parathion these would be reflected by the excre-
tion levels of the di-ethyl alkyl phosphate metabolites. Both pilots and
loaders were representative and reflective of persons chronically exposed
to this pesticide and we noted that 66% of the urines from the loaders had
higher DETP levels than DEP levels whereas the urines from the pilots
only 39% had higher DETP levels than DEP. Very useful quantitative Informa-
tion was also obtained from the study of the phenolic derivatives utilizing
the Shaflk et al. multi-residue procedure. Paranltrophenol was identified
In all of the urines of the pilots and loaders which means that however ex-
amined these high and intermediately exposed group of people always had
qualitative evidence of parathion exposure. Trace amounts of this parathion
metabolite were also identified in the mechanic in 7 out of 9 specimens. Penta-
chlorophenol (POP) traces were found in all 87 urines; the mean concentration
was 0.01 ppm with a range of 0.004-0.024 ppm. These indicate minimal inciden-
tal exposure to this wood preservative and these may be indicative of general
population exposure rather than work exposure.
The identification of 2,4,5-trlchlorophenol was probably reflective of inciden-
tal exposure to Ronnel since there was no history of this insecticide being
used by Allied Helicopters Inc. Similarly, 2,4-DCP and 3,5,6-TC pryidinol
which are phenolic derivatives of VC-13 and Dursban and must have reflected
incidental exposure to these pesticides in a domestic setting or even in the
ambient air (as will be seen in another section of this report both insecti-
cides have been regularly identified in the air sampling program).
15
-------
Figure 4 - Combined alkyl phosphate excretion in an aircraft loader
(Maynard W.) during ethyl-methyl parathion exposure.
PPM
1.0
0.8
0.6
0.4
0.2
TOTAL Me PARATHION EQUIVALENT = 5.3 ppm
TOTAL Et PARATHION EQUIVALENT = 9.4 ppm
ATROPINE
i i i i i
6 28 7 11 12 14 16 22 23 24 25 26 27 28
FEB. MARCH
16
-------
Thus the combination of data from the urinary alkyl phosphates and the phenolic
derivatives provide highly informative qualitative data of the occupational and
incidental exposure of the agricultural worker, and qualitatively indicate the
potential of the multi-residue surveillance of different occupational groups.
Quantitative interpretation is much more complex as will be described hereinafter.
Discussion - The ultimate long term goal of these studies is to try and find
qualitatively and quantitatively a urine profile of the di-alkyl phosphates
which is prognostic of excessive exposure, significant cholinesterase inhibition
and incipient cholinesterase inhibition. If a screening test can be identified
which can be used to monitor the pesticide exposed worker than pesticide handl-
ing can be put on a more rational basis and the worker and Industry will have
the potential for a routine industrial hygiene program. It is our hope that
the urinary metabolite will become the ultimate occupational surveillance para-
meter. The studies reported so far have confirmed, a) the potential of the di-
alkyl phosphates and phenolic derivatives as diagnostic indices of organophos-
phate and carbarnate pesticide poisoning. Collectively the can provide very
specific Information as the nature of the intoxicant in acute poisoning, b)
they have also been shown to be very useful toxicological monitors during an
acute poisoning. They provide the essential information as to the degree of
the organophosphate intoxicant on any point in time during the acute phase
in Illness and they provide toxicological data as to when specific antidotes
can be discontinued. This potential is ill understood and ill recognized by
physicians having to handle long drawn acute organophosphate intoxications.
c) based on a small sample the di-alkyl phosphates appear to have good correla-
tion with cholinesterase Inhibition and these findings confirm Shafik's earlier
observation, however, much more information is needed on the dynamics of these
metabolites under chronic exposure before there is any likelihood of identifying
a quantitative or qualitative profile which is sufficiently indicative of ex-
cessive exposure that can be relied upon as an-occupational surveillance index.
Perhaps, it will be the DETP-DEP ratio under chronic or occupational exposure
to parathion which might provide the clue.
In order to explain the next thrust of our studies next year it is perhaps
timely to list some of the unknown variables, these include:
1. The duration of metabolite excretion following a single
non-toxic exposure to a single pesticide.
2. The effects of a single exposure to multiple pesticides.
3. The quantitative and qualitative urinary profiles of
non-occupational exposure, i.e., how many of these meta-
bolites, if any, can be detected in the general popula-
tion—does food, house dust or the use of insecticide
strips or sprays in the home environment result in the
pesticide excretion?
It is to these unknown areas that we will turn our study design and the remainder
of this report describe single exposures to single and multiple pesticides.
The first group to be studied was a group of six structural pest control opera-
tors working in the Dade County Housing and Urban Development Program. Two
of these (C.L. and M.H.) were sprayers, and the four others were maintenance
men and so were peripherally exposed to pesticides. This group was first stu-
died while working with Baygon (propoxur). A 1.5% Baygon solution was used
during a period of 8 hours. Grab samples of urine and blood for cholinesterase
17
-------
levels were obtained to see if Iso-propoxyphenol (IFF) could be identified by
the Shaflk et al method in this type of exposure. The chollnesterase and
Iso-propoxyphenol are shown in Table 4, These preliminary findings confirmed
that IPP could be readily identified in this type of work exposure. The name
group was similarly tested after they switched from a 1.5% Baygon solution to
a 2% Dursban application. Blood cholinesterases and eight sequential urines
were obtained from three spraymen (C.L., M.H., and M.K.). Following the switch
to Dursban, the average plasma cholinesterase was noted to have declined by
50% though the average red blood cell levels remained unchanged in the group.
3,5,6-TC-pyridinol, the phenolic metabolite of Dursban was readily identified
both during and after this occupational exposure. Urinary concentrations
ranged from 0.29-1.03 ppm. Peak concentrations were reached between nine
and twelve hours after exposure which suggested that this might be the optimal
time for surveillance by this technique if grab urine samples were to be used.
This information prompted us to try and identify structural pest control opera-
tors with single pesticide exposures and whose work practices promoted the
study of pre*exposure baseline urines. Ve have also sought operators who
could be studied on the basis of single work exposures% Eyeready Pest Control
Company was a firm who employed two operators whose work practices fulfilled
these experimental design requirements. Each operator worked six to eight
hour shifts on Saturdays only; spending the rest of the week attending college,
Both agreed to participate in the study and to provide sequential urines,
The first study was a Baygon^ study. Pre-exposure urines and bloods were
collected. Max P. used a hand spray and Edward S. a power spray. Ed wore
rubber gloves and respirator; both mixed their Individual spray solutions
reducing a 14% Baygon concentrated solution to a 0.5% solution for applica-
tion. They sprayed from 8:00 a.m. to 4:00 p.m. The sequential IPP excretion
over this period is shown in Table 5 and Figures 5 and 6.
