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ABSTRACT: Excessive alcohol consumption represents a major risk factor for morbidity and mortality. It is therefore indispensable to be able to detect at-risk drinking. Ethyl glucuronide (EtG) is a specific marker of alcohol consumption. The determination of ethyl glucuronide in urine or blood can be used to prove recent driving under the influence of alcohol, even if ethanol is no longer detectable. The commercialization of an EtG specific immunological assay now allows to obtain preliminary results rapidly and easily with satisfying sensitivity. Moreover, the detection of ethyl glucuronide in hair offers the opportunity to evaluate an alcohol consumption over a long period. The EtG concentration in hair is in correlation with the amount of ingested alcohol. Thus, the analysis of ethyl glucuronide can be used to monitor abstinence, to detect alcohol relapse and to identify at-risk drinkers. However, a cut off allowing to detect chronic alcohol abuser reliably still does not exist. Therefore, it is recommended to perform the analysis of ethyl glucuronide in complement to the existing blood markers. A study financed by the Swiss Foundation for Alcohol Research is actually conducted by the West Switzerland University Center of Legal Medicine in order to establish an objective cut-off.
Praxis 11/2009; 98(22):1299-306.
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ABSTRACT: Fatty acid ethyl esters (FAEEs) are products of nonoxidative ethanol metabolism. After incorporation in hair, they should be suitable long-term markers of alcohol abuse.
Hair samples from 19 alcoholics in a treatment program, 10 fatalities with verified excessive alcohol consumption, 13 moderate social drinkers who consumed up to 20 g ethanol/day, and 5 strict teetotalers were analyzed in 1-12 segments for four FAEEs (ethyl myristate, ethyl palmitate, ethyl oleate, and ethyl stearate) by external degreasing with n-heptane, extraction with a dimethyl sulfoxide-n-heptane mixture, headspace solid-phase microextraction of the extracts, and gas chromatography-mass spectrometry with deuterated internal standards. The n-heptane washings were analyzed in the same way for FAEEs from the hair surface.
The sum of the four ester concentrations in hair calculated for the proximal 0-6 cm segment was 2.5-13.5 ng/mg (mean, 6.8 ng/mg) for the fatalities, 0.92-11.6 ng/mg (mean, 4.0 ng/mg) for 17 of the alcoholics in treatment, 0.20-0.85 ng/mg (mean, 0.41 ng/mg) for the moderate social drinkers, and 0.06-0.37 ng/mg (mean, 0.16 ng/mg) for the teetotalers. In almost all cases the segmental concentrations increased from proximal to distal. There was no agreement between the self-reported drinking histories of the participants and the FAEE concentrations along the hair length. Ethyl oleate was the dominant ester in all samples.
FAEEs are deposited in hair mainly from sebum. Despite large individual differences, FAEE hair concentrations can be used as markers for excessive alcohol consumption with relatively high accuracy.
Clinical Chemistry 01/2002; 47(12):2114-23. · 7.91 Impact Factor
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ABSTRACT: Fatty acid ethyl esters (FAEE) are products of the nonoxidative ethanol metabolism, which are known to be detectable in blood only about 24h after the last alcohol intake. After deposition in hair they should be suitable long-term markers of chronically elevated alcohol consumption. Therefore, a method for the analysis of ethyl myristate, ethyl palmitate, ethyl oleate and ethyl stearate from hair was developed based on the extraction of the hair sample by a dimethylsulphoxide (DMSO)/n-hexane mixture, separation and evaporation of the n-hexane phase and application of headspace solid-phase microextraction (HS-SPME) in combination with gas chromatography-mass spectrometry (GC-MS) to the extract. For use as internal standards, the corresponding D(5)-ethyl esters were prepared. The HS-SPME/GC-MS measurements were automatically performed using a multi-purpose sampler. The detection limits of the FAEE were between 0.01 and 0.04ng/mg and the reproducibility was between 3.5 and 16%. By application of the method to hair samples of 21 fatalities with known heavy alcohol abuse 0.045-2.4ng/mg ethyl myristate, 0.35-13.5ng/mg ethyl palmitate, 0.25-7.7ng/mg ethyl oleate and 0.05-3.85ng/mg ethyl stearate were measured. For social drinkers (30-60g ethanol per week), the concentrations were about one order of magnitude smaller. For 10 teetotalers negative results or traces of ethyl palmitate were found. It was shown by supplementary investigations in single cases that FAEE are also present in sebum, that there is no strong difference in their concentrations between pubic, chest and scalp hair, and that they are detectable in hair segments after a 2 months period of abstinence. From the results follows that the measurement of FAEE concentrations in hair is a useful way for a retrospective detection of alcohol abuse.
