Ciprofloxacin degradation in photo-Fenton and photo-catalytic processes: Degradation mechanisms and iron chelation

Ciprofloxacin(CIP)is a broad spectrum synthetic antibiotic drug of fluoroquinolones class.CIP can act as a bidentate ligand forming iron complexes during its degradation in the photoFenton process(PFP).This work investigates on PFP for the degradation of CIP to understand the formation mechanism and stability of iron complexes under ultraviolet(UV)-light illumination.A comparison was made with the UV-photocatalysis(UV/TiO_2)process where CIP doesn't form a complex.In PFP,the optimal dose of Fe~(2+)and H_2O_2were found to be 1.25 and10 mmol/L with pH of 3.5.An optimal TiO_2dose of 1.25 g/L was determined in the UV/TiO_2process.Maximum CIP removal and mineralization efficiency of 93.1%and 47.3%were obtained in PFP against 69.7%and 27.6%in the UV/TiO_2process.The mass spectra could identify seventeen intermediate products including iron-CIP complexes in PFP,and only seven intermediate products were found in the UV/TiO_2process with a majority of common products in both the processes.The proposed mechanism supported by the mass spectra bridged the routes of CIP cleavage in the PFP and UV/TiO_2process,and the decomposition pathway of Fe~(3+)-CIP chelate complexes in PFP was also elucidated.Both in PFP and UV/TiO_2processes,the target site of HO~·radical attack was the secondary-N atom present in the piperazine ring of the CIP molecule.The death of Escherichia coli bacteria was 55.7%and 66.8%in comparison to the control media after 45 min of treatment in PFP and UV/TiO_2process,respectively.     

Comparison of UV and UV-LED activated sodium percarbonate for the degradation of O-desmethylvenlafaxine

As an active metabolite of venlafaxine and emerging antidepressant, O-desmethylvenlafaxine (ODVEN) was widely detected in different water bodies, which caused potential harm to human health and environmental safety. In this study, the comparative work on the ODVEN degradation by UV (254 nm) and UV-LED (275 nm) activated sodium percarbonate (SPC) systems was systematically performed. The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis (14.99%) than UV direct photolysis (4.57%) due to the higher values of photolysis coefficient at the wavelength 275 nm. Significant synergistic effects were observed in the UV/SPC (80.38%) and UV-LED/SPC (53.57%) systems and the former exhibited better performance for the elimination of ODVEN. The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes, and the pseudo-first-order rate constant (k_obs) increased with increasing SPC concentration. Radicals quenching experiments demonstrated that both ·OH and CO₃·⁻ were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO₃·⁻ (1.58 × 10⁸ (mol/L)⁻¹ sec⁻¹) was reported for the first time based on competitive kinetic method. The introduction of HA, Cl⁻, NO₃⁻ and HCO₃⁻ inhibited the ODVEN degradation to varying degrees in the both processes. According to quantum chemical calculation, radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by ·OH. In addition, the oxidation of ODVEN may involve the demethylation, H-abstraction, OH-addition and C-N bond cleavage. Eventually, the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process, although the UV/SPC process possessed a higher removal rate of ODVEN.     

多点进水A/O组合工艺处理高速公路服务区污水

采用"多点进水A/O工艺+砂滤+活性炭过滤"联合工艺处理某高速公路新建服务区污水,处理能力500 m3/d,沉淀池出水水质达到《污水综合排放标准》(GB/T 8978-1996)中一级标准,最终出水水质达到《城市污水再生利用城市杂用水水质》(GB/T 18920-2002)的要求。实践证明,采用多点进水A/O组合工艺处理高速公路服务区污水是完全可行的,污水经处理后完全达标,可供类似工程借鉴和参考。     

Coastal changes in the Ebro delta: Natural and human factors

The development of the delta of the River Ebro (Ebre) has, during recent centuries, been controlled by both natural and man-induced factors. Deforestation by man of the Ebro drainage basin favoured a fast progradation of the deltaic system until this century, when many dams were constructed along the river Ebro and its tributaries. As the sediment load of the river has been retained behind the dams, the river sediment discharge has been drastically reduced and erosive processes have become dominant in the Ebro delta coastal area, changing it from a river-wave to a sea-wave-dominated coast. This situation leads to a reshaping of the nearshore delta area and a redistribution of the pre-existing beach sediment, and significant erosion has already occurred in some zones. If these conditions continue in the future, severe changes will take place in the Ebro delta, in addition to the effects of a relative sea level rise. The future development of this delta may be similar to that of abandoned deltaic lobes, but faster. The present study shows, how coastal changes generated by anthropogenic factors can be faster and more drastic than those induced only by natural factors.     

