Exposure to multiclass pesticides among female adult population in two Chinese cities revealed by hair analysis.

The high use of pesticides worldwide and the constant exposure of humans to these toxic-by-design chemicals have drawn the attention on the possible consequences on human health. However, information on the exposure of the general population to pesticides remain very limited in most countries, especially in urban areas. In the present work, hair analysis was conducted to investigate the exposure of 204 urban women living in two Chinese cities (Baoding and Dalian) to 110 pesticides and 30 metabolites of the following families: organochlorines, organophosphates, carbamates, pyrethroids, neonicotinoids, phenylpyrazoles, acid herbicides, urea herbicides and azoles. Results showed that 71 pesticides and 23 metabolites were found in the hair samples, with concentrations ranging up to 1070 pg/mg in hair. In each hair sample, the number of detected chemicals ranged from 25 to 50, demonstrating the cumulative exposure to pesticides among Chinese women in the studied regions. The concentrations of 38 chemicals (e.g., p-nitrophenol, diethyldithiophosphate, λ-cyhalothrin, permethrin, carbendazim and tebuconazole) were significantly different between women in Baoding and Dalian, indicating the regional differences in exposure to pesticide. Using a multiple regression analysis, we found that concentrations of a few dominant pesticides were associated with age, body mass index (BMI), cooking frequency and regions. These results can provide baseline information on exposure of female adult Chinese population to multiple pesticides and support future studies focused on the health effects associated with pesticide exposure.

Tracking main environmental factors masking a minor steroidal doping effect using metabolomic analysis of horse urine by liquid chromatography-high-resolution mass spectrometry.

There is an urgent need to implement holistic and untargeted doping control protocols with improved discriminatory power, compared to conventional methods that only target doping agents. Metabolomics, which aims to characterize all metabolites present in biological matrices, could fulfill this need. In this context, the aim of this study was to evaluate the impact of environmental factors on the ability to obtain a metabolic signature of stanozolol administration in horse doping situation. Urine samples from 16 horses breeded in two different places were collected over a one-year period, before, during and seven months after the administration of stanozolol, a horse doping agent. Metabolomic analysis was performed using ultra-high pressure reverse phase liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (MS). Results showed a major impact of the nutritional regimen, drug administration (for de-worming purpose) and breeding place on the metabolite profiles of horse urines, which hampered the detection of metabolic perturbations induced by stanozolol administration. After having used MS/MS experiments to characterize some MS features related to these environmental factors, we showed that highlighting and then removing the features impacted by these confounding factors before performing supervised multivariate statistical analyses could address this issue. In conclusion, adequate consideration should be given to environmental and physiological factors; otherwise, they can emerge as confounding factors and conceal doping administration.

Interlaboratory trial for the measurement of total cobalt in equine urine and plasma by ICP-MS.

Cobalt is an essential mineral micronutrient and is regularly present in equine nutritional and feed supplements. Therefore, cobalt is naturally present at low concentrations in biological samples. The administration of cobalt chloride is considered to be blood doping and is thus prohibited. To control the misuse of cobalt, it was mandatory to establish an international threshold for cobalt in plasma and/or in urine. To achieve this goal, an international collaboration, consisting of an interlaboratory comparison between 5 laboratories for the urine study and 8 laboratories for the plasma study, has been undertaken. Quantification of cobalt in the biological samples was performed by inductively coupled plasma-mass spectrometry (ICP-MS). Ring tests were based on the analysis of 5 urine samples supplemented at concentrations ranging from 5 up to 500 ng/mL and 5 plasma samples spiked at concentrations ranging from 0.5 up to 25 ng/mL. The results obtained from the different laboratories were collected, compiled, and compared to assess the reproducibility and robustness of cobalt quantification measurements. The statistical approach for the ring test for total cobalt in urine was based on the determination of percentage deviations from the calculated means, while robust statistics based on the calculated median were applied to the ring test for total cobalt in plasma. The inter-laboratory comparisons in urine and in plasma were successful so that 97.6% of the urine samples and 97.5% of the plasma samples gave satisfactory results. Threshold values for cobalt in plasma and urine were established from data only obtained by laboratories involved in the ring test. Copyright © 2017 John Wiley & Sons, Ltd.

Evaluation of horse urine sample preparation methods for metabolomics using LC coupled to HRMS.

BACKGROUND: Horse urine is the medium of choice for the implementation of metabolomic approaches aimed at improving horse doping control. However, drug analysis in this biofluid is a challenging task due to the presence of large amounts of interfering compounds. METHODOLOGY & RESULTS: A comparative study of sample preparation has been conducted to evaluate five sample-preparation methods, namely acetonitrile precipitation, proteinase K hydrolysis, membrane filtration and sample dilution with water by factors of five and 20, for metabolome analysis using liquid chromatography coupled to high resolution mass spectrometry. Assessment was performed at both global and targeted levels, by using a few thousand features obtained from peak detection software, and internal standards and 100 annotated or identified metabolites. CONCLUSION: By considering the number of detected signals, their intensity and their detection repeatability, acetonitrile precipitation was selected as the most efficient sample-preparation method for the analysis of horse urine metabolome in liquid chromatography coupled to high resolution mass spectrometry conditions.