Risk assessment and binding mechanisms of potentially toxic metals in sediments from different water levels in a coastal wetland

The excessive accumulation of potentially toxic metals (Pb and Cd) in coastal wetlands is among the main factors threatening wetland ecosystems. However, the effects of water table depth (WTD) on the risk and binding mechanisms of potentially toxic metals in sediments remain unclear. Here, sediments from different WTD obtained from a typical coastal wetland were evaluated using a newly developed strategy based on chemical extraction methods coupled with high-resolution spectroscopy. Our findings indicated that the WTD of the coastal wetland fluctuates frequently and the average enrichment factor for Pb was categorized as minor, whereas Cd enrichment was categorized as moderate. High-resolution spectroscopy techniques also demonstrated that organic functional groups and partly inorganic compounds (e.g., Fe-O/Si-O) played a vital role in the binding of Pb and Cd to surface sediments. Additionally, mineral components rather than organic groups were mainly bound to these metals in the bottom sediments. Collectively, our findings provide key insights into the potential health effects and binding characteristics of potentially toxic metals in sediments, as well as their dynamic behavior under varying sediment depths at a microscale.     

《京都》15年后:分阶段减排政策与“绿色悖论”问题

低碳经济的政策分析,通常囿于单一国家层面的局部均衡结果,较少考虑到全球整体行动的外部影响,但从《联合国气候变化框架公约》建立以来的全球一致减排行动,却产生了一些意料之外的负面效果。本文通过梳理《京都议定书》签订以来,全球低碳经济合作中遇到的新挑战,以及碳交易市场的建设状况,采用制度分析与新古典框架下的市场均衡分析方法,讨论了全球一致减排行动所触发的"绿色悖论"问题。研究发现,造成"绿色悖论"的主要原因,一方面是由于国际合作存在制度设计上的缺陷,《京都议定书》及其关键性的附件一,将重点放在如何限制发达工业国的减排设计上,但却忽视了发展中国家在协议期内有可能出现的增排问题,以及发达国家向发展中国家污染转移的碳泄漏等问题;另一方面,当对不可再生资源的使用征税、以及对其替代品进行补贴时,将会导致在当前期对于化石能源的加速开采,并可能导致对同时期的化石燃料替代品的其他可再生资源的开采速度也大幅度加快,造成了在双重加速开采下的全球绿色福利损失以及CO2排放量的急剧升高,化石能源消费与温室气体排放面临到比协议签署前更为严峻,甚至与全球合作减排框架的设计初衷相悖的结果。研究结果表明,非全局性的减排公约和分阶段的减排政策,是造成"绿色悖论"现象的重要条件,缺少了大量发展中国家和一些重要工业国的缔约,使得负面的环境外部性难以克服;同时,减排任务和责任有所区别的分阶段设计,会把在未来行动期内可预见到的更高地化石能源使用成本转嫁到当前的行动期,造成短时间内资源与环境的迅速破坏。但本文的研究也表明,社会最优经济与对可再生能源进行补贴是克服"绿色悖论"现象的两条可行路径,且需要有与其相匹配的政府政策的支持。由此,本文的主要政策建议是,中国需要加强在国际气候公约中的影响力,提升自身话语权;以碳税政策作为发展低碳经济制度设计的主要政策工具;加快技术进步、提高能源使用效率,对于可再生能源研发进行补贴;根据国情不断优化碳税税率,并适时调整与其相匹配的新能源补贴等相关政策。     

Physiologically based pharmacokinetic modeling of perfluoroalkyl substances in the human body

Currently, there are limited data on the levels of perfluoroalkyl substances other than perfluorooctane sulfonic acid and perfluorooctanoic acid in the human body. Most of this information has been extracted from biological monitoring of plasma while the occurrence of perfluoroalkyl substances in other human tissues is rarely studied. The objective of the present study was to develop a physiologically based pharmacokinetic model to assess the concentration of perfluoroalkyl substances in human tissues, based on an existing model previously validated for perfluorooctane sulfonic acid and perfluorooctanoic acid. Experimental data on concentrations of perfluoroalkyl substances in human tissues from individuals in Tarragona County (Catalonia, Spain) were used to estimate the values of some distribution and elimination parameters needed for the simulation. No significant correlations were found between these parameters and the chain lengths. The model was finally validated for five perfluoroalkyl substances.     

蒙脱土原位生长MoS2复合材料光催化降解罗丹明B的机理研究

通过在Na⁺-MMT表面生长MoS₂来提高窄带隙半导体光生电子分离速率及稳定性.利用阳离子填充法及水热法成功制备了复合光催化剂Na⁺-MMT/MoS₂,并通过FT-IR、SEM、TEM、Raman、XRD、TG、XPS、UV-DRS和ESR等表征进一步证明了材料的成功负载及光、电化学性能. 同时,以有机染料罗丹明B为待降解染料来评价光催化剂的催化性能,发现其在80 min可有效降解罗丹明B,降解率达96%.经过5次循环使用后,Na⁺-MMT/MoS₂复合光催化剂仍具有较好的光催化性能.因此,利用MMT的表面电负性及稳定的片层结构负载MoS₂,可形成光生电子迁移通道进一步提高电荷迁移速率及光催化剂的稳定性.本研究可为黏土材料调控窄带隙半导体制备环境友好型光催化剂提供新思路.     

