丙二醇醚類化合物之暴露評估

The Exposure Assessment of Propylene Glycol Ethers

施慧中(Hui-Chung Shih)

指導教授 ： 蔡詩偉

國立臺灣大學/公共衛生學院/環境衛生研究所/博士(2012年)

https://doi.org/10.6342/NTU.2012.00608

摘要

由於丙二醇醚類化合物兼具親水與親酯性使其普遍應用於電子、塗料及油墨工業且以進口為主。隨作業環境的改善及個人防護的加強，空氣暴露已非此類經皮吸收物質的主要暴露途徑，而傳統採樣分析方法已不足以因應低濃度範圍樣品的偵測，本研究以75μm CAR/PDMS為採集介質分別運用被動式及頂空SPME採樣技術完成空氣中及尿中丙二醇醚類化合物採樣分析方法評估並確認其可行性，另亦以Tape Stripping採樣技術初步完成皮膚暴露評估方法建立。
研究結果顯示：於30°C一大氣壓下PGME、 PGMEA、DPGME的實驗採樣率為(6.93±0.12)×10-1、(4.72±0.03)×10-1及(3.29 ± 0.20)×10-1 cm3 min-1，分別為理論採樣率的46、38及29倍。除SPME注射針頭不銹鋼材被懷疑是造成SPME理論與實驗採樣率誤差可能因素外，理論擴散係數公式未考量此類親水親脂特性物質於雙極性纖維與水分子間競合能力亦是造成誤差因素之一。採樣風速(0-0.18 m/s)及濕度(10- 80%RH)均證明SPME對PGME及PGMEA的採樣結果無明顯影響，而溫度則影響PGEs的採樣結果，將SPME與OSHA 99方法於作業環境現場作配對採樣結果比較，其線性關係良好(r=0.9984)且具一致性(斜率=0.97±0.03)，且作業現場勞工暴露結果相對誤差均可在±10%以內。因此，當不同的擴散係數被考量及在不同溫度下實驗採樣率被適度校正時，則PGEs的濃度仍可有效量測。經離心、酸鹼調整或鹽析前處理對尿液PGEs樣品採樣結果均無明顯影響，但適度的攪拌則可明顯增加纖維吸附量，CAR/PDMS 纖維與PGME及PGMEA尿液樣品間之擴散係數(Kfw)分別為2.099±0.043及 8.080±0.291，而盲樣測試結果顯示分析誤差均可控制在±5%內。運用SPME不同採樣技術於PGEs空氣及尿液樣品偵測除可省去傳統衍生分析或萃取濃縮時使用大量有機溶劑、樣品污染或損失的缺點，且將萃取、淨化、濃縮一步完成，因而可降低方法偵測濃度下限，使其在微量危害物分析上具可行性。
本研究採膠帶撕貼法將皮表危害物以膠帶移除，藉以測得角質層危害物含量並評估受測者皮膚暴露量。針對12位自願受測者，於室溫下進行手指、手掌至手臂等七個貼膚部位測試，實驗結果顯示在10cm2貼膚面積下2μl添加量具有最佳移除率，且無經皮水分散失問題。Tape Stripping結果顯示10分鐘採樣已達皮膚滲透吸附平衡狀態，此時PGME於手背皮膚滲透lag time為0.32分鐘，皮膚滲透質量通量(Flux)為0.75±0.07 mg cm-2hr-1，滲透係數Kp值為0.39±0.10 cm/hr。手部一次貼膚樣品PGME及PGMEA之平均回收率分別為54.69% (CV=3.29 %)及69.25%(CV=1.95 %)，同部位連續三次貼總移除率分別達89.16%及87.06%。於不同部位一、二、三次貼皮膚樣品相對於PGME總移除率比率分別為89.2%：9.3%：1.5%，顯示藉由一次貼的結果即可有效推估皮表PGME的總移除率。膠帶撕貼法移除率不受人體體脂肪(BMI)與皮表油脂多寡之影響，但受皮表溫度及個體皮膚表面細緻度差異之影響，初步評估膠帶撕貼法可適用於職場勞工皮膚PGEs暴露評估。

關鍵字

丙二醇醚類化合物 ； 固相微萃取 ； 膠帶撕貼法 ； 皮膚暴露 ； 方法評估

並列摘要

A solid-phase microextraction (SPME) device was used as a sampler for airborne and urinary propylene glycol ethers (PGEs), including propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and dipropylene glycol monomethyl ether (DPGME). The experimental sampling constants at 30°C and 1atm were (6.93±0.12)×10-1, (4.72±0.03)×10-1, and (3.29 ± 0.20)×10-1 cm3 min-1 for PGME, PGMEA and DPGME, which were 46, 38 and 29 times to theoretical values. The adsorption of chemicals on the stainless steel needle of the SPME fiber, both the hydrophilic and lipophilic properties and the surface action of adsorbed H2O on the biopolar crosslinked SPME fiber, were suspected to be the reasons why significant differences between theoretical and experimental sampling rates. The correlations between the results for PGME from both SPME device and OSHA organic method 99 were found to be linear (r=0.9984) and consistent (slope=0.97±0.03). Face velocity (0-0.18 m/s) was also proven to have no effects on the sampler. However, the effects of temperature and humidity have been observed. Therefore, the adjustments of experimental sampling constants at different environmental conditions will be a must.
Centrifugal, filteration and salt out the samples had no significant interference of the sampling results of the urinary samples, but had been effected by stirring. The SPME fiber-urine solution distribution coefficient(Kfw) were 2.099±0.043 and 8.080±0.291 for PGME and PGMEA, respectively. The relative error of the unknown samples could control within ±5%.
A tape stripping of the stratum corneum was developed for the measuring of dermal exposure to PGEs. Including 12 human volunteers were exposed to an a priori determined amount of PGEs at different sites on both hands and arms. It was found that the first tape stripping will removed 54.69% (CV=3.29%) and 69.25%(CV=1.95%) for PGME and PGMEA, respectively. The results showed that tape stripping 10min will reach the steady state, the lag time of the back of hand was 0.32min, the flux at steady state was 0.75±0.07 mgcm-2hr-1 and the permeation coefficient Kp was 0.39±0.10 cm/hr. The 1st strip , the 2nd strip and the 3rd strip samples versus to total recovery were 89.16: 9.34: 1.50 and 90.24: 8.56: 1.19 for PGME and PGMEA ,respectively. Besides, human BMI and skin oiliness were found to have no correlations with the removal of PGEs from the first tape stripping. However, significant differences were observed between females and males dermal sampling, probably due to the differences in surface temperature and roughness of the skin. The results indicate that this tape stripping technique influenced by environmental condition and individuals. Tape stripping was a appropriate technique to to quantify the dermal exposure results to PGEs.

並列關鍵字

Propylene glycol monomethyl ether ； solid-phase microextraction ； tape stripping ； dermal exposure ； method evaluation

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