Université Paris-Est, Laboratoire Géomatériaux et Environnement, 5 Bd Descartes, 77454 Marne-la-Vallée Cedex 2, France.
Chemosphere. 2010 Oct;81(5):594-602. doi: 10.1016/j.chemosphere.2010.08.032. Epub 2010 Sep 15.
The electrochemical abatement of the antibiotic sulfamethoxazole (SMX) from aqueous solutions at pH 3.0 has been carried out by anodic oxidation and electro-Fenton (EF) processes with H(2)O(2) electrogeneration. The electrolyses have been performed using a small, undivided cell equipped with a Pt or thin film boron-doped diamond (BDD) anode and a carbon-felt cathode. The higher performance of the EF process with 0.2mM Fe(2+) in a BDD/carbon felt cell is demonstrated. This is due to the higher production of ()OH radicals, as well as to the simultaneous degradation at the anode surface and in the bulk solution. At low current, the oxidation at the anode was predominant; at high current, SMX was pre-eminently degraded in the bulk. SMX was quickly destroyed under all the conditions tested, following pseudo first-order kinetics; however, the almost total removal of the total organic carbon was only achieved in the BDD/carbon felt cell. The reaction by-products were quantified by chromatographic techniques and thus, the reaction pathway for the mineralization of SMX by EF has been elucidated. Hydroxylation of SMX on the sulfanilic ring is suggested as the first step, followed by the formation of p-benzoquinone and 3-amino-5-methylisoxazole. Their oxidative cleavage led to the formation of five carboxylic acids that were finally mineralized to CO(2); the release of NH(4)(+), NO(3)(-), and SO(4)(2-) accounted for almost 100% of the initial nitrogen and sulfur content. The absolute rate constants for the oxidative degradation of SMX and the detected aromatic by-products have also been determined.
在 pH 3.0 条件下,采用阳极氧化和电芬顿(EF)工艺,利用 H(2)O(2)电化学产生,对水溶液中的抗生素磺胺甲恶唑(SMX)进行了电化学消除。 这些电解反应是在一个配备 Pt 或薄膜掺硼金刚石(BDD)阳极和碳纤维毡阴极的小型、未分隔电池中进行的。 结果表明,在 BDD/碳纤维毡电池中,添加 0.2mM Fe(2+)的 EF 工艺性能更高。 这是由于 ()OH 自由基的生成更高,以及在阳极表面和在整个溶液中同时降解。 在低电流下,阳极氧化占主导地位; 在高电流下,SMX 在主体溶液中主要被降解。 在所有测试条件下,SMX 都能快速被破坏,遵循准一级动力学; 然而,只有在 BDD/碳纤维毡电池中才能实现总有机碳的几乎完全去除。 通过色谱技术对反应副产物进行了定量分析,从而阐明了 EF 矿化 SMX 的反应途径。 建议磺胺甲恶唑在磺胺基环上的羟化作用是第一步,随后形成对苯醌和 3-氨基-5-甲基异恶唑。 它们的氧化裂解导致形成五个羧酸,最终矿化为 CO(2); NH(4)(+)、NO(3)(-)和 SO(4)(2-)的释放几乎占初始氮和硫含量的 100%。 还确定了 SMX 和检测到的芳族副产物的氧化降解的绝对速率常数。