梯级水库群环境风险分析

为提高梯级水库群环境风险管理水平,加强流域生态环境保护,以溪洛渡-向家坝梯级水库为研究对象,基于灾害系统理论和系统动力学,对溪洛渡-向家坝梯级水库环境风险进行了系统梳理,辨识了梯级水库环境风险承载体、风险源、风险诱因,分析了环境风险传递机理,采用贝叶斯理论进行库区水体藻类爆发概率计算。结果表明:溪洛渡-向家坝梯级水库环境风险通过水流、电流、系统动力学流进行传播,并会影响到电站机组和水工建筑物的安全,由于水动力减弱和库区污染物排放,导致库区水体藻类爆发概率为2.42%,死鱼概率为1.21%,在此基础上,绘制环境风险传递拓扑图,并提出相应的环境风险管控措施。     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

Precursors and potential sources of ground-level ozone in suburban Shanghai

• Air masses from Zhejiang Province is the major source of O₃ in suburban Shanghai. • O₃ formation was in VOC-sensitive regime in rural Shanghai. • O₃ formation was most sensitive to propylene in rural Shanghai. A high level of ozone (O₃) is frequently observed in the suburbs of Shanghai, the reason for this high level remains unclear. To obtain a detailed insight on the high level of O₃ during summer in Shanghai, O₃ and its precursors were measured at a suburban site in Shanghai from July 1, 2016 to July 31, 2016. Using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and concentration weighted trajectories (CWT), we found that Zhejiang province was the main potential source of O₃ in suburban Shanghai. When the sampling site was controlled by south-western winds exceeding 2 m/s, the O₃-rich air masses from upwind regions (such as Zhejiang province) could be transported to the suburban Shanghai. The propylene-equivalent concentration (PEC) and ozone formation potential (OFP) were further calculated for each VOC species, and the results suggested that propylene, (m+p)-xylene, and toluene played dominant roles in O₃ formation. The Ozone Isopleth Plotting Research (OZIPR) model was used to reveal the impact of O₃ precursors on O₃ formation, and 4 base-cases were selected to adjust the model simulation. An average disparity of 18.20% was achieved between the simulated and observed O₃ concentrations. The O₃ isopleth diagram illustrated that O₃ formation in July 2016 was in VOC-sensitive regime, although the VOC/NO_x ratio was greater than 20. By introducing sensitivity (S), a sensitivity analysis was performed for O₃ formation. We found that O₃ formation was sensitive to propylene, (m+p)-xylene, o-xylene and toluene. The results provide theoretical support for O₃ pollution treatment in Shanghai.     

CWPO体系中污泥炭催化降解头孢氨苄废水

通过加入正丁醇以共沸蒸馏法对剩余污泥进行脱水,再对污泥进行干燥、焙烧和改性得到污泥炭催化剂.将污泥炭催化剂用于催化湿式过氧化氢氧化体系,处理头孢氨苄废水.采用响应面法中的中心组合设计实验,考察反应温度、初始pH和过氧化氢投加量对TOC降解率的影响,反应温度和过氧化氢投加量具有显著交互作用.在最佳实验条件下(T=50℃、pH=3.00、H_2O_2=0.071 mol·L~(-1)),TOC去除率为59%,接近预测的TOC去除率(60%),在95%的置信区间内,说明该模型可靠.SEM、TEM、TPD-MS、XPS和FT-IR等分析结果表明污泥炭表面存在纳米尺寸片状结构,这种结构中存在酚羟基、羰基、羧基等活性官能团和醌类结构,且ICP-OES、EDAX和~(57)Fe穆斯堡尔谱等分析结果表明,污泥炭中含有不同价态的Fe,能有效地催化过氧化氢分解,将头孢氨苄转化为苯甲酸、丁二酮等小分子物质,再进一步完全氧化.     

磺酰脲类除草剂的微生物降解研究进展

磺酰脲类除草剂属于高效、低毒、高选择性的新型除草剂,被广泛应用于水稻、玉米、小麦、大豆等田间杂草的防控,其用量也呈逐年增加的趋势,但其微量的除草剂残留易对后茬敏感作物产生药害.利用微生物降解土壤中的除草剂残留有望成为一种修复污染的有效方法.本文综述了近几年国内外筛选出的能够降解磺酰脲类除草剂菌株的来源和所属微生物类群,以及除草剂降解酶的研究进展,此外,对相关微生物对不同除草剂的降解途径也进行了简要介绍,最后提出了目前有待解决的问题并对未来该领域的研究趋势进行了展望,可为后续寻找高效的微生物降解菌种及利用基因工程法修复受污染的土壤、水源提供参考.     

