西安市重污染与清洁天PM2.5组分及其活性氧物质对比

针对重霾污染,在西安市冬季重污染日(2015-11-30~2015-12-09)和清洁日(2016-01-13~2016-01-22)各进行了为期10d的PM_(2.5)采集,测量其中的有机碳、元素碳,及NH_4~+、NO_3~-、SO_4~(2-)等无机水溶性离子,探讨两种污染条件下的组分特征及其成因.结果表明:观测期,重霾日和清洁日PM_(2.5)质量浓度分别为(170±47.5)μg·m~(-3)和(48.6±17.9)μg·m~(-3),且重霾日伴随低能见度、高湿静风等多种不利气象条件;重霾日二次无机离子(NH_4~+、NO_3~-、SO_4~(2-))组分占PM_(2.5)质量浓度的49.8%±13.1%,而清洁日为19.4%±5.95%,并且重霾日硫氧化速率(sulfur oxidation ratio,SOR)和氮氧化速率(nitrogen oxidation ratio,NOR)分别为0.282±0.157和0.269±0.124,远高于清洁日(SOR和NOR分别为0.189±0.057和0.077±0.046),重霾日二次有机组分浓度[(6.22±3.87)μg·m~(-3)]是清洁日[(1.44±1.63)μg·m~(-3)]的5倍,表明二次污染及不利气象条件是造成重霾期间相关组分浓度升高的重要原因.最后,通过二氯荧光黄双乙酸盐(2',7'-DCFH)化学荧光分析法测定了其中活性氧物质(reactive oxygen species,ROS)的浓度,探讨其对于二次无机组分形成的影响,结果表明观测期ROS平均浓度(以H_2O_2计)分别为(4.99±1.54)nmol·m~(-3)(重霾期),(0.492±0.356)nmol·m~(-3)(清洁期),二次反应及积累效应可能是西安重霾条件下ROS浓度升高的主要原因.NO_3~-、SO_4~(2-)与ROS均呈现正相关(P0.05),表明ROS可能通过二次氧化过程参与到二次无机组分形成过程中.     

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.     

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%.     

Shifts in microbial community structure and diversity in a MBR combined with worm reactors treating synthetic wastewater

The chemical oxygen demand (COD) and NH₃-N removal, membrane fouling, sludge characteristics and microbial community structure in a membrane bioreactor (MBR) coupled with worm reactors (SSBWR) were evaluated for 210 days. The obtained results were compared to those from a conventional MBR (C-MBR) operated in parallel. The results indicated that the combined MBR (S-MBR) achieved higher COD and NH₃-N removal efficiency, slower increase in membrane fouling, better sludge settleability and higher activities of the related enzymes in the activated sludge. Denaturing gradient gel electrophoresis was used to analyze the microbial community structures in the C-MBR and the S-MBR. The microbial community structure in the S-MBR was more diverse than that in the C-MBR. Additionally, the slow-growing microbes such as Saprospiraceae, Actinomyces, Frankia, Clostridium, Comamonas, Pseudomonas, Dechloromonas and Flavobacterium were enriched in the S-MBR, further accounting for the sludge reduction, membrane fouling alleviation and wastewater treatment.     

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.     

Performance and microbial community of a membrane bioreactor system——Treating wastewater from ethanol fermentation of food waste

In this study, a lab-scale biological anaerobic/anaerobic/anoxic/membrane bioreactor(A_-~3MBR) was designed to treat wastewater from the ethanol fermentation of food waste,a promising way for the disposal of food waste and reclamation of resources. The 454 pyrosequencing technique was used to investigate the composition of the microbial community in the treatment system. The system yielded a stable effluent concentration of chemical oxygen demand(202 ± 23 mg/L), total nitrogen(62.1 ± 7.1 mg/L), ammonia(0.3 ±0.13 mg/L) and total phosphorus(8.3 ± 0.9 mg/L), and the reactors played different roles in specific pollutant removal. The exploration of the microbial community in the system revealed that:(1) the microbial diversity of anaerobic reactors A_1 and A_2, in which organic pollutants were massively degraded, was much higher than that in anoxic A_3 and aerobic MBR;(2) although the community composition in each reactor was quite different, bacteria assigned to the classes Clostridia, Bacteroidia, and Synergistia were important and common microorganisms for organic pollutant degradation in the anaerobic units, and bacteria from Alphaproteobacteria and Betaproteobacteria were the dominant microbial population in A_3 and MBR;(3) the taxon identification indicated that Arcobacter in the anaerobic reactors and Thauera in the anoxic reactor were two representative genera in the biological process. Our results proved that the biological A_-~3MBR process is an alternative technique for treating wastewater from food waste.     

Simultaneous removal of Cu(II) and Cr(VI) by Mg–Al–Cl layered double hydroxide and mechanism insight

Mg–Al–Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20 mg/L) and Cr(VI) (40 mg/L) were completely removed within 30 min by Cl-LDH in a dosage of 2.0 g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200 mg/L) and Cr(VI) (400 mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg²⁺ and Al³⁺ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl⁻ in Cl-LDH interlayer, isomorphic substitution of Mg²⁺ with Cu²⁺, formation of Cu₂Cl(OH)₃ precipitation, and the adsorption of Cr(VI) by Cu₂Cl(OH)₃. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH.     

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.     

Simulated reaction of formaldehyde and ambient atmospheric particulate matter using a chamber

The reaction of HCHO with Beijing winter's real ambient particulate matter(PM) inside a 3.3 m~3 Teflon Chamber was conducted in this study. NO_2, O_3 and H_2O gases were removed from the ambient aerosol before entering into the chamber. The decays of HCHO were monitored(acetylacetone spectrophotometry method) during the reactions at different PM number concentrations(N_a) and relative humidities(RHs), and the formed particulate formate was detected by IC and XPS techniques. The results showed that when RH was10%–15%, the decay rate of HCHO in the chamber was higher with the existence of PM from relatively clean days(with number concentration(N_a) 200,000 particle/L, 0.35–22.5 μm)compared to dirty days(N_a 200,000 particle/L, 0.35–22.5 μm). When RH increased to 30%–45%, PM can hardly have significant influences on the decay of HCHO. The formations of formate on the reacted PM were consistent with the HCHO decay rates at different ambient PM N_aand RH conditions. This is a first study related to the "real" ambient PM reacted with HCHO and suggested that in the clean and low RH days, PM could be an effective medium for the conversion of HCHO to formate.