基于大气被动式采样的人体头发中类二(口恶)英多氯联苯暴露的途径

本研究通过分析采集自云南省开远市的13个树皮混合样品和13个相应的头发混合样品中DL-PCBs的水平、同族体分布及相关性,研究了当地人群对DL-PCBs的主要暴露途径.结果表明,云南开远树皮和头发样品中DL-PCBs的含量分别为4.0~88.9 pg·g^-1和4.1~19.3 pg·g^-1,其在当地环境和人体中的污染程度均较轻.树皮和头发样品中主要的DL-PCB同族体均是PCB-118,分别占总含量的48%和61%.树皮样品中DL-PCBs的各同族体具有相同的源,其主要的来源可能是大气的长距离输移.云南开远市居民头发中的PCBs可能来源于内部暴露和外部暴露的综合作用,其中外部暴露对低氯代PCBs的贡献要高于高氯代PCBs.     

黄山PM10中二元羧酸类化合物的季节变化特征及其来源

为研究黄山大气PM_(10)中二元羧酸类化合物的季节变化特征,分别于2015年夏季、冬季在黄山山顶采集PM_(10)样品,并分析二元羧酸、酮羧酸和α-二羰基化合物.结果表明,无论在夏季还是冬季,草酸(HOOC—COOH,C_2)均是浓度最高的二元羧酸,其次是丙二酸(HOOC—CH_2—COOH,C_3)、丁二酸[HOOC—(CH_2)_2—COOH,C_4],这与其它高海拔地区的分子组成是相似的.大部分二元羧酸的浓度呈冬低夏高的季节变化特征,但是冬季己二酸(C_6)和邻苯二甲酸(Ph)的浓度约高于夏季的2倍,表明冬季黄山大气受周边地区所排放的人为污染物的影响更大.作为二元羧酸的重要前体物,乙二醛(Gly)与甲基乙二醛(mGly)的浓度呈冬高夏低的季节变化特征,表明夏季黄山气溶胶的氧化性比冬季强.主成分分析(PCA)结果表明,黄山冬季SOA主要来自人为源的长距离传输,而夏季SOA主要是当地生物源经二次氧化形成.气溶胶无机模型(AIM)的计算结果表明,黄山夏季的C_2主要是经酸催化反应二次形成的.     

泉州市大气PM2.5镧系元素组成特征及来源解析

2014年3月、4月和7月分别采集了泉州市5个采样点共49个PM_(2.5)样品,采用电感耦合等离子体质谱(ICP-MS)测定样品镧系元素(Loid)及其他微量金属元素浓度水平.分析了PM_(2.5)镧系元素组成特征和配分模式,利用La-Ce-V三元图和化学质量平衡(CMB)受体模型解析了泉州市大气PM_(2.5)污染来源.结果表明:(1)泉州市大气PM_(2.5)总镧系元素(Σ Loid)浓度为2.490~5.708 ng·m~(-3)(含量65.682~126.529μg·g~(-1)),轻重镧系元素比值(L/H)为12.086~14.319;(2)PM_(2.5)镧系元素配分模式与福建土壤相似,PM_(2.5)中Ce元素表现为正异常,而Eu元素表现为负异常;(3)城市扬尘、燃煤尘、汽车尾气尘和垃圾焚烧飞灰是泉州市大气PM_(2.5)的主要来源,贡献率分别为18.9%、10.9%、30.6%和30.2%.     

Metal distribution characteristic of MSWI bottom ash in view of metal recovery

Bottom ash is the major by-product of municipal solid waste incineration(MSWI), and is often reused as an engineering material, such as road-base aggregate. However, some metals(especially aluminum) in bottom ash can react with water and generate gas that could cause expansion and failure of products containing the ash; these metals must be removed before the ash is utilized. The size distribution and the chemical speciation of metals in the bottom ash from two Chinese MSWI plants were examined in this study, and the recovery potential of metals from the ash was evaluated. The metal concentrations in these bottom ashes were lower than that generated in other developed countries. Specifically, the contents of Al,Fe, Cu and Zn were 18.9–29.2, 25.5–32.3, 0.7–1.0 and 1.6–2.5 g/kg, respectively. Moreover,44.9–57.0 wt.% of Al and 55.6–75.4 wt.% of Fe were distributed in bottom ash particles smaller than 5 mm. Similarly, 46.6–79.7 wt.% of Cu and 42.9–74.2 wt.% of Zn were concentrated in particles smaller than 3 mm. The Fe in the bottom ash mainly existed as hematite, and its chemical speciation was considered to limit the recovery efficiency of magnetic separation.     

