TiO_2光催化氧化水体中微污染磺胺类药物
摘要
磺胺类药物(SAs)是临床治疗、畜牧业和水产养殖业中的常用抗菌药物。随着我国农业的快速发展,其作为兽药、渔药的使用量与日俱增。有研究表明磺胺类药物进入环境后降解较慢,可能长期存留。药物残留不仅对生态系统产生不良影响,还可以通过食物链富集作用危害到人体健康。Ti02光催化氧化具有性质稳定、无毒、催化活性高、无二次污染、能矿化某些难生物降解污染物等优点,被广泛应用于持久性有机污染物、个人护理品等难生物降解有机物的去除研究。
实验采用Ti02和Ti02/EP对水体中低质量浓度磺胺嘧啶(SDZ)和磺胺甲恶唑(SMX)进行了光催化降解,探讨了各种因素对SDZ和SMX光催化降解效果的影响。结果表明：
(1) UV/TiO2光催化降解微量SDZ,最好水平组合是：pH值约为7、Ti02浓度为0.08g/L和光照强度为1000μw/cm2,初始浓度为5mg/L,反应时间为50 min时,SDZ降解效率超过99%。
(2)进行UV-TiO2/EP光催化降解SDZ和SMX,在最适水平组合：Ti02最佳负载量为20 wt%,质量浓度为5 mg/L,pH=6.7,紫外光照射强度为1000μw/cm2,反应时间达到45 min和30 min时,SDZ和SMX的降解率达到94%和96%。
(3)同时考察了水体中常见无机离子和腐植酸对SAs降解效率的影响。HC03-在低浓度时能促进SDZ和SMX的光催化降解,高浓度时促进作用不明显；S042-和C1-对SDZ和SMX的光催化降解有轻微的抑制作用；HA对SDZ和SMX光催化降解有抑制作用,浓度越高,抑制作用越强。
(4)通过高活性的羟基自由基(·OH),攻击SDZ分子中的S-N键和S-C和C-S断裂,形成中间产物：4-(2-氨基毗啶-1(2H)-基)苯胺、磺胺酸、4-(2-氨基吡啶-1(2氢)-基)磺酸。然后活性·OH再次攻击苯胺和4-(2-氨基吡啶-1(2氢)-基)磺酸的苯环、C-N和C-S键,最终使其彻底降解为8042-,N03-,NH4+,CO2等无机离子以及无机物。由此推测SDZ光催化降解途径可能有三种。
实验证明,UV-TiO2光催化氧化能够有效降解水中的低质量浓度磺胺类药物,实验为低浓度磺胺类药物污染的水体修复提供一些基础数据。
Sulfonamides are synthetic antimicrobial agents, which are used in aquaculture, animal husbandry and human medicines commonly. With the agriculture development in our country, the usage amount of sulfonamides as veterinary and fisher drugs increase every day. Some researches showed that self-decomposition of sulfonamides was slow and a considerable amount of its still remained for a long time in environment. TiO2 is considered to be the most suitable for widespread environmental photocatalytic applications due to its considerable photocatalytic activity, high stability, non-environmental impact and low cost.
The degradation of trace sulfadiazine and sulfamethoxazole in water by TiO2 and TiO2 /EP was investigated. The effects of various parameters on the performance of degradation rates were studied too. It is provided some basic data for treating trace sulfadiazine and sulfamethoxazole in water. Results are showed that:
(1) The photodegradation of trace SDZ in wastewater by using UV/TiO2 can get a good result at the optimal conditions. The degradation efficiency of SDZ reached 99% under the conditions of initial concentration of SDZ of 5.0 mg/L, TiO2 dose of 0.08g/L, solution pH of neutral, radiation intensity of 1000 uw/cm2 and reaction time of 50 min.
(2) The photodegradation of trace SDZ (SMX) in wastewater by using UV-TiO2/EP can get a good result at the optimal conditions. The degradation efficiency of SDZ (SMX) reached 94%(96%) under the conditions of initial concentration of 5.0 mg/L, TiO2 loading of 20 wt%, solution pH of 6.7, radiation intensity of 1000μw/cm2 and reaction time of 45 (30)min.
(3) The degradation efficiency of SDZ and SMX were enhanced at low concentration and was not remarkable at high concentration by HCO3-. The degradation efficiency of SDZ and SMX were slightly inhibited by SO42- and Cl-, and it was strongerly inhibited by HA, the inhibition was stronger as the concentration higher.
