可见光响应型CuO/BiVO4的光催化活性研究

采用浸渍法制备了CuO/BiVO4光催化剂,通过X射线衍射(XRD)、热重/差示扫描量热(TG/DSC)和傅立叶红外光谱(FTIR)对其进行了表征,并在可见光照射下考察了其光催化氧化亚甲基蓝(MB)的动力学特性。结果表明,Cu的掺杂并未改变BiVO4的晶型结构;Cu(NO3)2/BiVO4在热处理(30～300℃)过程中,NO3-已经完全分解,Cu最终以CuO的形式存在于CuO/BiVO4光催化剂体系中;掺杂不同量Cu的CuO/BiVO4中的Cu2+/Bi+(摩尔比)实测值与理论值相近,该系列光催化剂的合成过程具有较高的可信度;在可见光照射下,CuO/BiVO4光催化降解MB反应符合表观一级反应动力学特征;当Cu2+/Bi+为0.050时,反应动力学速率常数(k)达到最高值(0.4334h-1),此时的k比单体BiVO4作用下的提高了1.04倍;由于异质结的存在,CuO/BiVO4与单体BiVO4相比,电子和空穴的利用率大大增加,使得CuO/BiVO4的光催化活性较单体BiVO4有了大幅度提高。     

生物法-人工湿地组合工艺处理小城镇混合污水研究

为适应小城镇污水处理高效、低耗、管理简单的要求,开展了生物法(水解酸化/生物接触氧化)-人工湿地组合工艺(A/BCO-CW)处理小城镇片区混合污水的研究。结果表明,A/BCO系统在停留时间为3～6 h条件下,对悬浮物和有机物有高的去除效率,COD、BOD5和TSS去除率分别达到63.1%、67.7%和66.2%,避免了人工湿地堵塞和提高处理效率,减少了所需湿地面积44%。全年运行结果表明,在0.30～0.59 m/d水力负荷率下,垂直流-表面流-水平潜流人工湿地组合系统对COD、BOD5和TSS平均去除负荷达9.4、5.1和7.2 g/(m2.d)(42%、71.2%和85.2%);COD、BOD5去除速率常数为74.6±12.1 m/y、166±30.5 m/y,这些数值均处于文献中k值范围的高量程内。A/BCO-人工湿地系统对COD、BOD5和TSS具有好的处理效果,出水水质能够稳定达到《地表水环境质量标准》(GB 3838-2002)的IV类水标准,2种处理方法有效组合起来,所开发的低成本、高效率、可持续运行的城镇废水处理组合系统,将会在实际应用尤其是高有机负荷污水处理中发挥良好效用。     

混凝与Fenton联用处理垃圾渗滤液的效能及成本

为对混凝/Fenton工艺与Fenton/混凝工艺处理垃圾渗滤液的效果和成本进行比较,分别对年轻渗滤液和老龄渗滤液原液按照混凝/Fenton工艺与Fenton/混凝工艺2种技术路线进行处理。实验结果表明,Fenton试剂对年轻垃圾渗滤液和老龄垃圾渗滤液COD去除率最高的反应条件为pH=3.5、H2O2和Fe2+的摩尔比为6、H2O2和渗滤液原液的COD质量比为3、反应时间4 h;在PAC与渗滤液原液的COD质量比为0.6时,PAC混凝对渗滤液原液的COD去除率最高。在对渗滤液COD去除率最高的Fenton反应和PAC混凝反应条件下,混凝/Fenton工艺对年轻渗滤液和老龄渗滤液的COD去除率分别为90.56%和86.56%;Fenton/混凝工艺对年轻渗滤液和老龄渗滤液的COD去除率分别为89.99%和85.99%,2种技术路线对渗滤液COD的去除率相差不大,但先PAC混凝后Fenton氧化工艺比先Fenton后混凝工艺每t节省62.6元,是更优化的渗滤液处理工艺。     

