Carrieri Mariella, Bartolucci Giovanni B, Paci Enrico, Sacco Paolo, Pigini Daniela, Zaratin Laura, Cottica Danilo, Scapellato Maria L, Tranfo Giovanna
Department of Cardiac, Thoracic and Vascular Sciences, University of Padua, via Giustiniani 2, 35128 Padua, Italy.
Department of Occupational Medicine INAIL Research, Via Fontana Candida 1, 00040 Monte Porzio Catone, Rome, Italy.
J Chromatogr A. 2014 Aug 1;1353:114-20. doi: 10.1016/j.chroma.2014.02.018. Epub 2014 Feb 13.
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.
1,3 - 丁二烯(BD)是一种主要用于制造橡胶和乳胶的工业化学品;它也是一种普遍存在的环境污染物,主要来源是交通。职业接触BD可发生在其生产过程以及作为原材料使用的过程中。本研究的目的是对一种新型BD扩散采样器进行实验室和现场验证。填充有Carbopack X的Radiello扩散采样器在0.177 mg/m³、20°C和50%相对湿度(RH)条件下,8小时暴露时间的标称采样率为30.5 cm³/min。可使用一个模型根据温度、时间和RH来计算采样率。浓度在30 μg/m³以上时不影响采样率。根据国际标准化组织(ISO)13752通过实验室数据和现场比较计算得出的测量不确定度(k = 2)满足EN 482:2006对在阈限值 - 时间加权平均值(TLV - TWA)的0.1至0.5倍之间进行测量的要求(不确定度<50%)。对于现场验证研究,38名接触BD的工人和20名行政员工作为对照组,接受了环境和生物监测。通过扩散采样器(Radiello)与主动采样器比较来测量个人对BD的接触情况。检测到的暴露受试者的BD暴露水平较低(平均值为0.059,范围<0.010 - 1.340 mg/m³),但高于对照组水平,对照组均低于0.010 mg/m³。扩散采样与主动(泵送)空气采样之间的比较显示出良好的相关性,优化回归线的截距和斜率与理想值无系统偏差。还测定了在工作班次结束时收集的尿液样本中两种生物标志物的浓度:通过气相色谱 - 质谱联用仪(GC - MS)测定未变化的BD,通过液相色谱 - 串联质谱仪(HPLC - MS/MS)测定代谢物二羟基丁基巯基尿酸(DHBMA)。暴露组生物标志物的尿排泄量平均高于对照组(尿BD:平均值8.8,范围<1 - 48.1 ng/l;DHBMA:平均值0.232,范围0.016 - 0.572 mg/l),而对照组为(尿BD:平均值6.4,范围2.6 - 14.5 ng/l;DHBMA:平均值0.205,范围0.037 - 0.602 mg/l),但仅未变化的BD有统计学显著差异,DHBMA无差异。总之,通过扩散采样器(Radiello)进行环境监测似乎是评估低水平空气中BD暴露的可靠方法,也是传统主动采样的便捷替代方法。