268 Med. Sci. Law (1979) Vol. 19, No.4
Printed in Great Britain
A Case of Fatal Dieldrin Poisoning ANNI STEENTOFT, Cando Pharm. Institute of Forensic Medicine, Department of Forensic Chemistry, University of Copenhagen, Denmark
SUMMARY
Dieldrin was developed in the United States and was made available commercially in 1948. Chemically, dieldrin is 1, 2, 3, 4, 10, 1o-hexachloro-6, 7-epoxy1, 4, 4a, 5, 6, 7, 8, 8a-octahydro-1, 4, 5, 8-dimethanonaphthalene and forms, together with aldrin and endrin, a triumvirate of insecticides derived from hexachlorodicyclopentadiene. High insecticidal activity combined with long residual action makes dieldrin an effective insecticide. Dieldrin is absorbed through the gastrointestinal tract, the respiratory tract and the skin. Several cases of chronic or acute non-fatal dieldrin poisoning have been reported, but only a very small number of fatal dieldrin cases with only fragmentary toxicological data have been described. This paper concerns a fatal intoxication due to dieldrin, including toxicological findings in blood, liver and muscle.
CASE REPORT A 43-year-old man suffering from schizophrenia was found in the morning dead beside his bed. In the kitchen a bottle was found containing the remainder of a dieldrin solution. The man had attempted suicide before. The quantity of dieldrin ingested was not known. The post-mortem examination revealed pulmonary and cerebral oedema and pulmonary congestion. Large amounts of foam were found in the respiratory tract.
TOXICOLOGICAL ANALYSIS Samples of blood, liver, muscle and stomach content were collected at post-mortem examination and stored at -20 DC pending toxicological examination. For the determination of dieldrin the method of de Faubert Maunder et al. (1964) was used with modifications. Five grams of liver and muscle homogenized with an equal volume of water and 5 g of blood are extracted with 60 ml of n-hexane. After drying with anhydrous sodium sulphate 25 ml of the hexane extract are extracted three times with 10 ml of N,N-dimethylformamide (DMF) saturated with n-hexane. The combined DMF extracts are washed with 10 ml of
n-hexane saturated with DMF. These 10 ml of n-hexane are then washed with 10 ml of DMF saturated with n-hexane, which is added to the original 30 ml of DMF extract. Finally, the combined DMF extracts are shaken with 200 ml of a 2 per cent aqueous sodium sulphate solution, and the n-hexane previously held in solution will separate. After 20 minutes for complete separation, the n-hexane phase is transferred to a centrifuge tube and carefully evaporated just to dryness at 35 DC under nitrogen. Gas chromatography: The residues were dissolved in at least 100 J.ll of benzene for gas chromatography. Gas chromatography was performed using a Pye model 104 gas chromatograph equipped with an electron capture detector. The column was packed with 3 per cent OV 17 on a 80-100 mesh AW-DMCS chromosorb W. The nitrogen flow was about 60 mllmin, and the oven temperature was maintained at 215°C. Under these conditions the retention time for dieldrin was about 2·4 minutes. Thin-layer chromatography: Thin-layer chromatography was performed using silica gel plates (HF 254 Merck) and as solvent system n-hexane-ether (90+10). For visualization the thin-layer plate was sprayed with 0·5 per cent o-dianisidine in methanol and then exposed to ultraviolet light. The dieldrin was identified as brownish spots. RESULTS The identity of dieldrin in the residues from blood, liver and muscle was confirmed by gas chromatography and also by thin-layer chromatography. The results from the quantitative gas chromatographic determination are presented in Table I. From the stomach content
Steentoft: Fatal Dieldrin Poisoning Table I. The concentration of dieldrin in blood, liver and muscle in a case of fatal poisoning
mg/kg
Blood
Liver
Muscle
0·5
29
3·7
only qualitative thin-layer chromatographic identification was performed. Recovery experiments using the method described above showed a recovery of about 75 per cent. Alcohol and drugs were not detected in the present case. DISCUSSION
269
human and in the dog. These results are well in accordance with the results in the present fatal case. Pribilla (1963) and Weinig et al. (1966) both reported a suicide with dieldrin. In both cases dieldrin was identified in the stomach content, but quantitative determination was not carried out. Conley (1960) reported a case with a 9-month-old girl, who accidentally ingested an unknown quantity of dieldrin and died about 20 hours after the intake. No toxicological findings were reported. Finally, a non-fatal case reported by Black (1974) should be mentioned. A 21-year-old man survived the intake of 9 g of dieldrin. The level of dieldrin attained in the serum was 1·16 mg/l, more than twice the blood concentration in the present case. Black (1974) indicated that early discovery and removal of the remaining dieldrin from the gastrointestinal tract contributed to the survival of the patient and drew the conclusion that the patient was extremely fortunate.