全氟辛烷磺酸盐(PFOS)对半滑舌鳎(Cynoglossus semilaevis)免疫相关基因表达的影响

为了解全氟辛烷磺酸盐(perfluorooctane sulfonate, PFOS)暴露对半滑舌鳎(Cynoglossus semilaevis)免疫功能的影响,在实验室条件下,运用RT-PCR方法分析了PFOS暴露对半滑舌鳎热休克蛋白hsp70、hsp90、C型凝集素(c-type lectin)和细胞色素c氧化酶(cytochrome c oxidase, cox)等4种免疫相关基因表达水平的影响。实验测定了上述4种基因在半滑舌鳎肝、鳃、肠及肌肉4种不同组织中随时间(0、24 h、48 h、96 h和7 d)的表达变化情况。结果表明,在4种组织中,hsp70基因的表达与对照相比为上调,其中,肝组织hsp70基因的表达量显著高于其他各组织,且表达高峰值的出现也早于其他各组织;hsp90基因在肝和鳃组织中表达量随时间不同而波动,在肠组织中表达上调,在肌肉中表达显著下调;c-type lectin基因表达量与对照组相比表达显著下调或无明显差异;cox基因在肝组织和肠组织中表达下调,在鳃和肌肉中表达上调。上述研究结果表明,PFOS能引起免疫相关基因的表达变化,对半滑舌鳎具有潜在的免疫毒性。肝组织中各免疫基因对PFOS胁迫的响应高于其他组织。本研究可为阐明全氟辛烷磺酸盐对半滑舌鳎的免疫毒性提供基础数据。     

Seasonal trend of ambient PCDD/Fs in Tianjin City, northern China using active sampling strategy

The spatial concentrations, seasonal trends, profiles and congener pairs of ambient polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were investigated within a seasonally active sampling scheme during Jun 2008 and Jan 2009 in Tianjin City, northern China. The PCDD/F concentrations ranged 14.2-172 fg I-TEQ/m³ (average 69.3 fg I-TEQ/m³) in summer and (89.8-1.01) × 10³ fg I-TEQ/m³ (average 509 fg I-TEQ/m³) in winter, respectively, except for the E-waste dismantling site where much higher values were observed (1.04 × 10³ fg I-TEQ/m³ in summer and 7.123 × 10³ fg I-TEQ/m³ in winter). The results indicated a significantly seasonal trend with higher TEQ values in winter as compared with summer, which could be related to increased emission sources and seasonal variations of the atmospheric boundary layer height. 2,3,4,7,8-PeCDF was the dominant contributor to the total PCDD/F toxic equivalents, and 2,3,7,8-TCDD was detected at almost all the sampling sites in winter. Most of the similarly substituted PCDD/F congener pairs exhibited high correlations, suggesting that they might have similar environmental fate or sources. But different seasonal and spatial distributions of PCDD/F concentrations indicated that the emission sources might be intermittent.     

Effects of physical and chemical characteristics of surface sediments in the formation of shallow lake algae-induced black bloom

Surface sediments are closely related to lake black blooms. The dissolved oxygen （DO） distribution and its penetration depth in surface sediments as well as the migration and transformation of redox sensitive elements such as Fe and S at the sediment-water interface are important factors that could influence the formation of the black bloom. In this study, dredged and undredged sediment cores with different surface properties were used to simulate black blooms in the laboratory. The Micro Profiling System was employed to explore features of the DO and ∑H2S distribution at the sediment-water interface. Physical and chemical characteristics in sediments and pore waters were also analyzed. The results showed that sediment dredging effectively suppressed the black blooms. In the undredged treatment, DO penetration depth was only 50 μm. Fe^2＋ concentrations, ∑H2S concentrations, and ∑H2S production rates were remarkably higher in surface sediments and pore waters compared to control and dredged treatments. Furthermore, depletion of DO and accumulation of Fe^2＋ and ∑H2S in surface sediments and pore waters provided favorable redox environments and necessary material sources for the blooms. The study results proved that physical and chemical characteristics in surface sediments are important factors in the formation of the black bloom, and could provide scientific guidance for emergency treatment and long-term pre-control of black blooms.     

轻型汽油车CH4和N2O排放因子研究

我国的机动车温室气体排放研究多集中于CO2排放,而CH4和N2O排放的相关研究主要是依据欧美开发的模型进行的,缺乏CH4和N2O实车测试的研究.本研究选取22辆轻型汽油车,利用底盘测功机开展了整车台架测试和采样分析,获得了车辆在NEDC工况下的CH4和N2O排放因子.结果表明,国Ⅰ~国Ⅳ阶段轻型汽油车CH4平均排放因子分别为0.048、0.048、0.038和0.028 g·km-1,N2O则分别为0.045、0.039、0.026和0.021 g·km-1.在轻型汽油车单车排放的CO2、CH4和N2O三类温室气体(以CO2当量计)中,CH4和N2O排放的分担率均随排放标准的加严而逐渐降低,其中CH4排放在温室气体排放中不足0.5%,N2O排放分担率在3.03%~6.35%之间.因此,排放标准的加严可以有效减少CH4和N2O的排放,以减缓机动车排放带来的温室效应.