UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

基于TMVOC的地下水位波动带苯系物迁移转化模拟

为探究水位波动情况下苯系物的迁移转化规律,提高石油污染场地地下水污染治理精度,以西北某傍河石化场地为研究对象,基于TMVOC模型对特征污染物苯系物开展泄漏模拟,通过情景模拟比较水位波动对苯系物迁移转化的影响,并从污染分布、相间转化等方面,解析地下水位稳定和波动状态下苯系物迁移转化过程差异.结果表明:①TMVOC模型较好地模拟了水位波动状态下苯系物迁移转化过程.②相较于水位稳定状态下,水位波动作用下苯系物污染深度增加0.5 m,污染面积增加25%,总质量增加12 kg.③水位稳定和波动状态下苯系物"气-液-NAPL（Non-Aqueous Phase Liquids）相"占比分别为0.17%、2.03%、97.8%和0.04%、3.69%、96.27%.④NAPL相苯系物饱和度分布与苯系物质量分布呈正相关,水位波动造成NAPL相初始饱和度降低,且初始水位面以下NAPL相饱和度升高.⑤对于苯而言,水位波动状态下非饱和带中苯在液相中的质量是水位稳定状态下的1.11倍,饱和带为10.15倍.研究显示,水位波动显著地影响了苯系物的迁移转化过程,促进了苯系物的溶解,并使更多的苯系物残留在地下介质中.      

某垃圾焚烧厂投产前后周边土壤二英类化合物的分布

为研究垃圾焚烧厂运行对周边土壤二英类化合物（PCDD/Fs）含量的影响,采集了珠三角地区某垃圾焚烧厂投产前和投产后周边土壤样品,分析研究了该垃圾焚烧厂运行对周边土壤中PCDD/Fs含量和组分的变化.结果表明:①2012年（投产前）珠三角地区某垃圾焚烧厂周边土壤PCDD/Fs含量较低,范围为163~591 ng/kg（毒性当量范围为0.198~0.863 ng I-TEQ/kg,I-TEQ为国际毒性当量因子折算的毒性当量值）;2017—2019年（投产后）周边土壤PCDD/Fs含量范围为151~1.75×103 ng/kg（毒性当量范围为0.812~3.88 ng I-TEQ/kg）,与其他研究相比处于较低的水平.②投产后,距该垃圾焚烧厂较近（1.5 km）的采样点（S1）土壤PCDD/Fs含量逐年增长,在较远（5.2 km）但人口较密集的采样点（S3）土壤PCDD/Fs含量整体较高,但呈逐年下降趋势.③投产后,土壤中的17种PCDD/Fs单体组分中,毒性当量贡献率最高的单体为八氯二苯并二英（OCDD）和2,3,4,7,8-五氯二苯并呋喃（2,3,4,7,8-PeCDF）,二者毒性当量贡献率范围为15.7%~45.4%.④在同一采样点土壤PCDD/Fs单体组分年间差异不明显,但同一年份不同采样点差异明显.研究显示,目前该垃圾焚烧厂周边土壤PCDD/Fs含量较低,但仍需要长期监测其可能带来的风险.      

特殊区域地表水环境背景值表征技术方法研究与应用

选取黑龙江省源头水保护区作为研究对象,根据DEM数据对保护区内随机布设的水质监测点控制单元进行划分并提取单元内的相关指标建立监测点背景特性量化模型,基于量化结果提出地表水环境背景值监测方案,建立背景值数据库.选取研究区自然属性指标与空间属性指标,以空间叠置技术与聚类分析方法对研究区地表水进行背景值分区,最终将黑龙江省分为六大地表水水质背景值地理分区,并计算了各分区地表水环境背景值表征范围.表征范围显示：依据现行标准进行水质评价,保护区内水质背景值已超出Ⅱ类水质标准限值.因此,基于水质背景值研究成果提出了考虑背景值影响下的水环境质量评价方法,并将方法应用于研究区,结果表明方法切实可行且优于单因子评价法.研究成果可为区域制定背景值影响下的水环境评价方法提供科学的数据支撑与理论依据.     

腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

滦河秋季大型底栖动物群落结构空间格局与关键环境影响因子识别

掌握水生生物的空间分布特征及其关键影响因子是科学制定生物多样性保护策略的基础.于2016年秋季对滦河53个样点开展了大型底栖动物和环境因子的现场调查,分析了大型底栖动物群落结构与空间分布特征,并识别出影响大型底栖动物物种空间分布的关键环境因子.结果表明:①滦河（河北省）共采集并鉴定出大型底栖动物206种,隶属于8纲22目70科144属,以纹石蚕（Hydropsyche sp.）和东方蜉蝣（Ephemera orientalis）为优势种.②根据滦河大型底栖动物群落结构相似性,53个样点在空间上被分为3组.第1组分布在滦河干流的中下游及支流下游,无指示物种;第2组分布在支流上游,指示种为纹石蚕、朝大蚊（Antocha sp.）和中华小长臂虾（Palaemonetes sinensis）;第3组分布在滦河干流中上游,指示种为东方蜉蝣和中华齿米虾（Neocaridina denticulate sinensis）.③第3组的分类单元数显著高于第1组和第2组;第1组的多样性指数显著高于第2组;第1组的均匀度指数显著高于其他2组.单因素方差分析（one-way ANOVA）发现,pH、TN、底质、河道变化、水质状况和河岸土地利用类型等环境因子在第2组与第3组之间差异显著,第2组明显高于第3组.典范对应分析（CCA）表明,栖境复杂性、河水水量状况和河岸土地利用类型是影响滦河大型底栖动物空间分布的关键环境因子.研究显示,降低河岸带干扰强度、恢复河道生境多样性是未来滦河大型底栖动物多样性保护恢复的重要管理措施.      

市级生态保护红线生态补偿框架初探——以济南市为例

生态补偿对于协调经济发展和环境保护具有重要意义,不同层次的生态补偿都急需探索。其中市级生态补偿因为具有"利益相关者明确、涉及范围小、行政管理方便"等优点,更容易优先推进。文章以济南市为研究案例,探索分析了市级生态保护红线生态补偿的利益相关者和资金框架结构,确定了各区县间生态保护红线的生态补偿分配比例,为其他城市乃至省级生态保护红线的生态补偿提供借鉴。