Effect of hair care and hair cosmetics on the concentrations of fatty acid ethyl esters in hair as markers of chronically elevated alcohol consumption

doi:10.1016/S0379-0738(02)00412-7

Forensic Science International

Volume 131, Issues 2–3, 28 January 2003, Pages 90-97

https://doi.org/10.1016/S0379-0738(02)00412-7 Get rights and content

Abstract

Fatty acid ethyl esters (FAEE) can be used as alcohol markers in hair. It was investigated in this study whether this diagnostic method is disturbed by hair care and hair cosmetics. Traces of ethyl myristate, ethyl palmitate, ethyl oleate and ethyl stearate were detected in all of 49 frequently applied hair care products by headspace solid phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC–MS). The highest concentration was 0.003% in a hair wax. From experiments with separated hair samples of alcoholics as well as from the evaluation of the FAEE concentrations and the data about hair care of 75 volunteers (alcoholics, social drinkers and teetotalers) follows that usual shampooing, permanent wave, dyeing, bleaching or shading are of minor importance as compared to the drinking amount and other individual features. However, false positive results were found after daily treatment with a hair lotion containing 62.5% ethanol, with a deodorant and with a hair spray. As an explanation, it is assumed that FAEE are formed in the sebum glands also after regular topical application of products with a higher ethanol content.

Introduction

It was shown in previous papers [1], [2] that the concentrations of fatty acid ethyl esters (FAEE) in hair can be used as markers of chronically elevated alcohol consumption. A sum of the concentrations of ethyl myristate, ethyl palmitate, ethyl oleate and ethyl stearate (∑FAEE) above 1 ng/mg hair (up to 30 ng/mg) was found to be a strong evidence for excessive alcohol abuse, whereas for teetotalers and moderate social drinkers this concentration sum was as a rule below 0.4 ng/mg. FAEE are enzymatically formed from ethanol and free or bound fatty acids in almost all human tissues [3], [4]. From the relatively high concentrations in the washing solutions of the hair samples (external FAEE) as well as from the course of the FAEE concentrations along the hair length in comparison to the drinking history was concluded that they are incorporated into hair mainly from sebum after synthesis from ethanol and fatty acids or lipids in the sebum glands [2].

A considerable decrease of the drug concentrations in hair after cosmetic treatment was found by several authors [5], [6], [7], [8], [9]. This decrease depends not only on the type of cosmetic treatment but also on the degree of hair damage produced by the treatment. On the other hand, it was found in the statistic evaluation of practical hair analyses for THC that from the cases with positive results more subjects had dyed or bleached hair than from the cases with negative results [10]. Permed and bleached hair seems to have an increased sorption capacity for drugs from sweat, sebum or external sources [8]. A comprehensive description of the chemical composition of hair care products and of the chemical and physical processes during their application was published by Robbins [11].

The deposition from the external sebum layer into hair could be particularly sensitive to hair care and hair cosmetics. In principle, the FAEE concentrations could be affected by hair treatment in four different ways: (i) decrease by frequent shampooing, i.e. frequent removal of the sebum layer before deposition; (ii) decrease by chemical hydrolysis of the esters at high pH or by oxidation in the case of unsaturated esters; (iii) increase by deposition from hair care products containing FAEE; and (iv) increase by local synthesis from ethanol contained in hair care products. Therefore, in this paper, the results of a systematic study of the effects of different kinds of hair treatment are described. Furthermore, 49 hair care products were analysed for a possible FAEE content.

Section snippets

Hair samples

The scalp hair samples used in the hair treatment experiments were collected from fatalities who were post-mortem examined and had a history of heavy alcohol consumption known from police reports. Furthermore, hair samples of volunteers with certain kinds of cosmetic treatment before sampling were analysed and evaluated together with the data reported about the hair care. Since in these investigations also the lipids from the hair surface were analysed for FAEE the post-mortem samples were only

Content of FAEE in hair care products

According to patent literature, fatty acid alkyl esters are ingredients of several cosmetic products such as ointments or sun lotions. Isopropyl esters occur much more frequently but ethyl esters are also mentioned. Ethyl esters were prepared from rapeseed oil or other vegetable oils by transesterification with ethanol and are considered to be alternative fuel for diesel engines from renewable sources [13], [14]. Furthermore, they occur also in alcoholic beverages [15], [16]. Ethyl linoleate is

Conclusions

Scalp hair plays an important role in the individual appearance and sexual attractiveness and, therefore, is almost daily subjected to various procedures of hair care and hair cosmetics. Shampooing and cosmetic treatment (permanent wave, dyeing, bleaching or shading) in the usual frequency have no incisive effect on the use of FAEE as alcohol markers in hair and, in particular, do not lead to false negative results. Although some hair waxes contain FAEE in the same concentration range as hair

Acknowledgements

The authors thank the Deutsche Forschungsgemeinschaft (DFG) for the generous support of these investigations.

