苯并芘对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物对长江三峡库区上游特有珍稀鱼类的环境风险,本实验以稀有鮈鲫为对象,研究了低剂量多环芳烃(PAHs)暴露而引起的内分泌干扰效应.将成年稀有鮈鲫暴露于不同浓度(0、0.1、0.3、1.0和3.0μg·L-1)的苯并芘(Ba P)中28 d,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与繁殖相关基因的表达.结果显示:在雌鱼中,Ba P暴露后,睾酮(T)的含量显著升高,雌二醇(E2)的水平显著下降并改变了T/E2的比值;在雄鱼中,T和E2的含量都显著下降.雌雄鱼性激素的改变可能与类固醇合成相关基因(Cyp17、Cyp19a)表达量的改变有关.Ba P暴露显著抑制了雌雄鱼肝脏中卵黄蛋白原(VTG)基因的表达.以上检测到的激素或者基因表达的改变主要发生在高剂量(3.0μg·L-1)Ba P暴露下,而长江上游库区水体中多环芳烃含量较低(100 ng·L-1),因此推测,库区存在的多环芳烃不会对三峡库区上游水体中的鱼类产生内分泌干扰效应.     

PBDEs的来源特征、环境分布及污染控制

多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)生产应用、环境分布与生态风险之间的关系将如何影响我国的未来,具体涉及到工业、环境、健康、人类繁衍等的社会问题.由于PBDEs阻燃效率高,热稳定性好,价格便宜,作为添加剂被广泛应用在电子、电器、化工、交通、建材、纺织、石油等领域的阻燃产品中.PBDEs进入环境后迁移扩散并富集于沉积物和生物体内,进入人体后引起肝脏毒性、内分泌干扰、神经毒性和生育能力下降等而危害人类的健康.基于此,从生产应用、品种生产量、分子的物理化学特性以及毒性等的文献数据分析了PBDEs的来源特征与环境危害,分析这些性质对环境分布与污染控制的基础支持关系;从沉积物、水体、大气、水生生物、人体5个方面考察了PBDEs的环境本底浓度变化、分配关系、迁移规律、时间效应,分析了生产、应用与扩散的多因素影响关系,发现全球性PBDEs污染物蔓延的现象,沉积物是主要的归趋场所,室内空气中的浓度远高于室外,水中浓度较低,水生生物和人体均能富集PBDEs,通过饮食、母乳和呼吸摄入,可实现代际传播,污染的分布呈现介质与区域的不同特征;污染控制需要考虑点源技术与面源修复的联合,结合PBDEs的物理性质、分子结构及其化学特性,统计分析了微生物法、光化学降解法和零价铁还原法的原理及其有效性,根据PBDEs在产品中存在与分布的特点,提出收集-分离-富集-超临界催化还原和氧化毁毒的工艺,针对实际环境(以电子垃圾塑料和流域水体及沉积物为对象)中的PBDEs进行回收或处理,结合材料如催化剂的应用,从动力学和热力学方面提高PBDEs无害化的效率.最后,从生产管理、环境监测、风险评价、技术集成等方面提出了未来的努力方向.     

雄黄矿区不同砷污染土壤中微生物群落结构及碳源利用特征

土壤砷污染是我国乃至世界范围内比较严重的环境问题.有关砷污染的生态毒理效应有很多研究,但对砷污染土壤中微生物群落的关注相对较少.本文以我国湖南省石门县雄黄矿地区长期砷污染土壤为例,采用PLFA及BIOLOG微平板技术考察了7个砷(As)污染程度不同的样点以及一个对照样点土壤微生物群落结构及碳源利用特征.结果发现,雄黄矿区存在多种重金属复合污染,除As含量较高以外,镉(Cd)和镍(Ni)的含量也超过了国家土壤环境质量三级标准.雄黄矿区土壤微生物的群落结构受到土壤有机碳(SOC)、有效磷(AP)、p H以及镁(Mg)、Cd、铁(Fe)、铜(Cu)含量的显著影响.各样点土壤微生物群落均以细菌为主,占微生物总量的71.54%~80.66%,真菌次之,放线菌最少.雄黄矿区土壤中的有效砷对微生物造成了较严重的胁迫.严重砷污染降低了微生物对于碳源利用的多样性以及均匀度.各样点微生物对于碳源的利用也表现出明显的差异.31种碳源中微生物利用较多的只有7类,分别属于糖类、胺类、羧酸类与多聚物,并且以糖类为主.     

我国生物质气化发电行业综合风险评价

针对我国生物质气化发电行业的现状,总结诸多风险的影响因素,建立了我国生物质气化发电行业综合风险评价体系。该评价体系主要包括5个一级风险影响因素:市场风险、技术风险、安全风险、管理风险、环境风险,每个一级影响因素包括4个二级风险影响因素。由层次分析法获得各个一级影响因素和二级影响因素的权重值,根据所构建的评价集和评分标准,结合模糊综合评价法对我国生物质气化发电行业现状的综合风险等级做定量定性分析。综合风险评价研究结果表明,生物质气化发电行业处于"较高"的风险等级,与实际情况相符。综合风险评价体系的构建合理,所建立的评价方法以及相应对策分析可为决策者提供参考依据。     

Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (·OH) and singlet oxygen (¹O₂) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of UOH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and ¹O₂. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.     

Mobility and sulfidization of heavy metals in sediments of a shallow eutrophic lake,Lake Taihu,China

The technique of DGT (diffusive gradients in thin films) using three diffusive gel thicknesses was applied to estimate the mobility and bioavailability of heavy metals in sediments and porewater of Lake Taihu, China. The DGT results showed significantly positive correlations between Co, Pb, Cd and Mn, and Ni and Fe concentrations in porewater. Cu and Zn showed a significantly negative correlation with Mn, due to Cu combination with carbonates and Zn derived from agricultural pollution, respectively. The rank order of average concentrations of Co, Ni and Cd at each station was DGT_1.92 > DGT_0.78 > DGT_0.39, suggesting stronger resupply from sediments to porewater when using thicker diffusive gels. Comparing centrifugation and DGT measurements, Co, Ni and Cd are highly labile; Mn and Fe are moderately labile; and Cu, Zn and Pb are slightly labile. The variations of AVS concentrations in sediment cores indicate that metal sulfides in deeper layers are easily diffused into surface sediments.     

Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.