Results - Firstly the men had negative urines at the commencement of the study
thus confirming their non-exposure history of the previous day. Secondly,
Max sustained more exposure than had Edward, a fact which may be attributed
to the different amount of exposure from the hand spray versus the power spray
and also the use of protective clothing. Thirdly, in both the peak exposure
time occurred five hours after completion of work. Fourthly, in one spray
operator (Max P.), his excretion of the metabolite was completed within 16 hours
after his last exposure; in the other sprayman (Edward S.) 36 hours was in-
sufficient time for the total excretion of the metabolite, trace amounts
still being detected at the end of this time. The total amount of IPP excreted
in the 30 hours for Max was 1,550 ug which is equivalent to 2,139 ug of Baygon.
In the other, Edward, S., 712 ug of IPP was excreted in 29 hours which is the
equivalent of 982 ug of Baygon. It is possible to relate this metabolite's
excretions to the original exposure of the intact pesticide. In order to
obtain a rough estimate of the percentage of the Intact pesticide that is
applied the micrograms of IFF are multiplied by a factor of 1.38 to convert
them to the intact pesticide of Baygon based on their molecular weight.
A second thirty six hour study was conducted in these spraymen following
their single 4*j hour exposure to 2^% Dursban and 0,75% of DDVF« Urine levels
of DMP would be indicative of DDVP exposure and Dursban would be identified
by DEP and DETP alkyl phosphate excretion and also by 3,5,6-TC prydinol
excretion. The excretion pattern of these metabolites in the two spraymen
are shown in Table 6 and Figures 7 and 8. Here again several interesting
findings were noted. Firstly, excretion of the metabolite from Dursban and
DDVP were still occurring 36 hours after this single 4% hour exposure. Secondly,
the maximum excretion of DMP was noted 6 to 9 hours after exposure. Thirdly,
Max never excreted DEP in contrast to Edward. This was also observed in a sub-
-------
Table 4. CttOLINESTERASE AND URINARY ISOPROPOXYPHENOL LEVELS IK BAYGON
(0.5%) IN STRUCTURAL PEST CONTROL OPERATORS AND ASSISTANTS
Identification
C.L.
M.H.
H.L.
C.J.
R.D.
Work
classification
Spray operator
ti ii
Maintenance
ii
ii
Cholinesterase
pH/hr
RBC Plasma
0.96
0.99
0.90
0.89
0.72
1.04
1.33
0.91
0.90
0.98
Iso-propoxyphenol (ppra)
7.99
0.98
0.32
<0.10
0.11
-------
fO
o
Table 5. TWENTY FOUR HOUR EXCRETION OF ISOPROPOXYPHENOL IN TWO SPRAYMKN
OCCUPATIONALLT EXPOSED FOR SIX HOURS
Time of
Operator Voiding
Max P. 8:15 a.m.
12:30 p.m.**
4:10 p. .
6:05 p. .
9:30 p. .
11:30 p. .
8:00 a. .
2:30 p. .
Edward S. 8:20 a.m.
3:00 p.m.
9:45 p.m.
3:28 a.m.
1:00 p.m.
IPP (ppm)
UK/ml*
N.D.
0.07
0.26
0.63
2.3
2.5
0.56
0.12
N.D.
0.10
2.4
0.54
0.56
TO 0.5Z BATGON SPRAT SOLUTION
IPP
ue/hour
N.D.
1.69
18.38
56.6
249.1
149.4
22.8
3.5
N.D.
4.8
70.8
5.9
16.6
Baygon (ug/hour)
equivalent
N.D.
2.33
25.4
78.1
343.8
206.2
31.5
4.8
N.D.
6.6
97.7
8.1
23.0
Corrected for 800 mOsm/1
**exposure period
-------
Figure 5 - OriBaryKBXctetion of Xso-propoxyphenol (Baygon 0.5%) in a structural
pest control operator (Max P.) following six hours of exposure.
350
300
250
200
150
100
50 •
Jjg IPP/HOUR
;2>- jug BAYGON
EQUIVALENT/HOUR
j
8:30 12:30 4:10 6:05 9:30 11:30
AM PM
HOUR
8:00
AM
2:30
PM
21
-------
Figure 6 - Urinary excretion of Iso-propoxyphenol (Baygon 0.5%) in a
structural pest control operator (Edward S.) following six
hours of exposure.
100
80
60
40
20
0
1
-
-©- jug IPP/HOUR
-©- jug BAYGON
EQUIVALENT/HOUR
^ /•>
i i i
8:20 3:00 9:54 3:28 1:00
AM PM AM HOUR PM
1-3-73 11-4-73
.-2
-------
Table 6. THIRTY-TWO HOUR URINARY EXCRETIONS OF 3.5,6-TC PYRIOINOL AND
BMP, DBP. DETP IN TWO STRUCTURAL PEST CONTROL OPERATORS
to
Operator
Max P.
Sdward S.
Time of
Voiding
8:15 a.m.
2:45 p.m.
6:20 p.m.
8:00 p.m.
9:45 p.m.
11:45 p.m.
12:30 a.m.
8:42 a.m.
10:50 a.m.
1:30 p.m.
8:27 a.m.
2:49 p.m.
6:35 p.m.
11:00 p.m.
5:00 a.m.
8:20 a.m.
3:45 p.m.
6:25 p.m.
8:00 p.m.
3,5,6-TC
Pyridinol
ue/hour
N.D.
1.1
2.1
3.4
2.4
3.0
3.3
2.7
3.2
2.2
N.D.
2.4
3.5
4.1
3.7
4.3
4.1
7.1
7.5
Dursban
equivalent
N.D.
1.95
3.72
6.02
4.25
.5.31
5.84
4.78
5.66
3.89
N.D.
4.25
6.20
7.26
6.55
7.61
7.26
12.6
13.3
DMP
ue/hour
N.D.
5.6
19.9
20.7
20.1
16.1
11.1
5.1
Tr.
N.D.
N.D.
9.5
33.9
29.0
14.7
6.2
5.8
6.8
7.1
DEP
ue/hour
N.D.
