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Three cases of maldison (Malathion) poisoning
Forensic Science, 2 (1973) 101-105 0 Eisevier Sequoia S.A., Lausanne - Printed in The Netheriands
CASE REPORT THREE CASES OF MALDISON
(MALATHION)
POISONING
J.F. LEWIN, R.J. NORRIS and J.T. HUGHES Ckernistry Division, Department of Scientific and Industrial Research, Petone (New Zealand)
SUMMARY Three
analytical
fatal suicidal poisonings methods
with maldison
and results. The analytical
(Malathion)
methods
are described together with
include thin-layer
and gas-liquid
chromatography.
During 1970 and 1971, there were in New Zealand three fatal poisonings using S-( 1,2di(ethoxycarbonyl)ethyl)-U,0-dimethylphosphorodithioate known as maldison (the registered common name for Malathion in New Zealand
r).
Maldison is widely available in New Zealand in a large number
ofpreparations.
It has a
low toxicity (the LDs e (rats, oral) is 1400-1900 mg/kg compared with parathion’, s-6 mg/kg) and very few fatalities have previously been reported in the literature. Hence, it is surprising attributed
that three fatal suicides in 18 months in a population of 2.8 million have been to maldison. It was therefore felt that these three cases should be recorded.
CASE HISTORIES
Case I A 70-year-old found
woman
was admitted
to hospital
in a state of collapse. On admission
died at 2.45 next morning
at 9.55 in the evening, having been
she was still conscious
though confused.
She
3.
Case 2
A %-year-old man, who had apparently been depressed, was reported missing. He was later found dead in a car, with a partially filled bottle of maldison beside him 4. Case 3
A 64-year-old
woman with a history
of depressive mental ill-health was found dead in
102
J.F.
her bathroom.
On a previous occasion
was an almost empty bottle
she had attempted
of 50% maldison emulsion,
LEWIN,R.J.NORRIS,J.T. HUGHES suicide using maldison. Nearby an empty glass, a half-full bottle
of DDT, and a full glass of a clear liquid ‘. POST-MORTEM FINDINGS Case 1 A strong smell of kerosene in the stomach contents was noted by the pathologist. There was evidence of early bilateral bronchopneumonia and the gastric mucosa was congested.
No other abnormalities
were found 3.
Case 2 The presence of widespread
atheroma
mucosa were noted by the pathologist. trachea and bronchi,
and infiltration
50 ml of a milky
material
in the
of blood into the posterior aspect of the upper lobe
of the right lung as in acute venous approximately
(not lethal) and of necrosis of the oesophageal Also noted was a clear, jelly-like congestion.
fluid,
The stomach
with a smell strongly
Evidence suggested that the deceased had probably
contents
consisted
of
suggestive of maldison.
swallowed this poison, then later had
vomited and inhaled the vomitus 4. Case 3 The pharynx, abundant,
strongly
haemorrhagic been extensive haemorrhage ingestion
oesophagus,
stomach
and upper small-intestine
were found to contain
smelling, opaque white fluid, while the tracheobronchial
congestion.
The oesophagus
inhalation
of the ingested
was found.
of an insecticidal
The pathologist
appeared
to have been corroded.
tree showed There had
fluid into the lungs, and peribronchial was of the opinion
poison with subsequent
inhalation
lung
that death was due to
of vomitus into the lungs 5.
ANALYSIS Case 1 A small portion of a steam distillate of acidified stomach contents was extracted with hexane, the extract evaporated and the residue taken up in methanol. The ultraviolet spectrum (350-225 run) was recorded on a Beckman DK2A spectrophotometer; it was identical to that of maldison (Fisk et al. 6). Thin-layer chromatography was carried out on glass plates coated in the laboratory with Merck Kieselgel GF254, developed in hexane:acetone (80:20), and then sprayed with acidic palladium chloride solution. Standard maldison gave a yellow spot with an RF value of 0.52.
IO.3
CASE REPORT
A direct n-heptane
extraction
of stomach contents
gave an identical spot to maldison
and additional spots (probably metabolites) with RF values of 0.42 and 0.97. The extract from the steam distillate gave only spots with RF values of 0.42 and 0.97, and none corresponding
to maldison.