Forensic Science International 10/2001; 121(1-2):76-88. · 2.30 Impact Factor
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ABSTRACT: A simple method for analysis of methadone and its two main metabolites EDDP and EMDP in hair was developed using automatic headspace solid-phase microextraction (HS-SPME) at a multipurpose sampler and gas chromatography-mass spectrometry with electron impact ionization and selected ion monitoring (GC-MS-SIM). The washed hair pieces were digested in the closed headspace vial in 1 ml 1 M NaOH containing 0.5 g NaCl and each 10 ng of the internal standards D9-methadone and D3-EDDP at 110 degrees C for 20 min. Then the HS-SPME was performed with a 65 microm polydimethylsiloxan/ divinylbenzene fiber at the same temperature in the same vial for another 20 min followed by the desorption in the GC injection port. The calibration curves were linear between 0.1 and 3 ng/mg (methadone and EMDP) and 10 ng/mg (EDDP) respectively, at higher concentrations a negative deviation from linearity was found. The detection limits were 0.03 ng/mg (methadone) and 0.05 ng/mg (EDDP and EMDP), and the reproducibility was 9.2% for methadone and 11.2% for EDDP (n= 12). The method was applied to hair samples of 26 drug fatalities. 19 cases were positive with 0.36-11.8 ng/mg methadone and 0.19 -10.8 ng/mg EDDP. EMDP was found only in two cases with 0.18 and 0.84 ng/mg. The methadone concentration range was in agreement with previous data, but the EDDP/methadone concentration ratios (0.19-0.67) were definitely higher than those determined by other methods.
Journal of chromatography. B, Biomedical sciences and applications 10/2000; 746(2):255-64.
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ABSTRACT: Headspace solid phase microextraction (HS-SPME) has advantages of high purity of the extract, avoidance of organic solvents and simple technical manipulation and can be used in combination with gas chromatography-mass spectrometry (GC-MS) in the hair analysis of a number of drugs. HS-SPME coupled with the hydrolysis of the hair matrix by 4% sodium hydroxide in the presence of excess sodium sulphate and of a suitable internal standard proved to be a convenient one-step method for the measurement of many lipophilic basic drugs such as nicotine, amphetamine derivatives, local anaesthetics, phencyclidine, ketamine, methadone, diphenhydramine, tramadol, tricyclic antidepressants and phenothiazines. Detection limits were between 0.05 and 1.0 ng/mg. From spiked 10-mg hair samples absolute recoveries between 0.04 and 5.7% were found. These recoveries decreased considerably if larger sample amounts were used, perhaps due to increased drug solubility in the aqueous phase or to elevated viscosity in the presence of dissolved hair proteins. Because of the phenolic hydroxyl group a change of pH after alkaline hair digestion (by adding excess orthophosphoric acid) was necessary for the detection of delta 9-tetrahydrocannabinol (delta 9-THC), cannabinol (CBN) and cannabidiol (CBD) by HS-SPME. Nevertheless, the detection limits were such that only CBN could be detected in hair of a consumer. Clomethiazole, a compound hydrolysed in alkali, was measured by HS-SPME after extraction with aqueous buffer. The detection limit was 0.5 ng/mg. Cocaine could not be detected by HS-SPME. The application of HS-SPME to hair samples from several forensic and clinical cases is described.
Forensic Science International 02/2000; 107(1-3):129-48. · 2.30 Impact Factor
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ABSTRACT: The analysis of suitable ethanol markers in hair would be an advantageous tool for chronic alcohol abuse control because of the wide diagnostic window allowed by this specimen and the possibility of segmental investigation. Between the markers practically used or thoroughly investigated in blood or urine, ethylglucuronide, fatty acid ethylesters, phosphatidylethanol, acetaldehyde adducts to protein and 5-hydroxytryptophol can be regarded as possible candidates also in hair, but preliminary data were found in the literature only for ethylglucuronide and acetaldehyde modified proteins. By using headspace gas chromatography and headspace solid phase microextraction in combination with gas chromatography-mass spectrometry (SPME-GC/MS), in alkaline hydrolysates of hair it was possible to determine between 17 and 135 ng/mg of ethanol beside acetone and several other volatile compounds with slightly higher ethanol values for alcoholics than for social drinkers and teetotalers. A part of this is ethanol only absorbed in the hair matrix from the surrounding environment and consequently is not applicable as a diagnostic criterion. By extraction with aqueous buffer, methanol or a methanol/chloroform mixture and subsequent alkaline hydrolysis it was found that another part is generated from ethylesters, which are preferentially deposited in the lipid fraction of hair. In a specific search for ethylesters of 17 carboxylic acids by GC/MS-SIM in most cases ethyl 4-hydroxybenzoate (0.1 to 5.9 ng/mg, a preservative in hair cosmetics) and in four cases traces of indolylacetic acid ethylester were found. Furthermore, diethyl phthalate (a softening agent, present also in many cosmetic products) was identified in the hair of alcoholics as well as of children. As potential markers of alcohol intake, ethyl palmitate, ethyl stearate and ethyl oleate were detected in hair samples of alcoholics by headspace SPME-GC/MS of the chloroform/methanol extracts.