During the 31 years in which dieldrin has been commercially available, only a few cases of fatal dieldrin poisoning have been reported, and in only very few of these cases has toxicological analysis been performed. Blood levels in a case of fatal dieldrin poisoning appear to be reported in only the present case and that of Schwar (1965). The case reported by Schwar (1965) is of a 31-year-old woman, who died a REFERENCES few minutes after an intravenous injection of a Black A. M. S. (1974) Self poisoning with dieldrin: dieldrin solution. The chemical analysis a case report and pharmacokinetic discussion. Anaesth. Intens. Care 4, 369-374. revealed no dieldrin in the stomach content, the liver, the kidney and the urine. The blood con- Brown V. K. H., Hunter C. G. and Richardson A. (1964) A blood test diagnostic of absorption of centration was determined to be 50 mgtl, a aldrin and dieldrin. Br. ]. Ind. Med. 21,283-286. blood concentration a hundred times higher Conley B. E. (1960) Occupational dieldrin poisoning. than in the present case where the dieldrin was ]. Am. Med. Assoc. 172,2077-2080. de Faubert Maunder M. J., Egan H., Godly E. W. taken orally. et al. (1964) Clean-up of animal fats and dairy The estimated lethal dose of dieldrin for the products for the analysis of chlorinated pesticide human is approximately 5 g. Brown et al. residues. Analyst 89,168-174. (1964) demonstrated both in the human and Pribilla O. (1963) Akute todliche Dieldrinvergiftung. Arch. Toxikol. 20,61-71. in the dog that concentrations of blood dieldrin of less than O· 2 mgll are not associated Schwar T. G. (1965) Intravenous dieldrin solution administration.]. Forens. Med. 12, 142-145. with symptoms of poisoning, and conversely Weinig E., Machbert G. and Zink P. (1966) Uber den that when blood dieldrin concentrations Nachweis des Dieldrins bei einer Dieldrinvergiftung. Arch. Toxikol. 22, 115-124. exceed 0·2 mgtl symptoms appear both in the
8th Conference on Accident and Traffic Medicine The 8th Conference on Accident and Traffic Medicine will be held in Aarhus, Denmark, from 8 to 12 June 1980. Further information can be obtained from IAATM, Dr Hanns Reich, DK-8210 Aarhus V, Denmark.
Printed in Great Britain
A Case of Fatal Dieldrin Poisoning ANNI STEENTOFT, Cando Pharm. Institute of Forensic Medicine, Department of Forensic Chemistry, University of Copenhagen, Denmark
SUMMARY
Dieldrin was developed in the United States and was made available commercially in 1948. Chemically, dieldrin is 1, 2, 3, 4, 10, 1o-hexachloro-6, 7-epoxy1, 4, 4a, 5, 6, 7, 8, 8a-octahydro-1, 4, 5, 8-dimethanonaphthalene and forms, together with aldrin and endrin, a triumvirate of insecticides derived from hexachlorodicyclopentadiene. High insecticidal activity combined with long residual action makes dieldrin an effective insecticide. Dieldrin is absorbed through the gastrointestinal tract, the respiratory tract and the skin. Several cases of chronic or acute non-fatal dieldrin poisoning have been reported, but only a very small number of fatal dieldrin cases with only fragmentary toxicological data have been described. This paper concerns a fatal intoxication due to dieldrin, including toxicological findings in blood, liver and muscle.
CASE REPORT A 43-year-old man suffering from schizophrenia was found in the morning dead beside his bed. In the kitchen a bottle was found containing the remainder of a dieldrin solution. The man had attempted suicide before. The quantity of dieldrin ingested was not known. The post-mortem examination revealed pulmonary and cerebral oedema and pulmonary congestion. Large amounts of foam were found in the respiratory tract.
