模拟土壤淋洗废液中重金属的选择性去除与淋洗液的回收研究

土壤淋洗废液中污染物的选择性去除是实现淋洗液回收的关键.本文以硫化钠（Na₂S）、乙基黄原酸钾（PEX）、二甲基二硫代氨基甲酸钠（DTC）作为重金属沉淀剂处理电子垃圾污染土壤模拟淋洗废液,在筛选出Na₂S作为理想重金属沉淀剂的基础上,研究初始pH值、反应温度、沉淀剂浓度等因素对Na₂S分离络合态重金属的影响,并通过软件模拟和产物表征等方式推测反应机理.结果表明：Na₂S对柠檬酸络合态重金属的分离顺序依次为Cu、Pb、Cd,符合硫化物溶度积原则;反应温度、初始pH值对Na₂S处理络合态重金属无显著影响,重金属去除率均保持在90%以上,柠檬酸的回收率约为95%;Visual MINTEQ模拟结果显示,S^2-投加前液相中重金属主要以H₂CA^-、HCA^2-和CA^3-结合形式存在,S^2-投加后液相中重金属则以HS^-和S^2-结合形式存在;扫描电镜及能谱（SEM-EDS）表明,S^2-与金属阳离子按物质的量比1：1生成硫化物沉淀物,沉淀主要呈团聚、成簇和圆片状存在;X射线衍射（XRD）分析结果表明,沉淀产物中存在CuS、CdS、PbS和CuPbS₂.本研究结果可为化学沉淀法处理重金属污染土壤淋洗废液提供技术参考.     

内质网应激在氟暴露致小鼠睾丸损伤中的作用

探讨了内质网应激在亚慢性氟暴露致小鼠睾丸损伤中的作用及分子机制.选用健康初断乳ICR雄性小鼠30只,随机分为对照组（C）、低氟组（LF）和高氟组（HF）,分别饮用自来水、5、30 mg·L^-1氟化钠水溶液90 d.亚慢性氟暴露结束后,以睾丸脏器系数、睾丸组织氧化/抗氧化酶和形态结构、精子质量、睾丸细胞凋亡、葡萄糖调节蛋白78（GRP78）、CCAAT/增强子结合蛋白同源蛋白（CHOP）、半胱氨酸天冬氨酸蛋白酶12（CASPASE-12）、半胱氨酸天冬氨酸蛋白酶3（CASPASE-3）为观测点.结果表明,与对照组比,LF组和HF组LDH、SOD、T-AOC活性下降,MDA含量上升,HF组GSH-PX活性下降,差异有统计学意义（p<0.05或p<0.01）;LF组可见细胞层次减少、间隙变大,成熟精子数量减少,HF组细胞溶解、层次紊乱,空泡化严重,少见成熟精子;LF组和HF组小鼠的精子活力降低,HF组小鼠精子数量下降,畸形率上升,差异有统计学意义（p<0.05或p<0.01）;LF组和HF组睾丸细胞凋亡指数上升,差异有统计学意义（p<0.01）;LF组和HF组Grp78、Caspase-12、Caspase-3基因表达水平上升,差异有统计学意义（p<0.05或p<0.01）.结果提示,除氧化应激以外,Caspase-12和Caspase-3基因表达异常可能是氟暴露致小鼠睾丸细胞凋亡异常的分子机制之一.     

金属改性对SAPO-34低温还原NO性能的影响

采用浸渍法制备金属改性SAPO-34分子筛催化剂,分析比较了不同单金属（Cu或Co）及不同比例双金属（Cu：Co=1：1、3：1、5：1,质量比）改性催化剂对NO的催化还原性能,评价了不同催化剂的N₂选择性,并采用扫描电子显微镜（SEM）、比表面积测试、X射线衍射分析（XRD）、NH₃-程序升温脱附（NH₃-TPD）等表征手段对催化剂的物化性能进行了分析.结果表明,单金属Cu改性催化剂具有较宽的温度区间,在250~450℃范围内NO的转化率始终保持在100%;双金属改性使NO转化率保持为100%的最低温度下降了25~50℃,显著拓宽了低温段窗口,其中,Cu₃Co₁/SAPO-34催化剂的低温催化还原性能最好,200℃即可实现100%的NO转化率,175℃下的转化率也高达80%以上.Cu-Co双金属改性SAPO-34分子筛催化剂具有优异的低温催化还原NO性能,具有在机动车尾气、工业废气的低温脱硝治理领域应用的潜力.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

