碘离子对次氯酸氧化一价铊动力学影响及机理研究

铊(Tl)是一种在环境水体中广泛存在的痕量重金属,由于其对生物体毒性巨大,国家和地方高度重视铊污染防治,并将其作为优先监测的重金属污染物之一。氧化法是一种常用并且有效的除铊方法,该方法通过将一价铊(Tl (I))预氧化为更容易沉积的三价铊(Tl (Ⅲ))来实现总铊的去除,但容易受到水体中卤素离子的影响。本研究以水处理中常用的次氯酸钠(NaOCl)作为典型氧化剂,通过采用ABTS分光光度法检测生成Tl (Ⅲ)的浓度变化,考察了环境中常见的卤素碘离子对Tl (I)在这种典型氧化过程动力学中的影响,并结合动力学模型对其机理进行了探究。结果表明,在HOCl氧化过程中,碘离子的加入在pH为6.0、7.0和8.0时均表现出了促进Tl (I)氧化的现象,其中碘离子浓度在高于100 μmol/L时才有明显的催化氧化作用,且在100～1 000 μmol/L浓度范围内反应速率随着碘离子浓度升高氧化速率加快。在酸性和中性条件下500 μmol/L碘离子催化HOCl氧化Tl (I)符合假一级动力学过程,且随着pH的升高反应速率常数逐渐降低。推测碘离子的催化氧化作用为碘离子被次氯酸氧化后,产生具有更强氧化性的次碘酸进而继续氧化Tl (I)。本研究探究了在次氯酸氧化Tl (I)过程中,以碘离子为代表的卤素离子的存在对氧化过程的影响,突出了碘离子在影响Tl (I)氧化动力学中的关键作用。这对于完善铊的氧化还原性质以及评估含卤水中铊的去除策略,保障饮用水安全具有重要意义。     

Effects of humic acid and surfactants on the aggregation kinetics of manganese dioxide colloids

The aggregation of common manganese dioxide (MnO₂) colloids has great impact on their surface reactivity and therefore on their fates as well as associated natural and synthetic contaminants in engineered (e.g. water treatment) and natural aquatic environments. Nevertheless, little is known about the aggregation kinetics of MnO₂ colloids and the effect of humic acid (HA) and surfactants on these. In this study, the early stage aggregation kinetics of MnO₂ nanoparticles in NaNO₃ and Ca(NO₃)₂ solutions in the presence of HA and surfactants (i.e., sodium dodecyl sulfate (SDS), and polyvinylpyrrolidone (PVP)) were modeled through time-resolved dynamic light scattering. In the presence of HA, MnO₂ colloids were significantly stabilized with a critical coagulation concentration (CCC) of ~300 mmol·L^-1 NaNO₃ and 4 mmol·L^-1 Ca(NO₃)₂. Electrophoretic mobility (EPM) measurements confirmed that steric hindrance may be primarily responsible for increasing colloidal stability in the presence of HA. Moreover, the molecular and/or chemical properties of HA might impact its stabilizing efficiency. In the case of PVP, only a slight increase of aggregation kinetics was observed, due to steric reactions originating from adsorbed layers of PVP on the MnO₂ surface. Consequently, higher CCC values were obtained in the presence of PVP. However, there was a negligible reduction in MnO₂ colloidal stability in the presence of 20 mg·L^-1SDS.     