Forensic Science International 02/2000; 107(1-3):201-23. · 2.30 Impact Factor
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ABSTRACT: Die Untersuchung eines Todesfalls nach oraler Aufnahme einer größeren Menge eines Kombinationsinsektizids bestehend aus Propoxur
und Tetramethrin sowie den Lösungsmitteln Isopropanol und Benzylalkohol ergab als wesentlichen morphologischen Befund eine
koagulationsnekrotische Verhärtung der Speiseröhre und der Magenwand. Die in Venenblut, Leber, Niere, Glaskörperflüssigkeit
und Liquor durch HPLC bzw. GC/MS bestimmten Konzentrationen lagen für Propoxur (< 0,3– 18 μg/g) im komatös-lateralen Bereich,
während Tetramethrin (bis 0,1 μg/g) nahezu vollständig abgebaut war. Weiterhin wurden als Propoxurabbauprodukt o-Isopropoxyphenol
(2,8–56 μg/g), Benzylalkohol (18–58 μg/g) sowie dessen Abbauprodukt Benzoesäure (85–140 μg/g), Isopropanol (0,45–1,1 mg/g)
und Aceton (0,01–0,03 mg/g) gefunden. Die Werte im Herzblut und in der Lunge waren hingegen bis zu 30-fach höher. Als Ursache
für diese immensen Konzentrationsunterschiede wird eine agonale Aspiration des erbrochenen, bis zu drei Größenordnungen höher
konzentrierten Mageninhaltes diskutiert. Der hauptsächlich postmortal angenommene Abbau von Propoxur zu o-Isopropoxyphenol
und von Benzylalkohol zu Benzoesäure ist in der Leber nahezu vollständing und in den übrigen Probenmaterialien sehr unterschiedlich
ausgeprägt. Als Todesursache ergibt sich eine Intoxikation durch den Acetylcholinesterasehemmer Propoxur in Kombination mit
der neurotoxischen Wirkung des Tetramethrins.
In a fatality after oral intake of a large amount of an insecticide spray consisting of propoxur, tetramethrine and the solvents
isopropanol and benzyl alcohol, a coagulation nectrotic fixation of the oesophagus and stomach were the main morphological
findings. The concentrations determined by HPLC and GC/MS in femoral blood, liver, kidney, vitreous humor and liquor were
in the comatose lethal range for propoxur (< 0.3–18 μg/g), whereas tetrametrin (up to 0.1 μg/g) was almost completely decomposed.
The propoxur decomposition product o-isopropoxyphenol (2.8–56 μg/g), benzyl alcohol (18–58 μg/g) and its oxydation product
benzoic acid (85–140 μg/g), isopropanol (0.45–1.1 mg/g) and acetone (0.01–0.03 mg/g) were also found. On the other hand, the
concentrations in heart blood and lung tissue were up to 30 times higher. As a reason for these immense concentration differences
an agonale aspiration of the highly concentrated liquid stomach content after vomiting immediately before death is discussed.
The extent of the metabolization of propoxur to o-isopropoxyphenol and of benzyl alcohol to benzoic acid, which is assumed
to proceed mainly postmortem, was quite different in the materials investigated and was almost complete in the liver. The
intoxication by the acetylcholine esterase inhibitor propoxur in combination with the neurotoxic effect of tetramethrine was
determined as the cause of death.
Rechtsmedizin 02/1998; 8(3):105-108. · 0.81 Impact Factor
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ABSTRACT: The local anesthetic lidocaine was determined in hair by hydrolysis of the samples with 4% NaOH in the presence of excessive Na2SO4 and subsequent headspace solid-phase microextraction with a 65-microm Carbowax/divinylbenzene fiber, and gas chromatography-mass spectrometry measurement with etidocaine as the internal standard. The calibration curve was linear between 0.1 and 1000 ng/mg. The detection and quantitation limits were 0.1 and 0.4 ng/mg, respectively. The method was applied to hair samples of 49 drug fatalities, and positive results were obtained in 32 cases with lidocaine concentrations between 0.4 and 400 ng/mg and 675 ng/mg in one extreme case. For comparison, morphine, 6-acetylmorphine, codeine, dihydrocodeine, methadone, cocaine, and benzoylecgonine were also determined by usual methods. From segmental investigations in four of the cases and from comparison with the hair concentrations of the other drugs, it follows that lidocaine was consumed for a longer period of time as an adulterant of cocaine and heroin preparations.
Journal of analytical toxicology 24(5):316-22. · 2.02 Impact Factor
