Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.     

Thioarsenate formation upon dissolution of orpiment and arsenopyrite

Thioarsenates were previously determined as dominant species in geothermal and mineral waters with excess sulfide. Here, we used batch leaching experiments to determine their formation upon weathering or industrial leaching of the arsenic-sulfide minerals orpiment (As₂S₃) and arsenopyrite (FeAsS) under different pH and oxygen conditions. Under acidic conditions, as expected based on their known kinetic instability at low pH, no thioarsenates formed in either of the two mineral systems. Under neutral to alkaline conditions, orpiment dissolution yielded mono-, di- and trithioarsenate which accounted for up to 43-55% of total arsenic. Thioarsenate formation upon arsenopyrite dissolution was low at neutral (4%) but significant at alkaline pH, especially under suboxic to sulfidic conditions (20-43%, mainly as monothioarsenate). In contrast to orpiment, we postulate that recombination of arsenite and sulfide in solution is of minor importance for monothioarsenate formation during alkaline arsenopyrite dissolution. We propose instead that hydroxyl physisorption lead to formation of As-OH-S surface complexes by transposition of hydroxyl anions to arsenic or iron sites. Concurrently formed ironhydroxides could provide re-sorption sites for the freshly released monothioarsenate. However, sorption experiments with goethite showed slower sorption kinetics of monothioarsenate compared to arsenite, but comparable with arsenate. The discovery that thioarsenates are released by natural weathering and industrial leaching processes and that, once they are released, have a higher mobility than the commonly-investigated species arsenite and arsenate requires future studies to consider them when assessing arsenic release in sulfidic natural or mining-impacted environments.     

活性艳橙K-7R分子印迹聚合物微球的制备及结合特性研究

以微米级聚苯乙烯微球为种球,活性艳橙K-7R为模板分子,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用单步溶胀聚合法在水相中制得了分子印迹聚合物微球(MIPs),并用平衡吸附实验研究了其吸附性能。通过Scatchard分析,结果表明,MIPs在识别K-7R过程中存在两类结合位点,高亲和力结合位点的平衡离解常数Kd1=14.855μmol/L,最大结合量Qmax1=1.282μmol/g;低亲和力结合位点的平衡离解常数Kd2=70.939μmol/L,最大结合量Qmax2=3.930μmol/g。该MIPs对K-7R有较高的亲和性和选择性。     

纳米生态基对水产养殖污水的处理效果

采用三因子四水平的正交设计,实验研究了纳米生态基在不同温度、溶解氧和水力停留时间下对水产养殖污水的处理效果,确定了纳米生态基处理养殖污水的最佳条件。结果表明,含氨氮和亚硝氮浓度较高的模拟养殖污水用纳米生态基挂膜,所需时间约为22 d。纳米生态基对氨氮的去除效果明显,平均去除率达到93.5%。对氨氮去除率的影响程度,水力停留时间>温度>溶解氧。当温度为30℃,DO为5.43 mg/L,HRT为0.33 h时,纳米生态基对氨氮的处理能力最佳,去除率达到94.6%。纳米生态基对亚硝氮的平均去除率为69.3%。对亚硝氮去除率的影响程度,水力停留时间>溶解氧>温度。当温度为21℃,DO为6.40 mg/L,HRT为0.33 h时,纳米生态基对亚硝氮的处理能力最佳,去除率为71.5%。纳米生态基处理养殖污水的最佳条件:温度为30℃,DO为6.40 mg/L,HRT为0.33 h。     

不同填料载体生物膜对微囊藻毒素的去除效果

利用自行设计的生物膜培养装置,通过对4种不同填料载体进行连续曝气循环培养生物膜,对湖水中的溶解态微囊藻毒素(MCs)的去除作用进行了研究。结果表明,填料载体上生物膜从形成到稳定大约需要3周;生物膜形成后对MCs的去除效率由高到低的顺序是:颗粒活性炭柱>多密孔球型滤料柱>塑料悬浮填料柱>陶瓷滤球柱。在实验水质条件下,当水力停留时间(HRT)=5 h,进水MCs浓度为21.5～47.25μg/L时,颗粒活性炭、多密孔球型滤料柱对MCs的去除率最高可达100%,塑料悬浮填料柱对MC-LR和MC-RR的去除率分别为70%和88%。当HRT=2.5 h时,塑料悬浮填料柱对MC-RR的去除率为MC-LR的2倍。生物膜对MCs的降解效果随温度(5～20℃)和溶解氧的升高而增加。塑料悬浮填料作为合适的生物膜挂膜填料载体对水源水的生物预处理具有良好的应用前景。     

