Accurate low-dose exposure assessment of benzene and monoaromatic compounds by diffusive sampling: sampling and analytical method validation according to ISO 23320 for radiello® samplers packed with activated charcoal.

The research study aimed at providing an accurate low-dose benzene exposure assessment method, by validating diffusive monitoring techniques for benzene personal exposure measurements at workplaces where benzene concentrations are expected in the low ppb range, such as in the present-day chemical, petrochemical, foundry, and pharmaceutical industry. The project was aimed at addressing the need for a robust and fully validated method to perform personal exposure measurements considering that the occupational exposure limit value for benzene is going to be significantly lowered in the next few years. Diffusive sampling offers a reliable alternative to pumped sampling methods, intrinsic safety in potentially explosive atmospheres, lightness, and ease of use. In this study, the radiello® diffusive sampler, with the packed activated charcoal RAD130 adsorbing substrate [suitable for solvent desorption and analysis by high-resolution gas chromatography-flame ionization detection (HRGC-FID)], was used. The experiments have been conducted following the ISO 23320 standard in the range from 0.005 to 0.1 ppm (16 to 320 µg/m3), yielding a full validation of the sampling and analytical method. The sampler performances have fulfilled all requisites of the ISO 23320 standard, in particular: bias due to the selection of a non-ideal sorbent is lower than 10% (no significant back diffusion of benzene due to concentration change in the atmosphere); bias due to storage of samples for up to 2 months is lower than 10%; nominal uptake rate for benzene on RAD130 is 74.65 mL/min; and expanded uncertainty of the sampling and analytical method is 20.6%. The sampling and analytical method is therefore fit-for-purpose for the personal exposure measurements aimed at testing compliance with occupational exposure limit values for benzene. The method is also fit for short-duration exposure monitoring related to specific tasks, and other volatile organic compounds, usually found in the same workplaces, such as aliphatic and aromatic hydrocarbons and some oxygenated compounds, have also been studied. In particular, n-hexane and isopropyl benzene, whose classification is currently under revision, can be efficiently monitored by this technique.

A new, sensitive and versatile assay for quantitative determination of α-fluoro-ß-alanine (AFBA) in human urine by using the reversed-phase ultrahigh performance-tandem mass spectrometry (rp-UHPLC-MS/MS) system.

A method for the quantitation of α-fluoro-ß-alanine (AFBA), the main metabolite of capecitabine (Cape) and 5-fluoruracil (5-FU), is described. Among antineoplastic drugs (ADs), 5-FU and Cape (the new oral prodrug) are the most commonly applied drugs in cancer therapy. The main objective of this study was to develop a reliable method that would be easy to run on a reversed-phase UHPLC system coupled to tandem mass spectrometry. AFBA was derivatized with Sanger's reagent to ensure complete yield of a stable 2,4 dinitrophenil-α-fluoro-ß-alanine derivative. This method was based on the use of a mixed-mode anion exchange solid phase extraction enabling urinary extracts to be clear of endogenous interferences affecting quantitative results. The assay was validated in human urine according to FDA criteria with the use of a labeled internal standard (ß-alanine-d4) to minimize experimental error. Good accuracy and precision were demonstrated by determining spiked urine QC samples in four consecutive days. The recovery of AFBA was between 70.0 and 82.6%, with a matrix effect that was 12.8%-18.5%. The lower limit of quantitation (LOQ) was 0.5 ng/mL with a coefficient of variation of 5.3%. This assay was successfully applied to determine the levels of this metabolite in a large number of urine samples taken from personnel who were occupationally exposed to ADs.

Validation of a radial diffusive sampler for measuring occupational exposure to 1,3-butadiene.

1,3-Butadiene (BD) is a major industrial chemical used in the manufacture of rubbers and latexes; it is also a ubiquitous environmental pollutant whose major source is traffic. Occupational exposure to (BD) can occur both during its production and during its use as a raw material. The objective of the study was the laboratory and field validation of a new diffusive sampler for BD. The nominal sampling rate of the Radiello diffusive sampler filled with Carbopack X is 30.5 cm(3)/min, at 0.177 mg/m(3), 20 °C and 50% relative humidity (RH), for an 8-h exposure time. A model can be used for calculating the sampling rate as a function of temperature, time and RH. The concentration does not affect the sampling rate above 30 µg/m(3). The measurement uncertainty (k=2), calculated both by laboratory data and by field comparison according to International Standard Organization (ISO) 13752, satisfies the EN 482:2006 requirement for measurements between 0.1 and 0.5 times the threshold limit value-time weighted average (TLV-TWA) (uncertainty<50%). For field validation study, 38 workers exposed to BD and 20 administrative employees, as the control group, underwent environmental and biological monitoring. Personal exposure to BD was measured by diffusive samplers (Radiello) in comparison with active samplers. The BD exposure levels detected for the exposed subjects were low (mean 0.059, range <0.010-1.340 mg/m(3)) but higher than the controls levels, all below 0.010 mg/m(3). The comparison between diffusive and active (pumped) air sampling showed a good correlation, with no systematic deviation from the ideal values of the intercept and slope of the optimized regression line. The concentrations of two biomarkers were also determined on urine samples, collected at the end of the work-shift: unchanged BD, by GC-MS, and the metabolite dihydroxybutylmercapturic acid (DHBMA), by HPLC-MS/MS. The urinary excretion of the biomarkers was on average higher in the exposed group (urinary BD: mean 8.8, range <1-48.1 ng/l; DHBMA: mean 0.232, range 0.016-0.572 mg/l) than in controls (urinary BD: mean 6.4, range 2.6-14.5 ng/l; DHBMA: mean 0.205, range 0.037-0.602 mg/l), but a statistically significant difference was achieved only for unchanged BD and not for DHBMA. In conclusion, the environmental monitoring measured by diffusive samplers (Radiello) appears to be a reliable method for the assessment of exposure to low levels of airborne BD and a convenient alternative to the conventional active sampling.

Field evaluation of thermal and chemical desorption BTEX radial diffusive sampler radiello compared with active (pumped) samplers for ambient air measurements.

The performance of two types of radiello diffusive samplers, filled with a thermally desorbable adsorbent (graphitised carbon Carbograph 4) and with a solvent desorbable adsorbent (activated charcoal), respectively, have been evaluated for the monitoring of BTEX in ambient air, by comparison with active (pumped) samplers. A two year survey was carried out in Padua, a medium-sized town, in a traffic site, close to a busy crossroad. The concentrations of BTEX were measured for 15 campaigns, during which four series of radial diffusive samplers were exposed for 2 day, 7 day, 10 day and 14 day time periods, respectively. Every series of chemical desorption samplers included three replicates; thermal desorption samplers included six replicates, three of them filled with freshly conditioned cartridges and three filled with regenerated cartridges. No significant difference in the levels measured either by new or by regenerated cartridges has been found. During three campaigns (summer 2004, winter and spring 2005) two active (pumped) samplers were added for each sampling period. The diffusive uptake rates have been calculated and modelled under various conditions of concentration, temperature and exposure time. The effects of the environmental factors on the performances of both solvent and thermally desorbable samplers have been evaluated. The repeatability of the whole measurement process (sampling and analysis) was calculated for every sampling duration. The comparison of concentration levels measured by diffusive and active sampling methods shows correlation coefficients R >or= 0.98 (p<0.01) for all the compounds. The uncertainty of the diffusive sampling method under field conditions, using active sampling as the reference method, has been assessed according to the ISO 13752 requirements. On field relative expanded uncertainty for benzene has been found below 20%.