An extract from the liver, prepared by the sodium tungstate
method followed by extraction values of 0.33: 0.42 and 0.97. Estimation stomach
of the amount
contents
chromatograph bromide
into ether, gave no maldison spot but gave spots with RF of maldison
by gas-liquid fitted
was used in a coiled glass column 2OO”C, with the glass-lined
mesh Chromosorb
incorporating
at an oven temperature
inlet), 8 and 260 ml/min,
under these conditions
grade (98.9%) maldison
of the
a caesium
port at 220°C. The carrier gas (helium),
at 12 (column
time (RT) for maldison
of reference
detector
extract
A600 gas-liquid
W packing coated with 5% DC 200
1.4 m X 3.2 mm operated
injection
and air-flow rates were maintained solutions
using an Aerograph
with an alkali flame-ionisation
ceramic pellet. A 60-80
The retention
was carried out on a hexane
chromatography
(Cyanamid,
hydrogen
respectively.
was two minutes. Australia),
of
Standard
prepared in ethyl
acetate and diluted serially in hexane, were used for comparison. Slight traces of an earlier eluting peak (RT = 0.8 X RTmaldison) were present in chromatograms of standards, indicating small amounts of S-( 1,2-di(ethoxycarbonyl)ethyl)-O,O-dimethylphosphorothiolate, the “oxon” or oxygen analogue of maldison, the amount indicated being less than 1%. The results obtained in this case showed that 250 mg maldison were present in the 70 g stomach contents. The oxygen analogue was detected in both the stomach contents and the liver, but not determined in either sample. Case 2 An indication
of the poison used was given by the pathologist
4. Consequently
the
stomach contents and blood were examined for maldison, and its presence was confirmed (4: 1); by the method of Farago 7 (thin-layer chromatography system 1; hexane:acetone on DC Alurolle Kieselgel F 254, Merck). In his paper 7 Farago estimated the amount of maldison by comparing the absorbance of maldison in the sample at 326 nm after thin. layer chromatography (palladium chloride reagent spray and elution into acetone-distilled water (4: 1)) with the absorbance of standard maldison similarly processed. This method
did not succeed in our hands because we were unable
to obtain reproducible
standard maldison absorbances, both when we used the aluminium-backed silica gel roll and when we used glass plates coated with silica gel. The blood cholinesterase activity I1 was found to be completely inhibited. Estimation of the amount of maldison in the stomach contents and blood was carried out using the gas-liquid chromatography method (as described for Case 1). The 27 ml of stomach contents received from the pathologist the blood contained 5 mg maldison per litre.
were found to contain
162 mg maldison;
104
J.1;. REWIN, R.9. NORRIS, J.T. HUGHES
Case 3 As in Case 2 there was evidence indicating in the stomach contents
the poison used 5. The presence of maldison
was again proved by the method of Farago (thin-layer
chromato-
graphy system 1). Maldison was also detected in the bottle (so labelled) and in the residue of the empty
glass. DDT was detected
by thin-layer
chromatography
in the bottle
so
labelled and in the full glass, but none was detected in the stomach contents. The cholinesterase
level in the whole blood was found to cause a pH change of 0.16
units per hour (normal
change is in excess of 0.4 units per hour) showing that the blood
cholinesterase
activity was severely inhibited.
Estimation
of the amount
of maldison
carried out as before by gas-liquid fatty,
was cleaned
dick ‘. Although
using the hexane-acetonitrile no standard
of the oxygen
amounts detected in the stomach contents of Watts and Storherr 9. The stomach analogue
in the stomach contents,
chromatography.
contents
contained
blood and liver was
The liver extract, partition
analogue
method
which was very
of Jones and Rid-
was available,
estimates
and blood were made using the sensitivity
648 mg maldison
in the 12 ml sample; the blood contained
oxygen analogue per litre; the liver contained
and
of the data
10-I 5 mg of the oxygen
0.67 mg maldison
and 1 mg of the
2.4 mg maldison per kg.
DISCUSSION
to maldison have been reported by Farago ’‘. His results
Four fatal suicides attributed are summarized
in Table I, together
with our results. A comparison
of the two sets of
results shows that our figures for blood, and that for liver, are significantly lower. This may well be related to the unknown intervals between ingestion and death, and between death and analysis in our laboratory.