基于流域地形地貌特征的分布式汇流方法

以长江三峡区间沿渡河流域为例,采用HEC-HMS水文模型系统为模拟工具,基于流域下垫面特征和水动力条件提出了一种分布式单位线方法,并应用于降雨径流过程模拟。以自然分水线划分子流域,基于DEM数据和GIS工具提取河网水系特征。采用7种模型评估指标,分别从总量平衡,过程拟合,高水流量和低水流量4个角度评判模型的模拟效果及精度,并给出了模型模拟结果的量化统计指标。模拟结果表明:25场洪水中,洪峰流量相对误差小于20%的有80%,径流深相对误差小于20%的有96%,Nash-Sutcliffe效率系数大于0.8的有84%。由此可知,提出的分布式汇流方法可有效利用流域下垫面特征和GIS工具提取模型参数信息,适应于无资料流域的降雨径流过程模拟应用。     

大型再生水厂不同工艺的COD、TN和TP去除效果及其影响因素分析

以北京某大型再生水厂为研究对象,通过统计分析历史数据,系统研究了2008和2013年不同工艺(倒置A2/O工艺、A2/O工艺、A2/OMBR工艺)中主要污染物COD、TN和TP去除效果的年际、年内汛期、寒冷季和温暖季的变化特征,并分析了2013年这3种污染物去除效果变化的影响因素.结果表明,同2008年相比,2013年不仅进水的COD浓度升高,TN浓度和TP浓度降低,导致进水的碳/氮/磷比值从2008年的100∶14.5∶1.4升高到2013年的100∶10.1∶0.9,而且主要污染物去除效果均有明显改善,改善幅度依次为TPCODTN.年内变化特征表现为:汛期进水COD、TN和TP的浓度降低但波动加剧,它们的去除率降低,因此汛期出水COD稳定、TN浓度降低而TP浓度波动;温暖季进水COD、TN和TP的浓度高,它们的去除率有不同程度提高,因此温暖季出水的TN浓度波动较大、COD和TP浓度稳定.冗余分析(RDA)结果表明,一期倒置A2/O工艺的出水TN和TP浓度同步波动,主要受工况变化影响,脱氮除磷的碳源竞争是导致出水TN浓度降低、TP浓度升高的重要原因.二期A2/O工艺的出水COD浓度和TN浓度主要受进水水质波动影响.三期A2/O-MBR工艺的出水水质最稳定,膜运行性能至关重要.     

青岛大气气溶胶中铁的溶解度及其影响因素

大气气溶胶的干湿沉降带来的铁对海洋初级生产和固碳能力有着重要影响,但这种影响从根本上决定于沉降铁的溶解度.本文利用2012年12月在青岛连续采集的31个总悬浮颗粒物(TSP)样品,分析了其中微量元素Fe的总浓度和溶解态浓度,讨论了颗粒物浓度、气溶胶来源及酸化过程对Fe溶解度的影响.结果表明,气溶胶中Fe的总浓度和溶解态浓度分别为(3248±1683)ng·m-3和(43.3±16.4)ng·m-3,溶解度为0.57%~4.86%,平均为1.63%±1.02%.随着气溶胶中总Fe浓度的增加,Fe溶解度呈现规律性降低.气溶胶中Fe的溶解度与富集因子(EF)无相关关系,而与无机和有机酸性离子存在显著正相关关系.气团后向轨迹的聚类分析显示,观测期间,64.5%的气溶胶样品主要受北方沙尘源(DS)影响,35.5%的样品主要受到华北城市群等人为源(AS)影响.AS样品中Fe的溶解度平均为2.06%,高于DS样品中的1.36%.两组样品中Fe的EF值相当,但AS样品中酸性离子与溶解度的相关关系明显好于DS组,表明酸化过程可能是造成两组样品Fe溶解度差异的主要原因.     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide (COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations (R² > 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes (ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide(COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations(R2 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes(ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

An integrated methodology for environmental impacts and costs evaluation in industrial processes

The development of methods for process analysis has contributed to the improvement of production systems. In this context, many models and methodologies have been established in the literature in order to evaluate environmental performance of industrial processes, since it has become an important issue for society. However, few of them analyze environmental impacts and related costs simultaneously. So, this work presents an integrated methodology to perform this evaluation, based on Life Cycle Assessment (LCA) and Activity-Based Costing (ABC) principles. The proposed methodology was applied in a metallurgical industry in Brazil. As result, it allowed to identify the production process stages which have critical environmental impacts and greatest contribution to increase environmental costs of the company.