N.D.
N.D.
2.1
1.2
1.7
2.0
3.3
2.8
DETP
ue/hour
N.D.
8.5
9.6
16.9
16
11.0
13.8
9.6
12.4
3.8
N.D.
1.4
9.1
11.0
8.6
4.8
1.3
9.3
11.2
-------
Figure 7. Comparisons of urinary 3,5,6-TC pyridinol metabolite and alkyl-
phosphate metabolites observed in a structural pest control
operator (M.P.), Miami, Florida 1973
20.0 r
15.0 -
10.0 -
5.0 -
0L
-
-
- .3— J""l_
r2
F— 1— J •— '
-Q> 3,5,6-TC
PYRIDINOL
-<7>- DETP
.3. -<3> DMP
-fl n
1 1 1 1 1 1 1 II
-S
1
8:15 2:45 6:20 1 9:45 12:30 AM 8:42 10:50 1:30
AM PM 8:00 n:45 HOUR PM
11-17-73
11-18-73
2A
-------
Figure 8. Comparisons of urinary 3,5,6-TC pyridinol metabolite and alky I
phosphate metabolites observed in a structural pest control
operator (E.S.), Miami, Florida 1973
3,5,6-TC
PYRIDINOL
DETP
DMP
DEP
8:27
AM
11 -17-73
2:49
PM
6:35 11:00
5:00
AM
11-18-73
8:20
3:45 6:25 8:00
PM
HOUR
25
-------
sequent experiment not herein reported; it was found that once again the same
sprayman (Max) had DETP but no DEP. Whether this reflects an inherent enzyme
defect is conjectural and is under further study. Fourthly, maximum excretion
of DETP was 6 to 9 hours after exposure but 3,5,6-TC pyridinol reaches a peak
much later. Fifthly, both men had detectable amounts of these urinary meta-
bolites even after 36 hours of study.
The Dursban and DDVP equivalent of the total exposure of the total exposure of
each sprayman was calculated on the basis of the di-alkyl phosphate metabolites.
In Edward S., 211 ug of DETP was excreted in 36 hours which is equivalent to
357 ug of Dursban. In addition, 50 ug of DEP was excreted in 36 hours which
is equivalent to 91 ug of Dursban. Together, therefore, this alkyl phosphate
metabolites reflect a total exposure of 448 ug of Dursban. In Max P., 293 ug
of DETP only were excreted which is equivalent to 496 ug of Dursban. Thus,
on the basis of the di alkyl phosphate the mono alkyl phosphate cannot be
measured as such, therefore the calculated intact pesticide is perforce of an
accured expression of the total exposure of these workers to the pertinent
pesticide.
26
-------
SECTION V
AIR SAMPLING STUDIES
B. Air Sampling - Background Information
While the routine monitoring of air for pesticides and other environmental
pollutants has assumed increased importance, available information on the
qualitative and quantitative profiel of air pollution has suffered from in-
adequacies in the air samplers being used, earlier analytical procedures and
the number and location of existing sample sites. In-house research in the
Environmental Protection Agency had addressed themselves to these problems on
chemical analyses and improvement in air sampling techniques and have made
significant progress in both areas. A new analytical method needed to be
evaluated and the introduction of a double impinger system into the air
sampler needed to be tested. The objectives of this project sought to evalu-
ate these new approaches. First study were conducted in the laboratory to
check the recovery of 25 pesticides, and secondly in the field-to evaluate
and test the double impinger sampler system in different locations in South
Florida.
Description of the various phases -
Pursuant to the objectives, the following phases were planned:
Phase I - In-house training of the chemists in new methodologies.
Phase II - To measure the percent recovery of 25 pesticides in a
double impinger system.
Phase III - To measure trapping efficiency and percent recovery of
25 pesticides in ethylene glycol.
Phase IV - To field test the equipment in three different locations
of South Florida.
Materials and Methods
In order to evaluate a new analytical method an investigation of several sub-
strates (cottonseed oil, etc) were first analyzed. Cottonseed oil, silica
gel and ethylene glycol were the materials selected to assess the trapping
potential of each. Duplicate experiments were also conducted with ethylene
glycol. 50 ml. of ethylene glycol was placed in each impinger, the first im-
pinger was spiked with 25 pesticides and the percentage recovery of each
pesticide in each Impinger measured. The second experiment tested the trapping
potential of ethylene glycol by drawing ambient air through a U shaped tube
in an oil bath spiked with the same 25 pesticides. Air was drawn in at 0.82
cubic feet per minute for a 12 hour period giving a total volume of 16.4 m of
air. After 12 hours the pesticide concentrations in each impinger were ana-
lyzed. Midwest Research Institute air samplers were placed in a Miami sub-
urb, at the Miami International Airport and at a remote site in the Everglades,
40 miles west of Miami. 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 first double Impinger system and at the com-
pletion of this 12 hour period, a second sample of air was drawn through the
second double impinger system. The vacuum pump was run at full capacity during
the 24 hour period. The 24 hour volume of air was recorded as was the wind
direction and wind velocity.
27
-------
This 24 hour sample was transferred to the University of Miami laboratory
and analyzed without delay. The analytical method used to measure these
air samples was by the Sherma and Shafik method.
Results
Ethylene glycol was found to be the most suitable trapping material. The
results of retention of 25 pesticides using ethylene glycol following a 12
hour run are shown in Table 7. Table 8 describes the trapping efficiency
of ethylene glycol for the 25 pesticides. Table 9 presents the air concen-
trations of pesticides identified in the three sampling sites. Simultaneous
samplings were done at the Everglades and suburban sites.
Discussion
The reproducibility of pesticide recovery in both spiked samples is testimony
of the reproducibility of the analytical method. Similarly, maximum entrap-
ment occurred in the first impinger and in the second impinger between 12 -
22% of the various pesticides trapped. The types of the several pesticides
identified in the various ampling sites emphasized the changing profile
of ambient pesticides in these areas. It will be observed that VC-13 was
identified on four occasions in the Miami suburbs, as also was Dursban.
These pesticides are currently being extensively used in homes and gardens
and their presence is illustrative of predominant organophosphate profile
of the Miami area.