TABLE I COMPARISON OF FARAGO’S Organs tested
CASES WITH THE PRESENT FINDINGS
Maldison (mg%) Our cases
Farago’s cases I
2
3
4
I
2
3
Stomach Blood
992 188
172 29
1296 99
31 10
357
600 0.5
5400 0.067 (plus 0.1 mg% of malaoxon)
Liver
166
130
170
20
0.24
CASE REPORT
105
ACKNOWLEDGEMENTS
The authors wish to acknowledge the analytical assistance of Miss A. McLean and Dr J.L. Love, Chemistry Division, DSIR, and of Mr M. Tyson, Occupational Health Unit, Department of Health.
REFERENCES
1 New Zealand
2 R. Ben-Dyke, Control, 3 4 5 6
7
8 9 10 11
Agricultural
Chemicals
D.M. Sanderson 9 (1970) 1199127.
Board, Nomerdature
and D.N. Noakes,
Acute
ofAgricultural
toxicity
Chemicals, 1911. World Rev. Pest
data for pesticides,
Dr PC. Cairney, personal communication. Dr E. McKenzie, personal communication. Dr J. Burkinshaw, personal communication. 4.5. Fisk, G.R. Czerwinski and J.H. Kenhart, A rapid screening technique for the identification of organic phosphate insecticides in gastric lavage fluid or dermal residues, J. Forens. Sci., 10 (1965) 473-419. A. Farago, Thin-layer chromatographic detection and quantitative determination of Malathion in biological materials, J. Forens. Sci., 12 (1967) 547-548. L.R. Jones and J.A. Riddick, Separation of organic insecticides from plant and animal tissues,Anal. Chem., 24 (1952) 569-571. R.R. Watts and R.W. Storherr, Gas chromatography of organophosphorus pesticides: Retention times and response data on three columns, .I. Assoc. Off: Anal. Chem., 5 2 (1969) 5 13 -5 21. A. Farago, Fatal, suicidal Malathion poisonings, Arch. Toxicol., 23 (1967) 11-16. H.O. Michel, An electrometric method for the determination of red blood cell and plasma cholinesterase activity,J. Lab. Clin. Med., 34 (1949) 1564-1568.
CASE REPORT THREE CASES OF MALDISON
(MALATHION)
POISONING
J.F. LEWIN, R.J. NORRIS and J.T. HUGHES Ckernistry Division, Department of Scientific and Industrial Research, Petone (New Zealand)
SUMMARY Three
analytical
fatal suicidal poisonings methods
with maldison
and results. The analytical
(Malathion)
methods
are described together with
include thin-layer
and gas-liquid
chromatography.
During 1970 and 1971, there were in New Zealand three fatal poisonings using S-( 1,2di(ethoxycarbonyl)ethyl)-U,0-dimethylphosphorodithioate known as maldison (the registered common name for Malathion in New Zealand
r).
Maldison is widely available in New Zealand in a large number
ofpreparations.
It has a
low toxicity (the LDs e (rats, oral) is 1400-1900 mg/kg compared with parathion’, s-6 mg/kg) and very few fatalities have previously been reported in the literature. Hence, it is surprising attributed
that three fatal suicides in 18 months in a population of 2.8 million have been to maldison. It was therefore felt that these three cases should be recorded.
CASE HISTORIES
Case I A 70-year-old found
woman
was admitted
to hospital
in a state of collapse. On admission
died at 2.45 next morning
at 9.55 in the evening, having been
she was still conscious
though confused.
She
3.
Case 2
A %-year-old man, who had apparently been depressed, was reported missing. He was later found dead in a car, with a partially filled bottle of maldison beside him 4. Case 3
A 64-year-old
woman with a history
of depressive mental ill-health was found dead in
102
J.F.
her bathroom.
On a previous occasion
was an almost empty bottle
she had attempted
of 50% maldison emulsion,
LEWIN,R.J.NORRIS,J.T. HUGHES suicide using maldison. Nearby an empty glass, a half-full bottle
of DDT, and a full glass of a clear liquid ‘. POST-MORTEM FINDINGS Case 1 A strong smell of kerosene in the stomach contents was noted by the pathologist. There was evidence of early bilateral bronchopneumonia and the gastric mucosa was congested.