不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比

通过实验对比考察了不同锆负载量的锆改性膨润土对水中磷酸盐的吸附作用.结果表明,锆改性膨润土对水中磷酸盐的吸附动力学过程符合准二级动力学模型,整个过程可以分为快速吸附阶段、缓慢吸附阶段和平衡吸附阶段,其中缓慢吸附阶段的吸附速率受膜扩散和颗粒内扩散所控制.锆改性膨润土对水中磷酸盐的吸附等温实验数据可以采用Langmuir、Freundlich、Sips和Dubinin-Radushkevich等温吸附模型进行拟合.实验条件下,磷酸盐吸附性能随pH增加而降低.溶液共存的Na~+、K~+和Ca~(2+)促进了锆改性膨润土对磷酸盐的吸附,并且Ca~(2+)的促进作用远远大于Na~+和K+,而溶液共存的HCO-3和SO2-4一定程度上抑制了锆改性膨润土对磷酸盐的吸附.锆改性膨润土吸附水中磷酸盐的主要机制为配位体交换并形成内层磷酸盐配合物.锆改性膨润土对水中磷酸盐的吸附能力随着锆负载量的增加而增加,而锆改性膨润土中单位质量ZrO_2对水中磷酸盐的吸附量则随着锆负载量的增加而降低.当ZrO_2负载量由3.61%增加到13.15%时锆改性膨润土的最大单层单位吸附量(以P计)显著地由3.83 mg·g~(-1)增加到9.03 mg·g~(-1),而继续增加ZrO_2负载量至19.63%时锆改性膨润土的最大单层单位吸附量则缓慢地提高到9.66 mg·g~(-1)(以P计).当ZrO_2负载量由3.61%逐渐增加到19.63%时,锆改性膨润土中单位质量ZrO_2的磷酸盐最大吸附量[m(P)/m(ZrO_2)]由106 mg·g~(-1)逐渐下降到49.2 mg·g~(-1).综合考虑吸附剂的经济成本和吸附容量,ZrO_2负载量为13.15%锆改性膨润土更为适合作为吸附剂去除水中磷酸盐.     

Research on the degradation mechanism of pyridine in drinking water by dielectric barrier discharge

Pyridine, an important chemical raw material, is widely used in industry, for example in textiles,leather, printing, dyeing, etc. In this research, a dielectric barrier discharge(DBD) system was developed to remove pyridine, as a representative type of nitrogen heterocyclic compound in drinking water. First, the influence of the active species inhibitors tertiary butanol alcohol(TBA),HCO_3~-, and CO_3~(2-)on the degradation rate of pyridine was investigated to verify the existence of active species produced by the strong ionization discharge in the system. The intermediate and final products generated in the degradation process of pyridine were confirmed and analyzed through a series of analytical techniques, including liquid chromatography–mass spectrometry(LC–MS), high performance liquid chromatography(HPLC), ion chromatography(IC), total organic carbon(TOC) analysis, ultraviolet(UV) spectroscopy, etc. The results showed that the degradation of pyridine was mainly due to the strong oxidizing power of ozone and hydroxyl radical produced by the DBD system. Several intermediate products including 3-hydroxyl pyridine, fumaric acid, 2, 3-dihydroxypyridine, and oxalic acid were detected. Nitrogen was removed from the pyridine molecule to form nitrate. Through analysis of the degradation mechanism of pyridine, the oxidation pathway was deduced. The study provided a theoretical and experimental basis for the application of DBD strong ionization discharge in treatment of nitrogen heterocyclic compounds in drinking water.     

