Mycotoxins Exposure of French Grain Elevator Workers: Biomonitoring and Airborne Measurements.

It is now recognized that additional exposure to mycotoxins may occur through inhalation of contaminated dust at a workplace. The aim of this study was to characterize the multi-mycotoxin exposure of French grain elevator workers using biomonitoring and airborne measurements. Eighteen workers participated in the study. Personal airborne dust samples were analyzed for their mycotoxin concentrations. Workers provided multiple urine samples including pre-shift, post-shift and first morning urine samples or 24 h urine samples. Mycotoxin urinary biomarkers (aflatoxin B1, aflatoxin M1, ochratoxin A, ochratoxin α, deoxynivalenol, zearalenone, α-zearalenol, ß-zearalenol, fumonisin B1, HT-2 toxin and T-2 toxin) were measured using a liquid chromatography-high-resolution mass spectrometry method. Grain elevator workers were highly exposed to organic airborne dust (median 4.92 mg.m-3). DON, ZEN and FB1 were frequent contaminants in 54, 76 and 72% of air samples, respectively. The mycotoxin biomarkers quantified were DON (98%), ZEN (99%), α-ZEL (52%), ß-ZEL (33%), OTA (76%), T-2 (4%) and HT-2 (4%). DON elimination profiles showed highest concentrations in samples collected after the end of the work shift and the urinary DON concentrations were significantly higher in post-shift than in pre-shift-samples (9.9 and 22.1 µg/L, respectively). ZEN and its metabolites concentrations did not vary according to the sampling time. However, the levels of α-/ß-ZEL were consistent with an additional occupational exposure. These data provide valuable information on grain worker exposure to mycotoxins. They also highlight the usefulness of multi-mycotoxin methods in assessing external and internal exposures, which shed light on the extent and pathways of exposure occurring in occupational settings.

Investigating Multi-Mycotoxin Exposure in Occupational Settings: A Biomonitoring and Airborne Measurement Approach.

Investigating workplace exposure to mycotoxins is of the utmost importance in supporting the implementation of preventive measures for workers. The aim of this study was to provide tools for measuring mycotoxins in urine and airborne samples. A multi-class mycotoxin method was developed in urine for the determination of aflatoxin B1, aflatoxin M1, ochratoxin A, ochratoxin α, deoxynivalenol, zearalenone, α-zearalenol, ß-zearalenol, fumonisin B1, HT2-toxin and T2-toxin. Analysis was based on liquid chromatography-high resolution mass spectrometry. Sample pre-treatments included enzymatic digestion and an online or offline sample clean-up step. The method was validated according to the European Medicines Agency guidance procedures. In order to estimate external exposure, air samples collected with a CIP 10 (Capteur Individuel de Particules 10) personal dust sampler were analyzed for the quantification of up to ten mycotoxins, including aflatoxins, ochratoxin A, deoxynivalenol, zearalenone, fumonisin B1 and HT-2 toxin and T-2 toxin. The method was validated according to standards for workplace exposure to chemical and biological agents EN 482. Both methods, biomonitoring and airborne mycotoxin measurement, showed good analytical performances. They were successfully applied in a small pilot study to assess mycotoxin contamination in workers during cleaning of a grain elevator. We demonstrated that this approach was suitable for investigating occupational exposure to mycotoxins.

Occupational exposure of cashiers to bisphenol S via thermal paper.

PURPOSE: In thermal paper, Bisphenol S (BPS) is one of the alternatives for bisphenol A (BPA). Due to its structural similarity to BPA, concern has been raised about the safety of BPS. Indeed, handling thermal paper receipts could be a source of occupational exposure to BPS among cashiers, as it was previously described for BPA. In this study, we investigated whether frequent contacts with thermal paper are associated with an increase in urinary BPS levels in cashiers. METHOD: Total (unconjugated and conjugated forms) and free (unconjugated) BPS were measured in urine samples from 17 cashiers and 15 controls, using LC-MS/MS. Spot urine samples, including pre-shift and post-sift samples and first morning void were collected from each volunteer. BPS concentration in thermal paper was determined and the number of receipts handled by cashiers was estimated as well. RESULTS: The median urinary total BPS concentration was 0.67 µg/L (0.52 µg/g creatinine) for controls and 2.53 µg/L (2.07 µg/g creatinine) for cashiers. Total BPS concentration was significantly higher in cashiers than in controls. Free BPS was detected in less than 20% of urine samples collected from controls and in less than 50% of urine samples collected from cashiers. CONCLUSION: The detectable levels of BPS in urine of controls suggest an exposure to BPS of the general population. In addition, frequent contact with thermal paper could be responsible for an increase in urinary concentration of total BPS in cashiers.