Preparation of hydrophobic hierarchical pore carbon–silica composite and its adsorption performance toward volatile organic compounds

Carbon–silica materials with hierarchical pores consisting of micropores and mesopores were prepared by introducing nanocarbon microspheres derived from biomass sugar into silica gel channels in a hydrothermal environment.The physicochemical properties of the materials were characterized by nitrogen physical adsorption(BET),scanning electron microscopy(SEM),and thermogravimetric(TG),and the adsorption properties of various organic waste gases were investigated.The results showed that microporous carbon materials were introduced successfully into the silica gel channels,thus showing the high adsorption capacity of activated carbon in high humidity organic waste gas,and the high stability and mechanical strength of the silica gel.The dynamic adsorption behavior confirmed that the carbon–silica material had excellent adsorption capacity for different volatile organic compounds(VOCs).Furthermore,the carbon–silica material exhibited excellent desorption characteristics:adsorbed toluene was completely desorbed at 150℃,thereby showing superior regeneration characteristics.Both features were attributed to the formation of hierarchical pores.     

Bioassay: A useful tool for evaluating reclaimed water safety

Wastewater reclamation and reuse has been proved to be an effective way to relieve the fresh water crisis. However, toxic contaminants remaining in reclaimed water could lead to potential risk for reuse, and the conventional water quality standards have difficulty guaranteeing the safety of reclaimed water. Bioassays can vividly reflect the integrated biological effects of multiple toxic substances in water as a whole, and could be a powerful tool for evaluating the safety of reclaimed water. Therefore, in this study, the advantages and disadvantages of using bioassays for evaluating the safety of reclaimed water were compared with those of conventional water quality standards. Although bioassays have been widely used to describe the toxic effects of reclaimed water and treatment efficiency of reclamation techniques, a single bioassay cannot reflect the complex toxicity of reclaimed water, and a battery of bioassays involving multiple biological effects or in vitro tests with specific toxicity mechanisms would be recommended. Furthermore, in order to evaluate the safety of reclaimed water based on bioassay results, various methods including potential toxicology, the toxicity unit classification system, and a potential eco-toxic effects probe are summarized as well. Especially, some integrated ranking methods based on a bioassay battery involving multiple toxicity effects are recommended as useful tools for evaluating the safety of reclaimed water, which will benefit the promotion and guarantee the rapid development of the reclamation and reuse of wastewater.     

Role of glycine on sulfuric acid-ammonia clusters formation: Transporter or participator

Glycine(Gly) is ubiquitous in the atmosphere and plays a vital role in new particle formation(NPF).However,the potential mechanism of its on sulfuric acid(SA)-ammonia(A)clusters formation under various atmospheric conditions is still ambiguous.Herein,a(Gly)_x·(SA)_y·(A)_z(z≤x+y≤3) multicomponent system was investigated by using density functional theory(DFT) combined with Atmospheric Cluster Dynamics Code(ACDC) at different temperatures and precursor concentrations.The results show that Gly,with one carboxyl(-COOH) and one amine(-NH_2) group,can interact strongly with SA and A in two directions through hydrogen bonds or proton transfer.Within the relevant range of atmospheric concentrations,Gly can enhance the formation rate of SA-A-based clusters,especially at low temperature,low [SA],and median [A].The enhancement(R) of Gly on NPF can be up to 340 at T=218.15 K,[SA]=10~4,[A]=10~9,and [Gly]=10~7 molecules/cm~3.In addition,the main growth paths of clusters show that Gly molecules participate into cluster formation in the initial stage and eventually leave the cluster by evaporation in subsequent cluster growth at low [Gly],it acts as an important "transporter" to connect the smaller and larger cluster.With the increase of [Gly],it acts as a "participator" directly participating in NPF.     