纳米颗粒对淡水藻类生长的影响:毒性机制与复合毒性

近年来,纳米颗粒在生活、工业生产中的应用日益广泛,而这些纳米颗粒的应用引起的一系列环境问题越来越被密切关注.纳米材料在使用过后不可避免地会释放到水环境中,不仅会影响水生生物的生长代谢,也会污染水体,影响水源水质.而藻类作为水生食物链的初级生产者,对于纳米颗粒在水环境中的积累和迁移起着至关重要的作用.本文首先总结了不同种类的纳米颗粒对水环境中不同藻类生长代谢的影响和相关的毒性机制,包括破坏细胞完整性、氧化应激胁迫、破坏光合系统、基因水平异常和有毒物质的释放等.其次,系统总结了纳米颗粒表面特性(如粒径、晶型、表面电荷、亲疏水性、光敏性、表面涂覆、老化和纳米颗粒的均相与非均相等)、水环境影响因素(如自然有机物质、环境胶体、离子强度、pH、硬度、光照和温度等)和藻类胞外聚合物对纳米材料毒性的影响.最后,还综述了水环境中关键污染物和纳米颗粒对藻类的复合毒性.对于纳米颗粒对水环境中藻类生长的毒性作用、影响机制以及复合毒性的系统总结,有利于全面了解纳米颗粒的环境行为和生物毒性.     

黄淮地区纳滤膜苦咸水软化分离性能研究

针对我国黄淮地区华北山前冲积平原与中部冲积平原交接部位的模拟苦咸水,构建纳滤(NF)膜法软化系统,考察了跨膜压差(0.6~2.1 MPa)、进水端切向流速(0.09~0.38 m/s)和进水温度(7~35 ℃)等操作条件对NF膜软化分离性能的影响。结果表明:在跨膜压差为1.2 MP,进水端切向流速为0.28 m/s,进水温度为15 ℃时,NF膜软化系统有较高的膜产水通量〔52.04 L/(m ²·h)〕,对主要成垢离子Ca ²⁺、Mg ²⁺、$CO_{3}^{2-}$和$SO_{4}^{2-}$的去除率分别达44.13%、73.72%、81.05%和99.13%,对总硬度的平均去除率达53.31%,NF膜有良好的软化性能;随着跨膜压差、进水端切向流速的增加及进水温度的下降,NF膜产水的pH逐渐降低,而浓水的pH呈逐渐升高的趋势。     

Release of deposited MnO2 nanoparticles from aqueous surfaces

Changes in solution chemistry and transport conditions can lead to the release of deposited MnO₂ nanoparticles from a solid interface, allowing them to re-enter the aqueous environment. Understanding the release behavior of MnO₂ nanoparticles from naturally occurring surfaces is critical for better prediction of the transport potential and environmental fate of MnO₂ nanoparticles. In this study, the release of MnO₂ nanoparticles was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D), and different environmental surface types, solution pH values and representative macromolecular organics were considered. MnO₂ nanoparticles were first deposited on crystal sensors at elevated NaNO₃ concentrations before being rinsed with double-deionized water to induce their remobilization. The results reveal that the release rate of MnO₂ depends on the surface type, in the decreasing order: SiO₂ > Fe₃O₄ > Al₂O₃, resulting from electrostatic interactions between the surface and particles. Moreover, differences in solution pH can lead to variance in the release behavior of MnO₂ nanoparticles. The release rate from surfaces was significantly higher at pH 9.8 that at 4.5, indicating that alkaline conditions were more favorable for the mobilization of MnO₂ in the aquatic environment. In the presence of macromolecular organics, bovine serum albumin (BSA) can inhibit the release of MnO₂ from the surfaces due to attractive forces. In presence of humic acid (HA) and sodium alginate (SA), the MnO₂ nanoparticles were more likely to be mobile, which may be associated with a large repulsive barrier imparted by steric effects.     

Impact of dissolved oxygen on the production of nitrous oxide in biological aerated filters

Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and microelectrode technology were employed to evaluate the Nitrous oxide (N₂O) production in biological aerated filters (BAFs) under varied dissolved oxygen (DO) concentrations during treating wastewater under laboratory scale. The average yield of gasous N₂O showed more than 4-fold increase when the DO levels were reduced from 6.0 to 2.0 mg?L^–1, indicating that low DO may drive N₂O generation. PCR-DGGE results revealed that Nitratifractor salsuginis were dominant and may be responsible for N₂O emission from the BAFs system. While at a low DO concentration (2.0 mg?L^–1), Flavobacterium urocaniciphilum might play a role. When DO concentration was the limiting factor (reduced from 6.0 to 2.0 mg?L^–1) for nitrification, it reduced NO ₂ ^- -N oxidation as well as the total nitrification. The data from this study contribute to explain how N₂O production changes in response to DO concentration, and may be helpful for reduction of N₂O through regulation of DO levels.