No other abnormalities
were found 3.
Case 2 The presence of widespread
atheroma
mucosa were noted by the pathologist. trachea and bronchi,
and infiltration
50 ml of a milky
material
in the
of blood into the posterior aspect of the upper lobe
of the right lung as in acute venous approximately
(not lethal) and of necrosis of the oesophageal Also noted was a clear, jelly-like congestion.
fluid,
The stomach
with a smell strongly
Evidence suggested that the deceased had probably
contents
consisted
of
suggestive of maldison.
swallowed this poison, then later had
vomited and inhaled the vomitus 4. Case 3 The pharynx, abundant,
strongly
haemorrhagic been extensive haemorrhage ingestion
oesophagus,
stomach
and upper small-intestine
were found to contain
smelling, opaque white fluid, while the tracheobronchial
congestion.
The oesophagus
inhalation
of the ingested
was found.
of an insecticidal
The pathologist
appeared
to have been corroded.
tree showed There had
fluid into the lungs, and peribronchial was of the opinion
poison with subsequent
inhalation
lung
that death was due to
of vomitus into the lungs 5.
ANALYSIS Case 1 A small portion of a steam distillate of acidified stomach contents was extracted with hexane, the extract evaporated and the residue taken up in methanol. The ultraviolet spectrum (350-225 run) was recorded on a Beckman DK2A spectrophotometer; it was identical to that of maldison (Fisk et al. 6). Thin-layer chromatography was carried out on glass plates coated in the laboratory with Merck Kieselgel GF254, developed in hexane:acetone (80:20), and then sprayed with acidic palladium chloride solution. Standard maldison gave a yellow spot with an RF value of 0.52.
IO.3
CASE REPORT
A direct n-heptane
extraction
of stomach contents
gave an identical spot to maldison
and additional spots (probably metabolites) with RF values of 0.42 and 0.97. The extract from the steam distillate gave only spots with RF values of 0.42 and 0.97, and none corresponding
to maldison.
An extract from the liver, prepared by the sodium tungstate
method followed by extraction values of 0.33: 0.42 and 0.97. Estimation stomach
of the amount
contents
chromatograph bromide
into ether, gave no maldison spot but gave spots with RF of maldison
by gas-liquid fitted
was used in a coiled glass column 2OO”C, with the glass-lined
mesh Chromosorb
incorporating
at an oven temperature
inlet), 8 and 260 ml/min,
under these conditions
grade (98.9%) maldison
of the
a caesium
port at 220°C. The carrier gas (helium),
at 12 (column
time (RT) for maldison
of reference
detector
extract
A600 gas-liquid
W packing coated with 5% DC 200
1.4 m X 3.2 mm operated
injection
and air-flow rates were maintained solutions
using an Aerograph
with an alkali flame-ionisation
ceramic pellet. A 60-80
The retention
was carried out on a hexane
chromatography
(Cyanamid,
hydrogen
respectively.
was two minutes. Australia),
of
Standard
prepared in ethyl
acetate and diluted serially in hexane, were used for comparison. Slight traces of an earlier eluting peak (RT = 0.8 X RTmaldison) were present in chromatograms of standards, indicating small amounts of S-( 1,2-di(ethoxycarbonyl)ethyl)-O,O-dimethylphosphorothiolate, the “oxon” or oxygen analogue of maldison, the amount indicated being less than 1%. The results obtained in this case showed that 250 mg maldison were present in the 70 g stomach contents. The oxygen analogue was detected in both the stomach contents and the liver, but not determined in either sample. Case 2 An indication
of the poison used was given by the pathologist
4. Consequently
the
stomach contents and blood were examined for maldison, and its presence was confirmed (4: 1); by the method of Farago 7 (thin-layer chromatography system 1; hexane:acetone on DC Alurolle Kieselgel F 254, Merck). In his paper 7 Farago estimated the amount of maldison by comparing the absorbance of maldison in the sample at 326 nm after thin. layer chromatography (palladium chloride reagent spray and elution into acetone-distilled water (4: 1)) with the absorbance of standard maldison similarly processed. This method
did not succeed in our hands because we were unable
to obtain reproducible
standard maldison absorbances, both when we used the aluminium-backed silica gel roll and when we used glass plates coated with silica gel. The blood cholinesterase activity I1 was found to be completely inhibited. Estimation of the amount of maldison in the stomach contents and blood was carried out using the gas-liquid chromatography method (as described for Case 1). The 27 ml of stomach contents received from the pathologist the blood contained 5 mg maldison per litre.