Influence of floc dynamic protection layer on alleviating ultrafiltration membrane fouling induced by humic substances

Cake layer formation is inevitable over time for ultrafiltration (UF) membrane-based drinking water treatment. Although the cake layer is always considered to cause membrane fouling, it can also act as a “dynamic protection layer”, as it further adsorbs pollutants and dramatically reduces their chance of getting to the membrane surface. Here, the UF membrane fouling performance was investigated with pre-deposited loose flocs in the presence of humic acid (HA). The results showed that the floc dynamic protection layer played an important role in removing HA. The higher the solution pH, the more negative the floc charge, resulting in lower HA removal efficiency due to the electrostatic repulsion and large pore size of the floc layer. With decreasing solution pH, a positively charged floc dynamic protection layer was formed, and more HA molecules were adsorbed. The potential reasons were ascribed to the smaller floc size, greater positive charge, and higher roughness of the floc layer. However, similar membrane fouling performance was also observed for the negative and positive floc dynamic protection layers due to their strong looseness characteristics. In addition, the molecular weight (MW) distribution of HA also played an important role in UF membrane fouling behavior. For the small MW HA molecules, the chance of forming a loose cake layer was high with a negatively charged floc dynamic protection layer, while for the large MW HA molecules it was high with a positively charged floc dynamic protection layer. As a result, slight UF membrane fouling was induced.     

Influence of environmental factors on arsenic accumulation and biotransformation using the aquatic plant species Hydrilla verticillata

Hydrilla verticillata(waterthyme) has been successfully used for phytoremediation in arsenic(As) contaminated water.To evaluate the effects of environmental factors on phytoremediation,this study conducted a series of orthogonal design experiments to determine optimal conditions,including phosphorus(P),nitrogen(N),and arsenate(As(Ⅴ))concentrations and initial pH levels,for As accumulation and biotransformation using this aquatic plant species,while also analyzing As species transformation in culture media after 96-hr exposure.Analysis of variance and the signal-to-noise ratio were used to identify both the effects of these environmental factors and their optimal conditions for this purpose.Results indicated that both N and P significantly impacted accumulation,and N was essential in As species transformation.High N and intermediate P levels were critical to As accumulation and biotransformation by H.verticillata,while high N and low P levels were beneficial to As species transformation in culture media.The highest total arsenic accumulation was(197.2±17.4) μg/g dry weight when As(V) was at level 3(375μg/L),N at level 2(4 mg/L),P at level 1(0.02 mg/L),and pH at level 2(7).Although H.verticillata is highly efficient in removing As(Ⅴ) from aquatic environments,its use could be potentially harmful to both humans and the natural environment due to its release of highly toxic arsenite.For cost-effective and ecofriendly phytoremediation of As-contaminated water,both N and P are helpful in regulating As accumulation and transformation in plants.     

Hygroscopicity measurement of sodium carbonate, β-alanine and internally mixed β-alanine/Na2CO3 particles by ATR-FTIR

Water-uptakes of pure sodium carbonate(Na_2CO_3),pure β-alanine and internally mixedβ-alanine/Na_2CO_3 aerosol particles with different mole ratios are first monitored using attenuated total reflectance Fourier transform infrared spectroscopy(ATR-FTIR) technique.For pure Na_2CO_3 aerosol particles,combining the absorptions at 877 and 1422 cm-1 with abrupt water loss shows the efflorescence relative humidity(ERH) of 62.9%–51.9%.Upon humidifying,solid Na_2CO_3 firstly absorbs water to from Na_2CO_3·H2 O crystal at 72.0% RH and then deliquesces at 84.5% RH(DRH).As for pure β-alanine particles,the crystallization takes place in the range of 42.4%–33.2% RH and becomes droplets at ～ 88.2% RH.When β-alanine is mixed with Na_2CO_3 at various mole ratios,it shows no efflorescence of Na_2CO_3 whenβ-alanine to Na_2CO_3 mole ratio(OIR) is 2:1.For 1:1 and 1:2 β-alanine/Na_2CO_3 aerosols,the ERHs of Na_2CO_3 are 51.8%–42.3% and 57.1%–42.3%,respectively.While β-alanine crystal appears from 62.7% RH for 2:1 and 59.4% RH for both 1:1 and 1:2 particles and lasts to driest state.On hydration,the DRH is 44.7%–75.2% for Na_2CO_3 with the OIR of 1:1 and 44.7%–69.0%for 1:2 mixture,and those of β-alanine are 74.8% for 2:1 mixture and 68.9% for two others.After the first dehumidification–humidification,all the water contents decrease despite of constituent fraction.And at ～ 92% RH,the remaining water contents are 92%,89% and 82%at ～ 92% RH,corresponding to OIR of 2:1,1:1 and 1:2 mixed system,respectively.