The qualitative profile of the pesticides identified is strikingly different
to air sampling studies conducted in previous years by virtue of the pre-
dominance of minimal traces of these new type of organophosphates in con-
trast to the usual presence of the organochlorine pesticides. The following
pesticides were not detected in the s,even samples sites: p,p'-DDT, o,p'-DDE,
B-BHC, HCB, Endrin, Trithlon, Ethian^ Rpnnelf Pa.rathion, a.nd methyl parar
thion. DDT was not found in any sample though p,p'-DDE was still present in
trace amounts. The traces of malathion are almost certainly reflective of
mosquito control practices. The Everglades sampling site which is 40 miles
away from the two other sites in the downtown Miami area and the nearest
agricultural area is more than 20 miles away, the preponderance ofoCBHC
related to 1 BHC in this site is difficult to explain. The identification
of Dursban in the Everglades is most surely reflective of aerial transport
from the urban coastline areas since Dursban is not agriculturally applied.
In addition to the 20 pesticides listed in Table 9, VC-13 and Dursban were
Identified in the second fraction; the percentage recovery through silica
gel of these two pesticides were 99 and 100% respectively.
28
-------
Table 7. RETENTION OF PESTICIDES IN ETBTLEHB GLTCOL
(12 hr. run-Flow .82 CFM (16.4 n3)
Concentrations In
nanoftrans
840
1620
2070
3765
2400
545
2300
80
100
200
600
800
800
80
801
180
400
800
200
200
400
800
800
400
400
Pesticide
Sonnel
Methyl Parathlon
Ethyl Parathlon
Trithlon
Ettiion
Dlazlnon
Malathion
BHC
Aldrln
pp« DDE
op DDT
pp1 DDD
pp« DDT
Llndane
B BHC
Heptachlor Epoxide
Dieldrln
End r in
Baygon
2,3,5-Landrin
Carbofuran
Matacil
Zectran
Carbaryl
Meaurol
Percent recovery
S
Impinger 1
73
85
91
93
96
88
97
62
23
94
84
80
90
91
79
81
96
93
70
74
73
69
65
99
85
S
ImplnRer 2
11
Tr
Tr
Tr
Tr
7
Tr
21
39
10
Tr
__
..
11
__
10
Tr.
Tr.
Tr.
16
__
10
—
~
s
Total
84
85+
91+
93+
96+
95+
97+
83
62
104
84+
80
90
102
79
91
96+
93+
70+
90
73
79
65
99
85
Percent recovery
S2
Impinger 1
76
93
96
97
102
87
94
70
17
81
81
82
89
97
81
82
98
93
88
83
83
77
70
98
98
S2
Impineer 2
10
Tr
Tr
Tr
Tr
8
Tr
22
38
11
Tr
__
__
7
__
7
Tr
Tr
Tr
10
.._
10
__
__
S2
Total
86
93+
96+
97+
102+
95
94+
92
55
92
81+
82
89
104
81
89
98+
93+
88+
93
83
87
70
98
98
-------
Table 8. ETHYLENE GLTCOL TRAPPING EFFICIENCY
(12 hr. run=Flow .82 CFM (16.4 m3 of air)
Concentrations in
U-tube (ng)
840
1620
2070
3765
2400
545
2300
80
100
200
600
800
800
80
801
180
400
800
200
200
400
800
800
400
400
Pesticide
Ronnel
Methyl Parathion
Ethyl Parathion
Trithion
Ethion
Diazinon
Malathion
(XBHC
Aldrin
p,p'-DDE
o,p'-DDT
p,p'-DDD
p.p'-DDT
Lindane
B-BHC
Heptachlor Epox.
Dieldrin
Endrin
Baygon
2,3,5-Landrin
Carbofuran
Metacil
Zee t ran
Carbaryl
Mesurol
Percent Recovery
AR
Impineer 1*
52
53
63
53
58
46
56
43
23
74
71
73
73
59
53
64
73
78
38
40
40
26
18
60
49
AR
Impinger 2*
19
15
17
13
14
16
16
22
22
20
17
16
16
20
15
21
17
18
18
21
16
12
Tr
13
12
Total*
71
68
80
68
72
62
72
65
45
94
88
89
89
79
68
85
90
96
56
61
56
38
18+
73
61
U-
Tube
7%
12%
Percent Recovery
AR2
Impineer 1
62
76
78
74
77
68
73
64
17
78
75
78
81
96
64
67
77
78
65
65
65
44
28
91
73
AR2
Impineer 2
23
16
18
16
17
18
14
28
30
25
19
19
19
25
11
20
16
18
20
24
16
• 17
TR
19
15
AR2
Total
85
92
96
90
94
86
87
92
47
103
94
97
100
111
75
87
93
96
85
89
81
61
28+
110
88
*(4 hour power failure)
-------
Table 9. AIR CONCENTRATIONS OF PESTICIDES (ng/m3) FROM DIFFERENT SAMPLING SITES IN SOUTH FLORIDA 1973
Pesticide
VC-13
Dursban
Dlazlnon
Malathlon
oCBUC
Heptachlor
Aldrin
Lindane
Dleldrln
p,p'-DDE
M3 Collected
Wind Direction:
Start
Finish
Suburban
Sample f 1
ng/m3
1.09
1.68
1.02
____
0.51
1.00
0.25
0.68
0.40
0.18
43.15
N-NE
S-SE
Sample $2
ng/m3
1.21
1.82
0.78
_____
0.65
0.52
0.13
0.41
0.35
____
48.92
SW
NW
Sample f 3*
ng/m3
0.76
2.04
2.27
7.24
0.95
0.51
0.18
0.93
0.42
— —
45.87
NE
N-NE
Sample 14*
ng/m3
0.63
1.47
0.30
____
1.37
0.58
0.10
0.62
0.46
0.19
53.71
ESE
SE
Everglades
Sample $5*
ng/m3
0.87
____
0.85
0.18
0.18
45.81
NE
NW
Sample 16*
ng/m3
0.77
0.30
— —
1.32
—.-_
0,19
0.20
— —
47.74
E-NE
E-SE
Miami Airport
Sample 87
ng/m3
2.95
6.10
1.00
1.68
0.97
2.65
0,89
0.42
0.67
0.62
49.94
SE
NW
*slmultaneous samples ('3 and 5, #4 and 6)
-------
SECTION VI
EEC STUDIES
C. EEC Studies - Scope, purpose and background information
Changes in the electroencephalograph 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 a parathion exposure. Brown reported persistent EEC changes simi-
lar 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 abnor-
mal EEC changes were noted with this amount of dieldrin intake. EEC changes
were prognostic of incipient convulsions due to over exposure to the diene
group of insecticides. The occurrence of this degree of incipient toxicity
is nowadays avoided by relying entirely on threshold blood levels of dieldrin.
