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%.     

Applicability of LIVE/DEAD BacLight stain with glutaraldehyde fixation for the measurement of bacterial abundance and viability in rainwater

Rainwater contains substantial bacteria and rain is an efficient pathway for the dissemination of bacteria from the atmosphere to land and water surfaces.However,quantitative information on rainwater bacteria is very limited due to the lack of a reliable method.In this study,the epifluorescence microscopy enumeration with the LIVE/DEAD BacLight Bacterial Viability Kit stain was verified to quantify the abundance of viable and non-viable bacterial cells in rainwater,with the 4',6-diamidino-2-phenylindole(DAPI) stain for the reference of total cell counts.Results showed that the total counts of bacterial cells by LIVE/DEAD BacLight staining were consistent with those by DAPI staining,and the average detection efficiency was(109 ± 29)%.The ratio of cell count with glutaraldehyde fixation to that without fixation was(106 ± 5)%on average.The bacterial concentration in negative control was usually an order of magnitude lower than that in rainwater samples.However,in case of small precipitation,the abundance in negative control could be more than that in rainwater samples.These results indicate that the enumeration with LIVE/DEAD BacLight bacterial viability assay coupled with glutaraldehyde fixation and careful negative control investigation is an approach applicable to the measurement of the concentration and viability of bacterial cells in rainwater.     

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.     

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.     

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.     

Assessment of the maximum allowed acid deposition load at current stage in China

Soil acidification caused by acid deposition has been significant in some forests in southern China. We present an approach for assessing the current stage maximum allowed load (SML) of acid deposition for terrestrial system in the country. The main idea was that soil base cation exchange as a finite buffer to acidity was included in the soil acidity mass balance calculation at current acidification stage. We calculated the SML for five forests in southern China. The usual critical loads for the same forests were also calculated by the steady state mass balance model for comparison. The results showed that the SML is a more tolerant limit than the critical load for the forests with soils not acidified seriously at current stage. However, the SML become a more stringent limit to acid deposition when the forest soils have acidified seriously to very low base cation saturation. In this case the SML assessment is beneficial for the soils recovering from a serious acidified state. Based on a national scale database, the SML mapping for non-agricultural soil system in China was carried out.     

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）.