Theoretical insights into the degradation mechanisms, kinetics and eco-toxicity of oxcarbazepine initiated by OH radicals in aqueous environments

As an anticonvulsant, oxcarbazepine (OXC) has attracted considerable attention for its potential threat to aquatic organisms. Density functional theory has been used to study the mechanisms and kinetics of OXC degradation initiated by OH radicals in aqueous environment. A total of fourteen OH-addition pathways were investigated, and the addition to the C8 position of the right benzene ring was the most vulnerable pathway, resulting in the intermediate IM8. The H-abstraction reactions initiated by OH radicals were also explored, where the extraction site of the methylene group (C14) on the seven-member carbon heterocyclic ring was found to be the optimal path. The calculations show that the total rate constant of OXC with OH radicals is 9.47 × 10⁹ (mol/L)⁻¹sec⁻¹, and the half-life time is 7.32 s at 298 K with the [·OH] of 10⁻¹¹ mol/L. Moreover, the branch ratio values revealed that OH-addition (89.58%) shows more advantageous than H-abstraction (10.42%). To further understand the potential eco-toxicity of OXC and its transformation products to aquatic organisms, acute toxicity and chronic toxicity were evaluated using ECOSAR software. The toxicity assessment revealed that most degradation products such as OXC-2OH, OXC-4OH, OXC-1O-1OOH, and OXC-1OH' are innoxious to fish and daphnia. Conversely, green algae are more sensitive to these compounds. This study can provide an extensive investigation into the degradation of OXC by OH radicals and enrich the understanding of the aquatic oxidation processes of pharmaceuticals and personal care products (PPCPs).     

光电催化氧化处理中各类活性物质的氧化机理

为了深入研究其中各类活性物质氧化机理,以难降解的3,4-二甲基苯胺（3,4-DMA）废水作为研究对象,通过研究不同抑制剂条件下的动力学规律,并以贡献度（k_f/K）来量化各活性物质的作用效果,得出氯类活性物质的贡献度为89.03%,羟基自由基（·OH）的贡献度为6.24%,而空穴和阳极直接氧化贡献度可以忽略.采用三聚氰胺法、二甲亚砜（DMSO）法和DPD法定性定量测定了空穴、·OH和自由氯的含量,结果表明：较高浓度的氯化钠降低了空穴和·OH的贡献度;·OH的产量符合零级动力学规律,其产生速率为0.106mg/（L·min）;自由氯的累积浓度分为3个阶段,第3阶段累积速率为0.159mg/（L·min）.自由氯仅占氯类活性物质氧化体系的一小部分,其他含氯氧化物质和氯类自由基的氧化占重要地位.通过GC-MS、UV-vis和TOC检测,发现在反应10.0min前,主要通过氯类活性物质对侧链的快速攻击,使3,4-DMA转化为苯甲醛等易分解的苯环类物质;10.0min后,主要通过·OH对苯环大π键的攻击,使苯环类物质转化为小分子物质,然后继续被·OH氧化直到矿化.     

Fe(VI)/CaO2双氧化体系降解水环境中的DMP

研究了高铁酸盐（Fe（VI））/过氧化钙（CaO₂）联合处理对邻苯二甲酸二甲酯（DMP）的降解性能及机理,分析了共存离子的影响.基于响应面方法中的Box-Behnken实验设计进行了多因素实验,采用二次多项式和逐步回归法拟合了DMP去除率与Fe（VI）投加量、CaO₂投加量和反应时间之间的关系,对实验条件进行了优化分析.结果表明,在初始pH值为中性条件下,Fe（VI）/CaO₂可以有效去除DMP,降解过程符合准一级动力学模型.当Fe（VI）/CaO₂/DMP物质的量比为1.1/4.4/1时,模型预测DMP最大降解率为95.57%,和验证实验得出的降解率90.14%相近,表明该响应面模型具有较好的模拟和预测能力.HCO₃^-和Mg²⁺对DMP的降解有一定抑制作用.自由基清除实验结果显示,羟基自由基（HO·）和超氧自由基（O₂^-·）对DMP的降解具有重要贡献,表明Fe（VI）和CaO₂可形成类芬顿试剂协同降解污染物.DMP的主要降解途径包括酯基水解、侧链氧化和苯环的羟基化;主要降解产物为邻苯二甲酸单甲酯,2,5-二羟基苯甲酸,间苯二甲酸,草酸等.     

微塑料对环境中有机污染物吸附解吸的研究进展

微塑料已成为新的全球性环境污染问题。作为强吸附剂,微塑料可以吸附共存的有机污染物,进而改变其环境行为和毒性;也可以通过解吸作用促进污染物在不同介质中的迁移。因而,微塑料与有机污染物的相互作用强度和机理是全面评估两者的环境风险和深度研究微塑料毒性机制的必要信息。目前微塑料研究处于快速发展的起始阶段,加之微塑料本身成分、粒径、表面风化情况的复杂性及共存有机污染物的多样性使两者的相互作用十分复杂,亟需理清微塑料吸附解吸作用的影响因素和相关机制。因而,本文详细综述了微塑料对有机污染物吸附解吸作用的研究进展,并着重从微塑料性质(成分、粒径和表面风化)、有机污染物性质和水环境介质性质方面探讨了吸附的影响因素和相互作用机制,希望为微塑料吸附有机污染物及吸附的后续影响研究提供借鉴与参考。     

农药在环境中的水解机理及其影响因子研究进展

农药的水降解与其在环境中的持久性是密切相关的,它是影响农药在环境中的归宿机制的重要依据之一,也是评价农药在水体中残留特性的重要指标。近些年来,国内外不少学者对农药尤其是有机磷、氨基甲酸酯、拟除虫菊酯和磺酰脲类等的水解进行了大量研究,其内容涉及到农药水化学降解机理及其各种因子如pH值、温度和黏土矿物等对农药水解的影响等,并取得了很多新的进展。但是所有这些研究主要集中于实验室内,而对其自然环境中各因子的贡献及其水解机制的了解则相对较少。今后应加强农药在自然条件下的水解动力学与机理以及黏土矿物和腐殖酸对农药在水体中的催化水解研究,以更好地评价农药在环境中的行为与归宿,为农药的合理使用提高科学依据。