were found to contain
162 mg maldison;
104
J.1;. REWIN, R.9. NORRIS, J.T. HUGHES
Case 3 As in Case 2 there was evidence indicating in the stomach contents
the poison used 5. The presence of maldison
was again proved by the method of Farago (thin-layer
chromato-
graphy system 1). Maldison was also detected in the bottle (so labelled) and in the residue of the empty
glass. DDT was detected
by thin-layer
chromatography
in the bottle
so
labelled and in the full glass, but none was detected in the stomach contents. The cholinesterase
level in the whole blood was found to cause a pH change of 0.16
units per hour (normal
change is in excess of 0.4 units per hour) showing that the blood
cholinesterase
activity was severely inhibited.
Estimation
of the amount
of maldison
carried out as before by gas-liquid fatty,
was cleaned
dick ‘. Although
using the hexane-acetonitrile no standard
of the oxygen
amounts detected in the stomach contents of Watts and Storherr 9. The stomach analogue
in the stomach contents,
chromatography.
contents
contained
blood and liver was
The liver extract, partition
analogue
method
which was very
of Jones and Rid-
was available,
estimates
and blood were made using the sensitivity
648 mg maldison
in the 12 ml sample; the blood contained
oxygen analogue per litre; the liver contained
and
of the data
10-I 5 mg of the oxygen
0.67 mg maldison
and 1 mg of the
2.4 mg maldison per kg.
DISCUSSION
to maldison have been reported by Farago ’‘. His results
Four fatal suicides attributed are summarized
in Table I, together
with our results. A comparison
of the two sets of
results shows that our figures for blood, and that for liver, are significantly lower. This may well be related to the unknown intervals between ingestion and death, and between death and analysis in our laboratory.
TABLE I COMPARISON OF FARAGO’S Organs tested
CASES WITH THE PRESENT FINDINGS
Maldison (mg%) Our cases
Farago’s cases I
2
3
4
I
2
3
Stomach Blood
992 188
172 29
1296 99
31 10
357
600 0.5
5400 0.067 (plus 0.1 mg% of malaoxon)
Liver
166
130
170
20
0.24
CASE REPORT
105
ACKNOWLEDGEMENTS
The authors wish to acknowledge the analytical assistance of Miss A. McLean and Dr J.L. Love, Chemistry Division, DSIR, and of Mr M. Tyson, Occupational Health Unit, Department of Health.
REFERENCES
1 New Zealand
2 R. Ben-Dyke, Control, 3 4 5 6
7
8 9 10 11
Agricultural
Chemicals
D.M. Sanderson 9 (1970) 1199127.
Board, Nomerdature
and D.N. Noakes,
Acute
ofAgricultural
toxicity
Chemicals, 1911. World Rev. Pest
data for pesticides,
Dr PC. Cairney, personal communication. Dr E. McKenzie, personal communication. Dr J. Burkinshaw, personal communication. 4.5. Fisk, G.R. Czerwinski and J.H. Kenhart, A rapid screening technique for the identification of organic phosphate insecticides in gastric lavage fluid or dermal residues, J. Forens. Sci., 10 (1965) 473-419. A. Farago, Thin-layer chromatographic detection and quantitative determination of Malathion in biological materials, J. Forens. Sci., 12 (1967) 547-548. L.R. Jones and J.A. Riddick, Separation of organic insecticides from plant and animal tissues,Anal. Chem., 24 (1952) 569-571. R.R. Watts and R.W. Storherr, Gas chromatography of organophosphorus pesticides: Retention times and response data on three columns, .I. Assoc. Off: Anal. Chem., 5 2 (1969) 5 13 -5 21. A. Farago, Fatal, suicidal Malathion poisonings, Arch. Toxicol., 23 (1967) 11-16. H.O. Michel, An electrometric method for the determination of red blood cell and plasma cholinesterase activity,J. Lab. Clin. Med., 34 (1949) 1564-1568.