Animal studies recently conducted in the U.S. Environmental Protection Agency
Perrine Primate laboratory by Dr. John Santolucito and others in the Pharmaco-
logical Branch have compared chronic and low level exposure effects of Carbaryl
on the EEC of monkeys. Similar abnormalities have been noted following para-
thion, dieldrin and DDT exposure. Using a portable EEC machine suitable for
battery operation in the field it was planned to conduct EEC studies in human
volunteers who were occupationally exposed to pesticides.
Description of the various phases
The first phase was the completion and in-house evaluation of the portable EEC
apparatus. The second phase was the training of project personnel in EEC
techniques and a medical review of the equipment and its application by the
Division of Electroencephalography, University of Miami School of Medicine.
The third phase was the implementation of any necessary modifications suggested
by this Division and pre-testing on non-exposed volunteers, and the fourth and
final phase, field application of the machine.
Materials and methods
The EEC machine to be used is a portable battery operated apparatus with facil-
ities for recording tracings on a tape unit. There will be digital conver-
sion of electronic recordings which are transcribed from electro-magnetic
tapes. These will be submitted to Dr. Santolucito in Research Triangle Park
for interpretation. It'was planned to use intracuticular scalp recordings
from needle electrodes rather than surface electrodes. These should dimish
the background interference. After obtaining signed consent forms, the tech-
nique to be used in testing was as follows: Three sterile disposable butterfly
infusion needles would be inserted at three sites into the following areas of
the scalp after cleaning this area with acetone. One anterior electrode placed
1*5" posterior to the nasion, a second left lateral electrode 14" to the left
of the occipital, and third, a right lateral electrode place IV to the right
of the occipital point. The subject would be examined in a recumbent position
with the eyes closed and tracing would be run for a fifteen minute period.
32
-------
Interim Report
Prior to the receipt of the portable unit in the second half of the project
year, the field investigator received instructions on electroencephalographic
techniques from the Division of Electroencephalography in the Department of
Neurology of the University of Miami School of Medicine. The director of
this Unit, Dr. E.T. Richey and his Blomedlcal Engineering representative re-
quested a review of the specifications of the apparatus and agreed to review
the procedure. Following a preliminary run on a non-exposed human volunteer,
Dr. Richey expressed concern with regard to low input impedence and questioned
whether the electrical tracing from the three scalp sites could be interpreted
with ease. It was not understood at this time that the frequency rather than
the actual wave patterns were being measured. Questions were also raised as
to whether there was any hope of altering the technique to obviate the necessity
of intracuticular electrodes in favor of using the conventional and acceptable
surface electrodes. It was agreed to provide the EEC Division with the speci-
fications of the apparatus from Biomedlcal Engineering, and to arrange a con-
ference with Dr. Santolucito prior to moving to phase 4 - the field applica-
tion. Additional safety modifications suggested by the Director of the Division
of EEC have been Implemented and'intracuticular electrode will still be used.
The machine is now ready for use in the field.
33
-------
SECTION VII
ACUTE PESTICIDE POISONING INVESTIGATIONS
D. Acute Pesticide Poisoning Investigations - Scope, purpose and background
Information - The two objectives of this work unit were:
1. To Investigate and confirm suspect pesticide poisoning cases
occurring in the Dade County area, and to document the clinical
and therapeutic responses observed at the bedside. These find-
ings, with medical confirmation of suspect cases, would be made
available to the Dade County Community Studies Pesticide Project.
2. To study pesticide metabolite dynamics in blood, urine and fat
in acute poisoning cases hospitalized in the Dade County area
and to determine the informative potential of these in the clinical
management of the case.
Although pesticide poisoning has not been a reportable disease in Florida,
the resources and experience of the Miami Pesticides Laboratory have become
known to most hospital Emergency Rooms and pathologlsts in the South Florida
area and so has been widely used. In the past, epdiemiologic and laboratory
confirmation has been offered through the Community Studies Program and it
was planned in this project to continue this function in the University and
to facilitate acquisition of pesticide poisoning incidence data in the area.
Results
Table 10 lists the confirmed fatal pesticide poisoning cases investigated by
this project and Table 11 lists the number of confirmed non-fatal cases.
Table 12 presents the clinical and analytical features of an additional 26
investigated cases of suspect pesticide illnesses which the project investi-
gated during this year.
In February, 1973, no further support was received at the Florida Community
Pesticide Studies terminated, therefore, the data has been made available to
the Pesticides Operations Office in Washington, D.C. and in the Southwest
Region IV (Drs. Evrard and Kessler) so that the material could be utilized
by the appropriate Federal authorities. Administratively, therefore, reports
were transferred from Jacksonville, Florida to Atlanta, Georgia.
Discussion
1 - Confirmed fatal cases - All three fatalities were due to organophosphate
exposure; these pesticides were identified in the various specimens and
are shown in the table and all were confirmed by gas liquid chromatography
in the flame photometric and electron capture detectors. One of the deaths
resulted from the ingestion of VC-13. This pesticide is becoming an in-
creasingly serious chemical problem in the area and the material is readily
available in most garden stores. Illness following ingestion of this
material is slow to evolve and the clinical picture is protracted in many
instances. In the past, the patient has Been hospitalized initially more
of a precautionary measure and then what usually happens is that quite
suddenly a severe and life threatening cholinergic crisis will develop
calling for heroic antidotal and resuscltative management, The danger of
this type of intoxication lies in the deceptively mild clinical picture
at onset, a feature which might tempt the inexperience to discharge the
34
-------
Table 10. CONFIRMED FATAL INTOXICATIONS IN SOUTH FLORIDA, DECODER 1972-DECEMBER 1973
01
Name Race/Sex Age
1. Juan M.
2. Henry K.
3. Walter M
W/M
W/M
W/M
20 y/o
76 y/o
51 y/o
Date of Type of
incident Exposure Material Confirmed clinical and laboratory tests
12/31/72
5/9/73
9/7/73
Ingest ion-
Suicide
Ingest ion-
Suicide
Ingest ion-
Suicide
Parathion
VC-13
Diazinon 51Z
RBC ChE 0.15 PI. ChE 0.15
Parathion in blood 18.3 ppb.