TOXICOLOGICAL ANALYSIS Samples of blood, liver, muscle and stomach content were collected at post-mortem examination and stored at -20 DC pending toxicological examination. For the determination of dieldrin the method of de Faubert Maunder et al. (1964) was used with modifications. Five grams of liver and muscle homogenized with an equal volume of water and 5 g of blood are extracted with 60 ml of n-hexane. After drying with anhydrous sodium sulphate 25 ml of the hexane extract are extracted three times with 10 ml of N,N-dimethylformamide (DMF) saturated with n-hexane. The combined DMF extracts are washed with 10 ml of
n-hexane saturated with DMF. These 10 ml of n-hexane are then washed with 10 ml of DMF saturated with n-hexane, which is added to the original 30 ml of DMF extract. Finally, the combined DMF extracts are shaken with 200 ml of a 2 per cent aqueous sodium sulphate solution, and the n-hexane previously held in solution will separate. After 20 minutes for complete separation, the n-hexane phase is transferred to a centrifuge tube and carefully evaporated just to dryness at 35 DC under nitrogen. Gas chromatography: The residues were dissolved in at least 100 J.ll of benzene for gas chromatography. Gas chromatography was performed using a Pye model 104 gas chromatograph equipped with an electron capture detector. The column was packed with 3 per cent OV 17 on a 80-100 mesh AW-DMCS chromosorb W. The nitrogen flow was about 60 mllmin, and the oven temperature was maintained at 215°C. Under these conditions the retention time for dieldrin was about 2·4 minutes. Thin-layer chromatography: Thin-layer chromatography was performed using silica gel plates (HF 254 Merck) and as solvent system n-hexane-ether (90+10). For visualization the thin-layer plate was sprayed with 0·5 per cent o-dianisidine in methanol and then exposed to ultraviolet light. The dieldrin was identified as brownish spots. RESULTS The identity of dieldrin in the residues from blood, liver and muscle was confirmed by gas chromatography and also by thin-layer chromatography. The results from the quantitative gas chromatographic determination are presented in Table I. From the stomach content
Steentoft: Fatal Dieldrin Poisoning Table I. The concentration of dieldrin in blood, liver and muscle in a case of fatal poisoning
mg/kg
Blood
Liver
Muscle
0·5
29
3·7
only qualitative thin-layer chromatographic identification was performed. Recovery experiments using the method described above showed a recovery of about 75 per cent. Alcohol and drugs were not detected in the present case. DISCUSSION
269
human and in the dog. These results are well in accordance with the results in the present fatal case. Pribilla (1963) and Weinig et al. (1966) both reported a suicide with dieldrin. In both cases dieldrin was identified in the stomach content, but quantitative determination was not carried out. Conley (1960) reported a case with a 9-month-old girl, who accidentally ingested an unknown quantity of dieldrin and died about 20 hours after the intake. No toxicological findings were reported. Finally, a non-fatal case reported by Black (1974) should be mentioned. A 21-year-old man survived the intake of 9 g of dieldrin. The level of dieldrin attained in the serum was 1·16 mg/l, more than twice the blood concentration in the present case. Black (1974) indicated that early discovery and removal of the remaining dieldrin from the gastrointestinal tract contributed to the survival of the patient and drew the conclusion that the patient was extremely fortunate.
During the 31 years in which dieldrin has been commercially available, only a few cases of fatal dieldrin poisoning have been reported, and in only very few of these cases has toxicological analysis been performed. Blood levels in a case of fatal dieldrin poisoning appear to be reported in only the present case and that of Schwar (1965). The case reported by Schwar (1965) is of a 31-year-old woman, who died a REFERENCES few minutes after an intravenous injection of a Black A. M. S. (1974) Self poisoning with dieldrin: dieldrin solution. The chemical analysis a case report and pharmacokinetic discussion. Anaesth. Intens. Care 4, 369-374. revealed no dieldrin in the stomach content, the liver, the kidney and the urine. The blood con- Brown V. K. H., Hunter C. G. and Richardson A. (1964) A blood test diagnostic of absorption of centration was determined to be 50 mgtl, a aldrin and dieldrin. Br. ]. Ind. Med. 21,283-286. blood concentration a hundred times higher Conley B. E. (1960) Occupational dieldrin poisoning. than in the present case where the dieldrin was ]. Am. Med. Assoc. 172,2077-2080. de Faubert Maunder M. J., Egan H., Godly E. W. taken orally. et al. (1964) Clean-up of animal fats and dairy The estimated lethal dose of dieldrin for the products for the analysis of chlorinated pesticide human is approximately 5 g. Brown et al. residues. Analyst 89,168-174. (1964) demonstrated both in the human and Pribilla O. (1963) Akute todliche Dieldrinvergiftung. Arch. Toxikol. 20,61-71. in the dog that concentrations of blood dieldrin of less than O· 2 mgll are not associated Schwar T. G. (1965) Intravenous dieldrin solution administration.]. Forens. Med. 12, 142-145. with symptoms of poisoning, and conversely Weinig E., Machbert G. and Zink P. (1966) Uber den that when blood dieldrin concentrations Nachweis des Dieldrins bei einer Dieldrinvergiftung. Arch. Toxikol. 22, 115-124. exceed 0·2 mgtl symptoms appear both in the
8th Conference on Accident and Traffic Medicine The 8th Conference on Accident and Traffic Medicine will be held in Aarhus, Denmark, from 8 to 12 June 1980. Further information can be obtained from IAATM, Dr Hanns Reich, DK-8210 Aarhus V, Denmark.