高效氨氧化菌群富集、驯化及其动态变化规律分析

利用选择性培养基对氨氧化菌群进行了连续驯化,得到了氨氮去除效率稳定的氨氧化菌群。采用平板菌落计数法结合聚合酶链式反应-变性梯度凝胶电泳(PCR-DGGE)技术考察了氨氧化菌群在连续传代过程中数量及群落结构的动态变化,并考察了pH值、碳源(HCO3-)浓度和氨氮浓度等因素对氨氧化菌群去除氨氮效率的影响。结果表明,通过连续驯化,氨氧化菌的比例由最初的1.8%提高到了31.3%。在碳源浓度为1.5 mg/L,NH4+-N初始浓度为200 mg/L,pH值为8的条件下,菌群对氨氮的去除率达99%以上。     

晚期垃圾渗滤液的部分亚硝化

利用实验室小试SBR在(33±1)℃的条件下,通过动态调控溶氧浓度(DO)(2～7 mg/L)和水力停留时间(2～5 d),经过130 d的运行成功启动了晚期垃圾渗滤液(NH4+-N含量1 227～2 133 mg/L)的部分亚硝化,使出水NO2--N∶NH4+-N稳定维持在1∶1左右,为后续的厌氧氨氧化工艺创造了进水条件。利用实时荧光定量PCR研究启动过程中的特异微生物氨氧化细菌的含量变化表明,氨氧化细菌的含量与NO2--N的生成速率和出水NO2--N稳定性有着显著相关性。     

响应曲面法优化复合絮凝剂的制备工艺

为了提高染料废水中COD和色度的去除效果,采用响应曲面法对聚硅酸类新型复合絮凝剂的制备工艺进行了优化实验研究。在单因素实验基础上采用Box-Behnken Design(BBD)实验设计方法,设计出了影响染料废水处理效果的3因素3水平共15组实验,其中n(Fe+Al):n(Si)的摩尔比为4～6,n(B+Mg):n(Si)的摩尔比为0.3～0.7,熟化时间为1～3 d。根据15组实验结果,以COD去除率和色度去除率为响应值分别建立了二次多项式响应曲面模型。模型优化结果显示,在n(Fe+Al):n(Si)摩尔比为5∶1,n(B+Mg):n(Si)为0.5∶1,熟化时间为2 d的条件下,制备得到的新型复合絮凝剂聚硅酸铝铁硼镁具有最佳的絮凝处理性能和脱色效果,能有效去除染料废水中的COD和色度,其中出水色度接近于0,COD的去除率达到87.65%,模型验证实验进一步验证了本文所建立的响应曲面法在复合絮凝剂制备工艺优化中的有效性。     

凹凸棒石粘土固定辣根过氧化物酶处理含酚废水

采用凹凸棒石粘土、可溶性淀粉和工业水玻璃作为制备凹凸棒石粘土基颗粒的材料,并将制备的凹凸棒石粘土基颗粒进行改性,得到了改性后的凹凸棒石基多孔材料,并将其作为固定辣根过氧化物酶的载体,再应用于含酚废水的处理研究,取得了良好的效果。实验结果表明,辣根过氧化物酶的最佳固定化条件为:单位酶活载体量1 mg、固定化时间1.5小时、固定pH值5。并且在固定化酶循环使用6次后,苯酚去除率仍能达到62.3%。     

Fenton 法降解抗生素磺胺间甲氧嘧啶钠

应用Fenton高级氧化技术降解水溶液中抗生素磺胺间甲氧嘧啶钠(SMMS),系统探讨了起始pH、CSMMS、CFe2+、CH2O2和温度等因素对SMMS降解效果的影响。结果表明:CSMMS=4.53 mg/L,pH=4.0,CH2O2=0.49 mmol/L,CFe2+=19.51μmol/L,T=25℃为最佳反应条件。在最佳条件下,87.4%的SMMS可以在120 min内降解。反应动力学研究表明Fenton氧化降解SMMS分为两个阶段,快速反应阶段和慢速反应阶段,并建立了两阶段动力学模型,模型拟合结果较好。研究结果为含有SMMS的污废水处理提供了基础数据和科学参考。