Gall Bladder - VC-13 - 37.5 ppm. by F.P.D.
Fat from kidney - VC-13 - 174 ppm. by F.P.D.
Urine = 2,4-DCP (chloroacetate derivative) 12
Liver - VC-13 - 3.6 ppm. by F.P.D.
Gastric content (294 mg. bloody) - 0.34 ppm
by F.P.D.
Whole blood - VC-13 - 1.0 ppm by F.P.D.
9/10/73 - RBC ChE 0.20 PI. ChE 0.07
Pre PAM- Diazinon in blood 34 ppb. by EC & I
9/10/73 - RBC ChE 0.25 PI. ChE 0.06
Post PAM - Diazinon in blood 17 ppb. by "
9/12/73 - RBC ChE 0.29 PI. ChE 0.09
Diazinon in blood 9 ppb. by EC &
9/13/73 - RBC ChE 0.30 PI. ChE 0.09 by " &
Diazinon in blood 10 ppb. E.G.
9/18/73 - RBC ChE 0.32 PI. ChE 0.09
Diazinon not found (FPD & EC)
p,p'-DDT <2, p.p'-DDE 7.1 and Dieldrin <1 pp
respectively .
-------
Che patient home If the probabiluty of a delayed onset of illness is not
appreciated. The halogenic portion of this organophosphate pesticide
favors deposition in fat, and this is the same reason for the slow evolu-
tion of symptoms. The fat solubility potential also calls for the daily
monitoring of blood for VC-13 and urine for the phenolic metabolite 2,4-
DCP. Atropine therapy must be continued as long as the parent compound
or its urinary metabolite can still be identified, and atropinization
may have to be continued for several days. Experience gained in this
special type of organophosphate exposure (halogenated organophosphate)
emphasizes the need for further study of acute and chronic exposure to
organophosphate pesticide that have fat soluble characteristics.
2 - Confirmed cases - Incidence Data ~ Eighteen non^fatal pesticide poison-
ings were confirmed in 1973. The types of poisonings, materials involved
and results of the appropriate analytical diagnostic tests are shown in
Table 11. Eighteen cases were due to organophosphate intoxications and
ten of these were from occupational exposure. In contrast to residue
problems in California, once again in South Florida, our investigations
have failed to confirm an episode of "picker poisoning", a topic of
current discussion of political importance and exhibiting succinct
geographical distribution characteristics. Arsenic and pentachloro-
phenol were the other agents Involved besides the organophosphate insecti-
cides.
The case of arsenic poisoning occurred in a 6 year old white male child
who was poisoned by some toys that he picked up in a garbage dump. Weed
killer had been discarded into the dump and has spilled over the toys.
The pentachlorophenol intoxication was observed In a carpenter and the
diagnosis was made on the basis of exposure, clinical picture and urine
results which were obtained eight weeks after his last exposure. The
patient was a 60 year old white male carpenter who had had extensive
exposure to pentachlorophenol which he used for termite control. Besides
complaining of weakness anorexia and loss of weight, the patient had
severe dermatitis with fissures of the skin. He also developed an exten-
sive generalized and painless lymphadenopathy which resembled Hodgkins
Disease. Lymph node biopsy, however, did not confirm this diagnosis,
the section showing only generalized chronic inflamatory changes.
Discussion 3 - Unconfirmed Cases - Twenty six cases of pesticide associated
illnesses were investigated, and on the basis of clinical findings, ex-
posure histories, pathological findings and appropriate laboratory ana-
lyses were considered not to be due to pesticide exposure. Five of the
cases were fatal, and at the time of death, health or agricultural offi-
cials suggested suspect pesticide exposure. The definitive diagnosis
was not made available to us in all cases but alcoholic seizures, acute
asthma with chronic obstructive lung disease, methaqualone overdose and
meningitis were the ultimate causes of death in four of the five uncon-
firmed cases. Of significant medico-legal importance was the occurrence
of an acute asthmatic attack in two agricultural inspectors, both had
been employed by the Florida State Department of Agriculture for many
years and both had a history of chronic bronchitis, emphysema and periodic
attacks of asthma. One of the Inspectors died after inspecting a celery
field; it was first thought that the cause of death was the result of
parathion residues on celery or an exposure from the drift from aerial
applications in the adjoining fields. Leaf residues were insignificant
and no paranitrophenol or paraoxon were found in the liver or kidney by
gas chromatography using the electron capture and flame photometric
36
-------
Table 11. CONFIRMED NON-FATAL INTOXICATIONS IN SOUTH FLORIDA, 1973
Race,
Name Sex
1. Abraham W. B/M
2. Frank R. B/M
3. Sammy G. B/M
4. April P. W/F
5. Maynard W. B/M
6. Felix S. Ind./H
7. James C. P.W/H
8. Jeral F.* W/M
9. Fernando B.W/M
0. Charles P. B/M
Age
(yrs)
61 y/o
57 y/o
21 y/o
19 mos.
27 y/o
21 y/o
25 y/o
18 y/o
5 y/o
25 y/o
Date of
incident
1/4/73
2/6/73
2/6/73
3/7/73
3/8/73
3/9/73
3/23/73
3/5/73
3/11/73
Type of
Exposure
Dermal-
Occupational
Occupational
11
Ingest ion-
Accidental
Occupational-
Dermal
Dermal-
Occupational
Ingestion-
Suicide
Oc cupat ional-
Accidental
Ingestion-
Accidental
Occupational-
Dermal
Material \
Phosdrin
Organo-
phosphate.
11
Dursban and
Diazinon
Organo-
phosphate
11
VC-13
Organo-
phosphate
Dematon
Parathion
Confirmed clinical and diagnostic tests
1/4/73 - Pre-PAM - Serum ChE 0.14
Post PAH - RBC Che 0.26 PI. ChE O.E
1/5/73 - RBC ChE 0.16 PI. ChE 0.12
Unable to detect Phosdrin by E.C.
RBC ChE 0.21 PI. ChE 0.49
RBC ChE 0.11 PI. ChE 0.15
Asymptomatic, taken off work
3/8/73 - RBC ChE 0.14 PI. ChE 0.10
3/7/73 - Gastric contents pH 1.72
Diazinon 45 ppm. and Dursban 213 ppm by F.PB
3/8/73 - Serum - Diazinon 0.6 ppm. and
Dursban 0.4 ppm. by F.P.D. and E.C.