Effect of oxide nanoparticles on the morphology and fluidity of phospholipid membranes and the role of hydrogen bonds

Engineered oxide nanoparticles (NPs) are widely applied in insulators, catalyzers, paints, cosmetic products, textiles and semiconductors. Their attachment on cell membrane may lead to cytotoxicity. The effects of Al₂O₃, Fe₂O₃, SiO₂, TiO₂ and ZnO NPs on membrane integrity and fluidity were studied using giant or small unilamellar vesicles in this study. Al₂O₃ and SiO₂ NPs disrupted the oppositely charged membrane, indicating the important role of electrostatic attraction. However, Fe₂O₃, TiO₂ and ZnO NPs did not cause serious membrane disruption as Al₂O₃ and SiO₂ NPs. Membrane fluidity was evaluated by the generalized polarity (GP) values of Laurdan fluorescent emission. SiO₂ NPs induce the membrane gelation of both positively and negatively charged membrane. Al₂O₃ and ZnO NPs induced the gelation of the oppositely charged membrane, but did not cause obvious membrane gelation to the like charged membrane. The phospholipid molecular structural changes after NP exposure were analyzed by Fourier transform infrared (FT-IR) spectroscopy. FT-IR spectra revealed the hydrogen bond formation between NPs and the carbonyl/phosphate groups of phospholipids. Al₂O₃ and SiO₂ NPs showed strongest evidence of hydrogen bonding on their FT-IR spectra. It was consistent with the microscopic observation and fluorescent data that Al₂O₃ and SiO₂ NPs caused more serious membrane disruption and gelation. This study on membrane damage provides further knowledge on the cytotoxicity of nanomaterials and the safety of NP application.     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.     

温度对合成钛酸盐纳米材料的影响及其对水中Cd (Ⅱ)的去除效果

为有效去除水中Cd（Ⅱ）,以TiO₂纳米粉和NaOH为原料,调节水热反应温度分别为100、120、150和190℃,制备出了不同形貌的TNs（钛酸盐纳米材料）,分别记为TNs-100、TNs-120、TNs-150和TNs-190,并对其形貌、结构、比表面积、化学组成等物理化学性能进行了表征;通过对水中Cd（Ⅱ）的静态吸附试验,考察了TNs对Cd（Ⅱ）的吸附性能.结果表明:随着合成温度的升高,TNs的形貌逐渐从纳米片演变成纳米管,管长逐渐变长,最后变成纳米棒.TNs-100的晶型结构主要是锐钛矿型;随着温度升高,结晶度逐渐增强;TNs-190出现了部分金红石相.TNs-150对Cd（Ⅱ）的吸附能力最强,最大平衡吸附量为254.66 mg/g,最佳吸附pH为5.0.再生的TNs-150对Cd（Ⅱ）循环吸附6次的去除率和解吸率均可达93%以上.TNs-150对Cd（Ⅱ）的吸附过程符合准二阶动力学方程和Langmuir吸附等温模型,吸附机制主要是TNs层间Na+和H+与溶液中Cd（Ⅱ）的离子交换.研究显示,TNs的饱和吸附量均高于同类吸附剂,能有效去除水中Cd（Ⅱ）.      

基于关键源区识别的饮用水水源保护区划研究

准确划定饮用水水源保护区是实现饮用水安全精细化管理的重要前提.基于源头削减和全过程协同管理的思路,将GIS平台、ArcSWAT模型、成本-效益分析技术相结合,以贵州省红枫湖饮用水水源保护区为例,通过对近5年（2010-2014年）水污染负荷特征进行模拟,识别影响水环境污染控制的关键源区,在此基础上划定水源保护区.结果表明:① 研究区总氮、总磷污染负荷主要来源为农业面源,其中农业种植和畜禽养殖的负荷贡献分别达到89.7%和91.8%,总氮和总磷负荷高风险区主要集中在流域西北部地势较高且农业耕作活动频繁区域;② 污染控制措施的成本效益分析表明,测土配方施肥、1°~15°坡耕地等高植物篱、保护性耕作、植被缓冲带的成本-效益比较高,在该区域水环境污染控制中具有较高的推广应用价值;③ 基于水污染关键源区识别结果,划定饮用水源四级风险区,其中一级、二级风险区总面积为97.6 km2,仅占原饮用水水源一、二级保护区面积的41.4%,可削减总氮、总磷负荷的60%~70%,所需的搬迁成本仅为原划定方案的35%.研究结果可为我国中西部人口密度大且逐水而居的地区饮用水水源保护区及管控政策的制订提供理论基础和技术参考.