TiO_2/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩(EP)为载体的TiO2催化剂(TiO2/EP),对使用较为广泛的抗生素磺胺嘧啶(SDZ)进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子(HCO3-、SO42-和Cl-)和腐殖酸(HA)对SDZ降解效果的影响。结果表明:SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm2,反应时间为45 min时,SDZ的降解率达到96%;HCO3-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO42-和Cl-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

Solution by dilution?—A review on the pollution status of the Yangtze River

The Yangtze River has been a source of life and prosperity for the Chinese people for centuries and is a habitat for a remarkable variety of aquatic species. But the river suffers from huge amounts of urban sewage, agricultural effluents, and industrial wastewater as well as ship navigation wastes along its course. With respect to the vast amounts of water and sediments discharged by the Yangtze River, it is reasonable to ask whether the pollution problem may be solved by simple dilution. This article reviews the past two decades of published research on organic pollutants in the Yangtze River and several adjacent water bodies connected to the main stream, according to a holistic approach. Organic pollutant levels and potential effects of water and sediments on wildlife and humans, measured in vitro, in vivo, and in situ, were critically reviewed. The contamination with organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans, polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and others, of water and sediment along the river was described. Especially Wuhan section and the Yangtze Estuary exhibited stronger pollution than other sections. Bioassays, displaying predominantly the endpoints mutagenicity and endocrine disruption, applied at sediments, drinking water, and surface water indicated a potential health risk in several areas. Aquatic organisms exhibited detectable concentrations of toxic compounds like PCBs, OCPs, PBDEs, and PFCs. Genotoxic effects could also be assessed in situ in fish. To summarize, it can be stated that dilution reduces the ecotoxicological risk in the Yangtze River, but does not eliminate it. Keeping in mind an approximately 14 times greater water discharge compared to the major European river Rhine, the absolute pollution mass transfer of the Yangtze River is of severe concern for the environmental quality of its estuary and the East China Sea. Based on the review, further research needs have been identified.     

Bioaccessibility of polychlorinated biphenyls in workplace dust and its implication for risk assessment

Human exposure to bioaccessible PCBs via indoor dust is limited around the world. In the present study, the workplace dust sample from commercial office, hospital, secondary school, shopping mall, electronic factory and manufacturing plant were collected from Hong Kong for PCBs analyses. Total PCBs concentrations ranged from 46.8 to 249 ng g⁻¹, with a median of 107 ng g⁻¹. Manufacturing plant showed the highest concentration among all of sampling sites. PCB 77 was found as the dominant congeners. The bioaccessibility of PCBs in small intestinal juice ranging from 8.3% to 26.0% was significantly higher than that in gastric condition, ranging from 4.8% to 12.4%. In addition, significant negative correlations (p < 0.05) were observed between K_OW and bioaccessibility for all workplace dust samples. Risk assessment indicated that the averaged daily dose of dioxin-like PCBs via non-dietary intake of workplace dust, considering the bioaccessibility of PCBs, were much lower than the TDI of dioxins (2.3 pg WHO-TEQ kg bw⁻¹ d⁻¹) established by Joint FAO/WHO Expert Committee on Food Additives.     

Hexabromocyclododecanes in surface sediments and a sediment core from Rivers and Harbor in the northern Chinese city of Tianjin