3/7/73 - Post PAM RBC Che 0.09 PI. 0.13
3/8/73 - RBC ChE 0.18 PI. 0.16
Hospitalized
90% Inhibition colormetric method
Case confirmed by clinical picture
80% Inhibition Fleisher Pope method
Case confirmed by clinical picture.
RBC ChE 0.48 PI. ChE 1.26 (5/16/73)
Case confirmed by hospital notes and
clinical picture.
us
*A second incident occurred on Hay 12th when patient was hospitalized for
spilling Phosdrin on akin and inhalation. Case confirmed by clinical
picture and atropine response.
-------
Tohi* 11 (Vr^f-i™,^ CONFIRMED NON-FATAL INTOXICATIONS IN SOUTH FLORIDA, 1973
Name
11. Wesley S.
12. Johnny L.
13. Stephen B.
14. Francisco C
15. William K.
16. Walter B.
17. Donald T.
Race,
a ex
B/M
B/M
W/H
. W/H
W/H
B/M
W/H
A^e
30
46
18
14
60
2
6
Date of
incident
3/3/73
1/8/73
5/9/73
6/20/73
7/2/73
9/10/73
10/17/73
Type of
exposure
Occupational
Dermal
Occupational-
Inhalation
Occupational-
Dermal
Ingest ion-
Accidental
Occupational-
Carpenter
Dermal-
Accidental
Ingest ion-
Accidental
Haterial
Organo-
phosphate
Parathion
Organo-
phosphate
Spectricide
(Diazinon 25%)
Pentachloro-
phenol
Parathion
Arsenic
Case confirmed by clinical picture and atropii
response .
Cholinesterase 13 ChE-tel units (Normal 45-90)
Serum ChE 20 (N 45-90) 1/9/73
RBC ChE 0.35 PI. ChE 0.32
5/10/73 RBC ChE 0.29 PI. ChE 0.34
Pre- treatment (Hospital Notes) ChE .45 (Norma
1.90-3.0) Post-treatment PI ChE 22 units (45-
units Normal range)
6/22/73 - RBC ChE 0.70 PI. ChE 0.08 (Michel
Method)
Serum PCP .513 ppm, Urine 0.3 ppm. (Analyzed
9/21/73 p.p'-DDE 39 ppb. p,p'-DDT 8 ppb.
dieldrin 1.5 ppb.
7/2/73 - RBC ChE 0.65 PI. ChE 0.68
Case confirmed by clinical picture and atropi
response.
9/15/73 - RBC ChE 0.50 PI. 0,72 (Analyzed 9/1
collected at 4:17 p.m.
9/15/73 - RBC ChE 0.62 PI. 0.87 (Analyzed 9/1
collected at 10:16 p.m.
p.p'-DDE 2 ppb., no p.p'-DDT, dieldrin Ippb.
No organophosphate found by F.P.D. and EC
Case confirmed by M.E.'s office
Urine 16 mg/ml. Gut Belt method
Field investigation made.
-------
detectorn. Other mechanisms involved in unconfirmed pesticide poison-
ings related to 1) the occurrence of dermatitides and 2) to the chance
finding of unusually low red blood cell or plasma cholinesterase. An
example of the former was the occurrence of erythema multifonne in a
52 year old white male whose home had recently been sprayed with Baygon.
Iso-propoxyphenol was not identified in the urine of the other members
of the family.
With regard to the latter, low cholinesterase values were identified in
a three week old black male infant with pneumonia and possible pesticide
exposure. In order to evaluate normal physiological occurrence of low
red blood cell and plasma cholinesterase in the newborn, five blood
samples were collected and analyzed from healthy premature babies of
the same birth weight as the case in suspect. The average red blood cell
of these infants were 0.444pH/hr and for plasma cholinesterase the
average level was 0.47 ApH/hr respectively.
At the request of Dr. Suggs and with Dr. Durham's permission, pseiido-
cholinesterase studies were conducted in individuals with low plasma
cholinesterase as well as their families. These studies were recon-
firmed by Dibucaine studies by Dr. Suggs in the Center for Disease
Control in Atlanta, Georgia. A ciguatera poisoning was also confirmed.
39
-------
SECTION vin
REFERENCES
1. Shafik., T.M., H.C. Sullivan and H. F. Enos. A Multiresidue Procedure
for Halo and Nitrophenols-Measurement of Exposure to Biodegradable
Pesticides Yielding These Compounds as Metabolites. J. Agr. Fd. Chen.
21:295-298, 1973.
2. Shafik, T.M., D. E. Bradway, H. F. Enos, and A. R. Yobs. Human Exposure
to Organophosphorus Pesticides. A Modified Procedure for the Gas Liquid
Chronatographic Analysis of Alkyl Phosphate Metabolites in Urine, j. Agr.
Fd. Chen. In Press
3. Michel, H.O. An Electrometric Method for the Determination of Red Blood
Cell and Plasma Cholinesterase Activity. J. Lab. Clin. Med. 34:1564-
1568, 1949.
4. Method for the Determination of Metabolite or Hydrolysis Products of
Organophosphorus Pesticides in Man. Perrine, U. S. EPA Office of
Research and Monitoring Analytical Manual, Sec. 6, 1972.
5. Shafik, T.M., H. C. Sullivan and H. F. Enos. A Method for the Deter-
mination of 1-Napthol in Urine. Bull, of Environ. Contam. and Toxicol.
6:34-39, 1971.
6. Sherma, J. and T. M. Shafik. A Multiclass, Multiresidue Analytical Method
for Determining Pesticide Residues in Air. Submitted for Publication
7. Holmes, J.H. Clinical Studies of Exposure to the Organophosphorus
Pesticides. New York, Academic Press, 1965.
8. Brown, H.W. Electroencephalographic Changes and Disturbance of Brain
Function Following Human Organophosphate Exposure. Northwest Med. 70:
845-846, 1971.
9. Metcalf, D.R. and J. H. Holmes. EEC, Psychological, and Neurological
Alterations in Humans with Organophosphorus Exposure. Ann. N.Y. Acad.
of Sci. 160:357-365, 1969.
10. Hunter, C.G., J. Robinson, and M. Roberts. Pharmacodynamics of Dieldrln
(BEOD) Part II: Ingestion by Human Subjects for 18-24 Months and Post-
Exposure for 8 months. Arch. Environ. Health 18:12-21, 1969.