(4) The mechanism of SDZ may involved in high oxidation ability of active hydroxyl radicals (·OH) which are strongly enough to break the S-N, C-S and S-C bond of SDZ. Froming the intermediate product:sulfanilicacid,4-(2-iminopyrimidine-1(2H)-vl)aniline, 4-(2-iminopyri-midine-1(2H)-vl) aniline salfacid. And then·OH again attacks benzene ring, C-N and C-S bond of the intermediate product, finally, SDZ is broken into SO42-, NO3-, NH4+, CO2 ect. Thus, we can concluded that the degradation of SDZ may have three pathway.
实验采用Ti02和Ti02/EP对水体中低质量浓度磺胺嘧啶(SDZ)和磺胺甲恶唑(SMX)进行了光催化降解,探讨了各种因素对SDZ和SMX光催化降解效果的影响。结果表明：
(1) UV/TiO2光催化降解微量SDZ,最好水平组合是：pH值约为7、Ti02浓度为0.08g/L和光照强度为1000μw/cm2,初始浓度为5mg/L,反应时间为50 min时,SDZ降解效率超过99%。
(2)进行UV-TiO2/EP光催化降解SDZ和SMX,在最适水平组合：Ti02最佳负载量为20 wt%,质量浓度为5 mg/L,pH=6.7,紫外光照射强度为1000μw/cm2,反应时间达到45 min和30 min时,SDZ和SMX的降解率达到94%和96%。
(3)同时考察了水体中常见无机离子和腐植酸对SAs降解效率的影响。HC03-在低浓度时能促进SDZ和SMX的光催化降解,高浓度时促进作用不明显；S042-和C1-对SDZ和SMX的光催化降解有轻微的抑制作用；HA对SDZ和SMX光催化降解有抑制作用,浓度越高,抑制作用越强。
(4)通过高活性的羟基自由基(·OH),攻击SDZ分子中的S-N键和S-C和C-S断裂,形成中间产物：4-(2-氨基毗啶-1(2H)-基)苯胺、磺胺酸、4-(2-氨基吡啶-1(2氢)-基)磺酸。然后活性·OH再次攻击苯胺和4-(2-氨基吡啶-1(2氢)-基)磺酸的苯环、C-N和C-S键,最终使其彻底降解为8042-,N03-,NH4+,CO2等无机离子以及无机物。由此推测SDZ光催化降解途径可能有三种。
实验证明,UV-TiO2光催化氧化能够有效降解水中的低质量浓度磺胺类药物,实验为低浓度磺胺类药物污染的水体修复提供一些基础数据。
Sulfonamides are synthetic antimicrobial agents, which are used in aquaculture, animal husbandry and human medicines commonly. With the agriculture development in our country, the usage amount of sulfonamides as veterinary and fisher drugs increase every day. Some researches showed that self-decomposition of sulfonamides was slow and a considerable amount of its still remained for a long time in environment. TiO2 is considered to be the most suitable for widespread environmental photocatalytic applications due to its considerable photocatalytic activity, high stability, non-environmental impact and low cost.
The degradation of trace sulfadiazine and sulfamethoxazole in water by TiO2 and TiO2 /EP was investigated. The effects of various parameters on the performance of degradation rates were studied too. It is provided some basic data for treating trace sulfadiazine and sulfamethoxazole in water. Results are showed that:
(1) The photodegradation of trace SDZ in wastewater by using UV/TiO2 can get a good result at the optimal conditions. The degradation efficiency of SDZ reached 99% under the conditions of initial concentration of SDZ of 5.0 mg/L, TiO2 dose of 0.08g/L, solution pH of neutral, radiation intensity of 1000 uw/cm2 and reaction time of 50 min.
(2) The photodegradation of trace SDZ (SMX) in wastewater by using UV-TiO2/EP can get a good result at the optimal conditions. The degradation efficiency of SDZ (SMX) reached 94%(96%) under the conditions of initial concentration of 5.0 mg/L, TiO2 loading of 20 wt%, solution pH of 6.7, radiation intensity of 1000μw/cm2 and reaction time of 45 (30)min.
(3) The degradation efficiency of SDZ and SMX were enhanced at low concentration and was not remarkable at high concentration by HCO3-. The degradation efficiency of SDZ and SMX were slightly inhibited by SO42- and Cl-, and it was strongerly inhibited by HA, the inhibition was stronger as the concentration higher.
(4) The mechanism of SDZ may involved in high oxidation ability of active hydroxyl radicals (·OH) which are strongly enough to break the S-N, C-S and S-C bond of SDZ. Froming the intermediate product:sulfanilicacid,4-(2-iminopyrimidine-1(2H)-vl)aniline, 4-(2-iminopyri-midine-1(2H)-vl) aniline salfacid. And then·OH again attacks benzene ring, C-N and C-S bond of the intermediate product, finally, SDZ is broken into SO42-, NO3-, NH4+, CO2 ect. Thus, we can concluded that the degradation of SDZ may have three pathway.
引文
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