In the present study, hexabromocyclododecanes (HBCDs) were investigated in the sediment from Haihe River (HR), Dagu Dainage Canal (DDC) and Tianjin Harbor (TH) at Bohai Bay using a total of 51 samples of surface sediments and a sediment core collected from May to September in 2010, and its diastereomer- and enantiomer-specific profiles were analyzed. The concentration of total HBCDs were generally high, with mean value and ranges of 31.0 and 1.35–634 ng g^?1 dw, respectively. The contamination followed the order of TH > DDC > HR. Higher levels (up to 634 ng g^?1 dw) occurred in the lower reach of HR and DDC located in an industrial area of Tianjin. This is the first time to report so high concentration of HBCDs in sediment in Southeast Asia. The γ-diastereomer dominated in most samples (44 out of 51), and this is in agreement with the diastereomer distribution pattern in industrial products, while α-HBCD was the dominant diastereomer in the other seven samples. However, only few samples exhibited γ-diastereomer ratio similar to that (75–89%) in technical products, indicating the inter-transformation and variable degradation of the different isomers. The high ratio of γ-diastereomer could be used as an indicator for fresh contamination input. Enantiomeric factors (EFs) of HBCD isomers in most of the samples were statistically different from technical products (p < 0.05), showing a trend of more easily enrichment of the (?)-HBCD-enantiomer compared to the (+)-HBCD-enantiomer. The δ- and ε-diastereomers were frequently detected but at low level. The HBCDs in the sediment core showed several peaks, and the greatest value occurred in 2005, when a plastic manufacture plant using HBCD was set up nearby.     

Hexabromocyclododecanes in limnic and marine organisms and terrestrial plants from Tianjin,China: Diastereomer- and enantiomer-specific profiles,biomagnification, and human exposure

To interpret the distribution of hexabromocyclododecanes (HBCDs) in various organisms, we measured the concentrations and diastereomer and enantiomer profiles of HBCDs in 21 different species of limnic and marine cohorts from Tianjin, China. The concentration ranges of HBCDs in limnic and marine organisms were 64.3–1111 ng g⁻¹ lw and 85.5–989 ng g⁻¹ lw, respectively. Living habitat and feeding habits had important impacts on HBCD diastereomer distribution. Most of the species appeared to preferentially select (+)-α-, (−)-β- and (−)-γ-HBCD. There is a tendency that the total and α-HBCDs were magnified as trophic level increased with trophic magnification factors (TMFs) around 2. The concentrations of HBCDs in the limnic and marine fishes were highest in the liver, followed by the gill, skin, and muscle. In terrestrial plants, the highest concentrations of HBCDs were observed in the leaf, followed by the root and the rhizosphere soil. Plants showed enantioselectivity for HBCD enantiomers, which varied with plant species and organs (leaf vs. root) of the same plant. Higher estimated daily intakes (EDIs) of HBCDs were observed from fish than from wheat.     

Effect of copper(II) on biodegradation of benzo[a]pyrene by Stenotrophomonas maltophilia

Benzo[a]pyrene (BaP) biodegradation by Stenotrophomonas maltophilia was studied under the influence of co-existed Cu(II) ions. About 45% degradation was achieved within 3 d when dealing with 1 mg L^?1 BaP under initial natural pH at 30 °C; degradation reached 48% in 2 d at 35 °C. Efficacy of BaP biodegradation reached the highest point at pH 4. In the presence of 10 mg L^?1 Cu(II) ions, the BaP removal ratio was 45% on 7th day, and maintained stable from 7 to 14 d at 30 °C under natural pH. The favorable temperature and pH for BaP removal was 25 °C and 6.0 respectively, when Cu(II) ions coexisted in the solutions. Experiments on cometabolism indicated that S. maltophilia performed best when sucrose was used as an additional carbon source. GC–MS analysis revealed that the five rings of BaP opened, producing compounds with one or two rings which were more bioavailable.     

潜流人工湿地水力学特性及工程设计

以净化低污染水体的潜流人工湿地水力学特性工程设计为重点,系统开展了室内外实验研究,并利用Peelet数分析了水平潜流人工湿地碎石床渗流返混程度。结果表明,潜流人工湿地集水花管孔口出流计算、基质填料内渗流计算、碎石床平均水力停留时间计算可分别借鉴薄壁孔口恒定淹没出流、线性或非线性渗流、活塞流理论;但受工程实际条件及运行淤堵等影响,工程实测结果均小于理论计算值。基于室内外实验成果,提出一套包括集配水系统水力计算、填料内渗流计算、平均水力停留时间计算在内的潜流人工湿地水力学特性计算方法和参数选择,可为人工湿地技术的工程设计提供借鉴。