40
-------
EEC
Dasanit
R
(R)
Section IX
GLOSSARY
electroencephalograph
(0,0-diethyl-O-p (methylsulfinyl) phenyl phosphorothioate ~ fenaulfo-
thion
Thimet" 0,0-Diethyl S-(ethylthio)-methyl phosphorodlthioate - phorate
Di-SystonR 0,0-Diethyl S-(2-(ethylthio)ethyl) phosphorodithloate - disulfoton
DMF 0.,.0-Dimethyl phosphate
DBF £,_0-Diethyl phosphate
DETP £,j>-Diethyl phosphorothionate thiophosphoric acid
DMTP £,£-Dimethyl phosphorothionate thiophosphoric acid
M.D. Non-detectable
ppm parts per million
parathion 0,0-Diethyl-O-p-nitrophenyl phosphorothioate
Methyl parathion 0.0-Dimethyl 0-p-nitrophenyl phosphorothioate
parathion 8E 8 pounds Ethyl Parathion in a gallon of liquid
parathion 6-3 Mixture of Ethyl and Methyl parathion
A mixture of chlorinate camphene compounds of uncertain identity -
* e combined chlorine 67-69%)
(0,0-Dimethyl S-(N-methylacetamide)phosphorodithloate - Timethoate
2, chloro, 4, ethyl 6 iso proylamlno-S, trlazene
(0,0-Diethyl S-(p-chlorophenylthio) methyl phosphorodithioate)
mevinphos (0,0-Diaethyl 2 methoxycarbonvl-1-methvl vinvl ohosohate)
manganese-Ethylenebisdithlocarbamate - maneb
methomyl. S-Methyl N (methyl-carbamoyl)oxy)thioacetlmldate
Baellluiq thurineienala (crystalline bacterial toxin)
dimethyl phosphate of 3-hydroxy-N-methyl-ciscrotonamlde ~ nonocrotoph(
methamidophos °»Si-Dimethyl phosphoramldothioate
(1,2 dibromo-2,2-dichloroethyl dimethyl phosphate)- naled
(R)
(R)
(R)
(R)
Toxaphene
Gygon
Aatrex
Trithion
PhoadrinR
DithaneR
LannateR
DipelR
AzodrinR
MonitorR
DibromR
Guthlon R
0,0-Dimethyl s-(4-oxo-l,2,3-benzotriazine-3-(4-H-yl methyl)- azinpho;
methyl
41
-------
ml/mOsm/1
3,5,6-TC pyrldinol
IPP
PNP
Baygon
(R)
Dursban
(R)
RBC
PI.
ChE
n
HUD
2,4, 5-T
2,4,5-TCP
2,4-DCP
Ronnel(R)
tr
VC-13
ug/ml
CFM
BHC
tfT BHC
milllliter per milliosmols per liter
3,5,6-trichloro-2 pyridinol
2-lso-propoxyphenol
paranltrophenol
Aprocarb 2-isopropoxyphenly-N-methyl carbamate
chlorpyrifos 0,0-Dimethyl 0-p-nitrophenyl phosphoro-
thioate
dichlorvos 2,2-dlchlorvinyl dimethyl phosphate
red blood cell
plasma
chollnesterase
number of persons
Housing & Urban Development (Dade County)
(2,4,5-tricholorophenoxyacetlc acid)
(2,4,5-trlcholorphenol)
2, 4-dichlorophenol
fenchlorphos 0,0-Dimethyl (2,4,5-tricholorphenol
phosphorothioate
trace amounts
dichlofenthion (0-(2,4-dichlorophenyl) 0,0-dietyl
phosphorothionate)
microgram per milliliter
cubic feet per minute
alpha isomer of 1,2,3,4,5,6-hexacloro-cylcohexane
Lindane gamma isomer of 1,2,3,4,5,6-hexachloro-
cyclo-hexane of 99f% purity
cubic meter
42
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-650/1-74-009
3. Recipient's Accession No.
4. Tide and Subtitle
PESTICIDES EPIDEMIOLOGICAL FIELD STUDIES
5- Report Date
June 1974
6.
7. Author(s)
Dr. John E. Davies
Performing Organization Rept.
No.
9. Performing Organization Name and Address
University of Miami School of Medicine
1600 N. W. 10th Avenue
Miami, Florida 33152
10. Proiect/Task/Work Unit No.
11. Contract/Gram No.
Grant No. 802112
Contract No. 68-02-1145
12. Sponsoring Organization 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 & Period
Covered Annual Report
12/18/72 - 12/31/73
14.
15. Supplementary Notes
16. AbstracisTne use of the multi-residue techniques for urinary metabolites appeared to be
provide the key to worker exposures from mixed organophosphate and carbamate exposures.
The findings of Shafik et al., were corroborated, and highly significant inverse correla-
tions of cholinesterase levels with the dialkyl phosphate urinary metabolites were demon-
strated under conditions of work exposure to the more toxic organophosphates such as
ethyl-methyl parathion and Phosdrin. DEP, DETP, DMP and DMTP were the only alkyl phos-
phates regularly found in these occupational exposures. Following 8 hours of a work ex-
posure to Dursban the appropriate dialkyl phosphate and phenolic derivatives persisted
in the urine for 36 hours and longer. These two groups of metabolites were exceedingly
informative in acute pesticide poisong and provided etiologic specificity and information
for the continued need of atropine therapy. Severe and protracted illness was observed
following intoxication by more polar and fat soluble organophosphates especially di-ethyl
dichlorophenol phosphorothioate (VC-13). This pesticide and its metabolites were detecte
in serum and in urine 48 days after exposure. Additionally air sampling of the South
Florida environment confirmed the disappearance of nr>T and -it-c
17. Key Words and Document Analysis. 17a. Descriptors
Urinary metabolite surveillance of the occupational pesticide worker
Urinary metabolites, di-alkyl phosphate and phenolic metabolites in multi-residue
techniques.
Fat soluble organophsophate intoxication - diagnosis and surveillance therapy.
The changing profile of pesticide environmental air sampling.
17b. Identifiers/Open-Ended Terms
17e. COSATI Field/Croup
18. Availability Scatement
19. Security Class (This
Report)
UNCLASSIFIED
iqClASSlFIEE
jrity Class (Th
20. Security Class (This
Page
llNCLASSIFIED
21. No. of Pages
22. Price
FORM NT IS-35 (IO-7OI
43
USCOMM-OC 40329-P7I
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