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This study aimed to assess alcohol consumption in a university student population though the combined analysis of the alcohol biomarkers ethyl glucuronide (EtG) and fatty acid ethyl esters (FAEEs) in hair samples. A total of 975 hair samples were analysed for EtG and FAEEs using liquid chromatography coupled to mass spectrometry (LC–MS/MS) and gas chromatography coupled to mass spectrometry (GC–MS/MS), respectively. The results were analysed using the cut-offs proposed by the Society of Hair Testing and receiver operating characteristic (ROC) curve analysis was performed to verify the adequacy of the proposed values for the study population. Good sensitivity and specificity were obtained for both biomarkers, especially for EtG, and a correlation was found with the self-reported alcohol consumption habit. In 56.3% of the abstinent, 65.8% of the moderate and 80.0% of the excessive drinking cases, self-reported alcohol consumption could be confirmed by combined alcohol biomarker analysis. Combined analysis of EtG and FAEEs in hair samples proved to be a valuable tool for the monitoring of alcohol consumption in a student population. For a feasible result interpretation, it is very important to document the use of hair products, cosmetic treatments and washing frequency, and for these to be considered during interpretation. Overall the participants were aware of their consumption pattern, however for doubtful cases and to account for academic calendars, repeated analysis of samples collected at different time frames would be advisable.
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Citation Excerpt :
It is also difficult to monitor the exact amount of cosmetic product applied by each volunteer, although attempts were made to ensure uniformity across the volunteers. In agreement with other authors [14,15] our data suggests that cosmetic products containing alcohol can cause an increase in observed FAEE levels in hair. Interestingly in addition to this there is the possibility that alcohol free products could also cause a minor increase in FAEE levels (volunteers 1 and 7) but within the UofM.
Fatty acid ethyl esters (FAEE) are direct metabolites of ethanol and have been shown to be suitable markers for the evaluation of alcohol consumption. Previous research has suggested that the regular use of alcohol containing cosmetic products can influence the concentration of FAEE detected in hair. In this study we investigated the influence of alcohol containing and alcohol free hair cosmetics (hairspray and waxes) on the FAEE concentrations in hair. The effect of cosmetic treatment was measured against the impact on ethyl palmitate in isolation as compared to the sum of four esters.
10 volunteers treated part of their scalp with cosmetic products every day during a 2 month period (alcohol free hairspray n = 2, hairspray containing alcohol (42% by volume) n = 3, alcohol free wax n = 2, wax containing alcohol (11% by volume) n = 3). After the 2 month period of cosmetic application hair samples from volunteers were collected from both sides of the scalp. Hair samples were washed with n-heptane, and then cut finely into small pieces. All samples were subjected to clean-up by HS-SPME and then GC PCI-MS/MS for analysis of FAEEs.
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Fatty acid ethyl esters (FAEEs) have been widely studied as specific markers of ethanol intake and mediators of ethanol-induced diseases. In the present study, a simple and rapid gas chromatography-mass spectrometry (GC-MS) method was established for the qualitative and quantitative analysis of six fatty acid ethyl esters (FAEEs), including ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate, ethyl linoleate, and ethyl arachidonate, in human whole blood. FAEEs were extracted from 200 μL of human whole blood by a modified liquid-liquid extraction, and the hexane layer was injected directly into GC-MS with ethyl heptadecanoate as the internal standard. The limits of detection (LODs) and limits of quantification (LOQs) were in the range of 5–50 ng/mL and 15–200 ng/mL, respectively. Linearity ranged up to 10 μg/mL with r² higher than 0.998. Accuracy was in the range of 90.3–109.7%, while intra-day and inter-day precision were 0.7–9.3% and 3.4–12.5%, respectively. This method was then applied to 38 real samples from forensic cases. Differences in the most common FAEEs between Chinese and Western subjects were discussed. The relationship of FAEE concentrations with age and gender was also investigated.

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Effect of hair care and hair cosmetics on the concentrations of fatty acid ethyl esters in hair as markers of chronically elevated alcohol consumption

Abstract

Introduction

Section snippets

Hair samples

Content of FAEE in hair care products

Conclusions

Acknowledgements

Forensic Sci. Int.

Prog. Lipid Res.

Prostaglandins Leukot. Essent. Fatty Acids

Forensic Sci. Int.

Forensic Sci. Int.

J. Chromatogr. A

J. Chromatogr. A

Forensic Sci. Int.

Fatty acid ethyl esters in hair as markers of alcohol consumption: segmental hair analysis of alcoholics, social drinkers, and teetotallers

Clin. Chem.