New insights on the UV/TiO2 photocatalytic treatment of thiomersal and its 2-sulfobenzoic acid product

E. M. de la Fournière, J. Meichtry, G. Custo, E. Gautier, M. Litter
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Abstract

Thiomersal (TM), a complex between 2-mercaptobenzoic acid (2-MBA) and ethylmercury (C2H5Hg+), is an antimicrobial preservative used in immunological, ophthalmic, cosmetic products, and vaccines. TM has been treated by UV/TiO2 photocatalysis in the presence or absence of oxygen at acidic pH. C2H5Hg+, 2-MBA, and 2-sulfobenzoic acid (2-SBA) were found as products. A 2-SBA photocatalytic treatment was undertaken to study sulfur evolution. Photocatalytic runs were performed using a UVA lamp (λmax = 352 nm), open to the air or under N2. A suspension of the corresponding TM or 2-SBA salt and TiO2 was prepared, and pH was adjusted. Suspensions were stirred in the dark for 30 min and then irradiated. TM, 2-MBA, 2-SBA, and C2H5Hg+ were quantified by HPLC, sulfur by TXRF, and the deposits on the photocatalyst were analyzed by chemical reactions. The mineralization degree was followed by TOC. Sulfate was determined using BaCl2 at 580 nm. Photocatalytic destruction of TM and total C2H5Hg+ was complete under N2 and air, but TM degradation was much faster in air. The evolution of TM and the products followed a pseudo-first-order kinetics. TiO2-photocatalytic degradation is a suitable technique for the treatment of TM and its degradation products. In contrast to other organomercurial compounds, TM degradation is faster in the presence of O2, indicating that the oxidative mechanism is the preferred pathway. A significant TM mineralization (> 60%, NPOC and total S) was obtained. TM was more easily degraded than 2-SBA. Sulfate was the final product.
紫外/TiO2光催化处理硫柳汞及其2-巯基苯甲酸产物的新进展
硫柳汞(TM)是2-巯基苯甲酸(2-MBA)和乙基汞(C2H5Hg+)之间的复合物,是一种抗菌防腐剂,用于免疫、眼科、化妆品和疫苗。在酸性条件下,对TM进行了有氧或无氧的紫外/TiO2光催化处理,得到产物为C2H5Hg+、2-MBA和2-磺酸(2-SBA)。采用2-SBA光催化法研究硫的析出。光催化运行使用UVA灯(λmax = 352 nm),对空气开放或在N2下进行。制备相应的TM或2-SBA盐与TiO2混悬液,调整pH。在黑暗中搅拌悬液30分钟,然后照射。HPLC法测定TM、2-MBA、2-SBA和C2H5Hg+, TXRF法测定硫,化学反应法测定光催化剂上的沉积。矿化程度依次为TOC。用BaCl2在580 nm处测定硫酸盐。在N2和空气条件下,TM和总C2H5Hg+完全被光催化破坏,但在空气条件下TM的降解速度要快得多。TM及其产物的演化遵循准一级动力学。二氧化钛光催化降解是处理TM及其降解产物的一种合适的技术。与其他有机化合物相比,TM在O2存在下降解速度更快,表明氧化机制是首选途径。获得了显著的TM矿化(> 60%,NPOC和总S)。TM比2-SBA更容易降解。硫酸盐是最终产物。
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