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我国水资源开发利用中亟待解决的几个认识问题

本文在分析８０年代在以来我国用水变化趋势基础上，探讨了北方地区的缺水程度，并对南水北调工程和可调水量提出了下些看法；文章还从水资源管理模式、法制和法规建设等方面阐述了对当前我国水资源管理政策方面的认识，从水的有效利用与水源保护、水的定价与成本回收、与水有关的社会与环境问题等方面论述了我国２１世纪将面临的有关水问题。     

A comparison of the water management systems in France and China

This paper compares legal systems for water management in France and China, with a focus on integrated water resources management and regarding in particular the formulation of policies and their implementation. The research shows that China has committed itself to the efficient management of water resources through the development of various policy tools during the current period. This commitment, however, has often been interrupted and distorted by politics, resulting in the neglect of socioeconomic and environmental priorities. France has developed a legislative framework and practical instruments to apply integrated water resources management at the river basin level since the 1960s. This experience and the current implementation of the European Water Framework Directive brings elements that can contribute to Chinese society meeting its water challenges.     

Volatile organic compounds in wintertime North China Plain: Insights from measurements of proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS)

The characteristics of wintertime volatile organic compounds (VOCs) in the North China Plain (NCP) region are complicated and remain obscure. VOC measurements were conducted by a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at a rural site in the NCP from November to December 2018. Uncalibrated ions measured by PTR-ToF-MS were quantified and the overall VOC compositions were investigated by combining the measurements of PTR-ToF-MS and gas chromatography-mass spectrometer/flame ionization detector (GC-MS/FID). The measurement showed that although atmospheric VOCs concentrations are often dominated by primary emissions, the secondary formation of oxygenated VOCs (OVOCs) is non-negligible in the wintertime, i.e., OVOCs accounts for 42% ± 7% in the total VOCs (151.3 ± 75.6 ppbV). We demonstrated that PTR-MS measurements for isoprene are substantially overestimated due to the interferences of cycloalkanes. The chemical changes of organic carbon in a pollution accumulation period were investigated, which suggests an essential role of fragmentation reactions for large, chemically reduced compounds during the heavy-polluted stage in wintertime pollution. The changes of emission ratios of VOCs between winter 2011 and winter 2018 in the NCP support the positive effect of “coal to gas” strategies in curbing air pollutants. The high abundances of some key species (e.g. oxygenated aromatics) indicate the strong emissions of coal combustion in wintertime of NCP. The ratio of naphthalene to C8 aromatics was proposed as a potential indicator of the influence of coal combustion on VOCs.     

Land use/cover change effects on floods with different return periods: a case study of Beijing, China

In this study, an approach integrating digital land use/cover change (LUCC) analysis, hydraulic modeling and statistical methods was applied to quantify the effect of LUCC on floods in terms of inundation extent, flood arrival time and maximum water depth. The study took Beijing as an example and analyzed five specific floods with return periods of 20-year, 50-year, 100-year, 1000-year and 10000-year on the basis of LUCC over a nine-year period from 1996 to 2004. The analysis reveals that 1) during the period of analysis Beijing experienced unprecedented LUCC; 2) LUCC can affect inundation extent and flood arrival time, and floods with longer return periods are more influenced; 3) LUCC can affect maximum water depth and floods with shorter return periods are more influenced; and 4) LUCC is a major flood security stressor for Beijing. It warns that those cities having experienced rapid expansion during recent decades in China are in danger of more serious floods and recommends that their actual land use patterns should be carefully assessed considering flood security. This integrated approach is demonstrated to be a useful tool for joint assessment, planning and management of land and water.