Occupational exposure of cashiers to Bisphenol A via thermal paper: urinary biomonitoring study.

PURPOSE: As an essential component of polycarbonate plastics and epoxy resins, Bisphenol A (BPA) is found in numerous industrial and consumer products. BPA may cause adverse health effects because of its endocrine activity. General population exposure to this compound mainly through diet is well documented. Thermal paper was also identified as a source of BPA through dermal intake. In this study, we investigated whether frequent contact with thermal paper is associated with an increase in urinary BPA excretion. METHODS: We evaluated the exposure to BPA in cashiers and in non-occupationally exposed workers from several workplaces. Urinary BPA was quantified in free (unconjugated) and total (unconjugated plus conjugated) forms in 24-h and spot urine samples using LC-MS/MS. BPA concentration in thermal paper was also measured from each workplace. In addition, participants provided information on job, food and drink, tobacco consumption and hands wash during the sampling period through a questionnaire. RESULTS: Urine samples were collected from 90 cashiers and 44 controls. Free and total BPA were detected in all samples. The median urinary total BPA concentration was 3.54 µg/L (2.89 µg/g creatinine) for controls and 8.92 µg/L (6.76 µg/g creatinine) for cashiers. For the free BPA, the median urinary concentration was 0.20 µg/L (0.21 µg/g creatinine) for controls and 0.28 µg/L (0.22 µg/g creatinine) for cashiers. Any correlation was found between the urinary concentration levels and the number of thermal receipts handled. Hand washes frequency, age, job length of service and tobacco consumption had also no effect on the BPA excretions. CONCLUSION: A significant increase in urinary total BPA concentration was observed for cashiers handling daily thermal paper receipts. However, no significant increase was observed in urinary free BPA concentration. These findings are particularly interesting for risk assessment since all available data on occupational exposure to BPA through thermal paper were obtained from models or from simulated experiments.

Characterization and validation of sampling and analytical methods for mycotoxins in workplace air.

Mycotoxins are produced by certain plant or foodstuff moulds under growing, transport or storage conditions. They are toxic for humans and animals, some are carcinogenic. Methods to monitor occupational exposure to seven of the most frequently occurring airborne mycotoxins have been characterized and validated. Experimental aerosols have been generated from naturally contaminated particles for sampler evaluation. Air samples were collected on foam pads, using the CIP 10 personal aerosol sampler with its inhalable health-related aerosol fraction selector. The samples were subsequently solvent extracted from the sampling media, cleaned using immunoaffinity (IA) columns and analyzed by liquid chromatography with fluorescence detection. Ochratoxin A (OTA) or fumonisin and aflatoxin derivatives were detected and quantified. The quantification limits were 0.015 ng m(-3) OTA, 1 ng m(-3) fumonisins or 0.5 pg m(-3) aflatoxins, with a minimum dust concentration level of 1 mg m(-3) and a 4800 L air volume sampling. The methods were successfully applied to field measurements, which confirmed that workers could be exposed when handling contaminated materials. It was observed that airborne particles may be more contaminated than the bulk material itself. The validated methods have measuring ranges fully adapted to the concentrations found in the workplace. Their performance meets the general requirements laid down for chemical agent measurement procedures, with an expanded uncertainty less than 50% for most mycotoxins. The analytical uncertainty, comprised between 14 and 24%, was quite satisfactory given the low mycotoxin amounts, when compared to the food benchmarks. The methods are now user-friendly enough to be adopted for personal workplace sampling. They will later allow for mycotoxin occupational risk assessment, as only very few quantitative data have been available till now.