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.     

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）.      

沈阳一次严重污染天气过程持续和增强气象条件分析

2015年11月7-9日沈阳出现罕见的持续严重污染天气,采用环流形势、地面常规气象观测、污染物浓度观测、风廓线雷达及雨滴谱资料等,对此次污染成因进行了研究.结果表明:在此次严重污染天气过程中,连续22 h AQI≥500,首要污染物均为PM_2.5,其异常峰值最高达到1308μg/m3;ρ（PM_2.5）与ρ（PM₁₀）、ρ（NO₂）和ρ（CO）的相关系数分别达到0.996、0.602、0.891,并且ρ（PM_2.5）与ρ（PM₁₀）、ρ（CO）的正相关性更为显著;在污染的同时出现了降水,11月7和8日的日降水量分别为9.9和2.3 mm,但降水对污染物的稀释和清除作用并不明显.稳定的大尺度环流和对流层内中低层大气层结持续稳定、连续4个时次的探空曲线显示925~850 hPa之间存在多个逆温层（逆温强度最大可达5℃）、相对湿度较大（日均相对湿度在75%以上）,是此次严重污染天气持续的有利气象条件.风廓线雷达探测的整层大气垂直速度很小,多介于-1~1 m/s之间,并且近地面2 m/s以下弱下沉的垂直速度为严重污染天气过程提供了较好的动力条件.此外,近地面风力可达3~4级,有利于上游污染物的水平输送.研究显示,此次严重污染天气过程还与外围秸秆集中燃烧所导致的大量污染物长距离输送有密切关联.      

基于碳密度-林龄关系的黑龙江省森林碳汇潜力预测

为了量化黑龙江省森林碳储量、预测森林碳汇潜力,利用蓄积量-生物量相关方程法对黑龙江省1994-2013年的森林碳储量进行估算,并依据1994-2013年4次全国森林资源清查中黑龙江省18种主要森林类型各林龄组数据,建立主要森林类型碳密度与林龄之间的关系;在此基础上,结合《黑龙江省林地保护利用规划（2010-2020）》预测2014-2020年黑龙江省森林的碳储量,并分析其碳汇潜力.结果表明:黑龙江省各森林类型碳密度与林龄关系拟合较好,18种森林类型中有14个的R2大于0.9;黑龙江省1994-2013年4次森林资源清查中森林碳储量分别为693.2、676.3、741.1和805.2 Tg;预计在第九次全国森林资源清查（2014-2018年）中,黑龙江森林碳储量将达到844.0 Tg,并且在预估期间其碳储量逐年递增,2020年将达到868.1 Tg.如果2013年黑龙江省现有森林都达到过熟林,其碳储量将会达到1.40×103 Tg,具有很高的碳汇潜力.为了进一步增加黑龙江省碳汇潜力,建议加强省内寒温带、温带山地针叶林和阔叶混交林的保护;在更新造林上要侧重于有固碳优势的森林类型（如赤松、杨树等）;加大对赤松、针阔混等近熟林、成熟林的保护力度,控制过熟林的数量.      

饱和持水量条件下不同氮添加对森林土壤氮素净转化的影响

为了研究在饱和持水量条件下不同氮沉降形态和水平对森林土壤氮素净转化及土壤N₂O排放的影响,选取中亚热带地带性森林红壤为研究对象,采用室内模拟试验方法,设置110%饱和持水量（WHC）的土壤水分,添加不同形态氮[（NH₄）₂SO₄、NaNO₃、NH₄NO₃]和不同含量[0 mg/kg（CK）、20.0 mg/kg（LN）、66.7 mg/kg（HN）,以干土计]的氮素,进行为期14 d的室内培养（20℃）.结果表明,与CK相比,（NH₄）₂SO₄和NaNO₃处理对土壤净氮矿化和氨化的影响不大,而（NH₄）₂SO₄处理的净硝化量在高氮水平下为负值,说明硝化很弱,但该处理的净氨化量高于其他处理,特别是NaNO₃处理的净氨化量较高,认为很可能存在NO₃--N异化还原为铵（DNRA）.NaNO₃处理能显著提高土壤净硝化量而显著降低w（SON）（SON为土壤可溶性有机氮）,NH₄NO₃处理同时降低了土壤w（NH₄+-N）和w（NO₃--N）,表现为氮固定作用,并且高氮水平的土壤w（MBN）（MBN为微生物量氮）显著高于低氮水平;NaNO₃和NH₄NO₃处理的土壤N₂O排放速率和培养周期内的累积排放量均显著高于CK,并且高氮水平显著高于低氮水平,而（NH₄）₂SO₄处理与CK相当,并且高氮水平下的N₂O累积排放量低于低氮水平.研究显示,在过饱和土壤水分条件下,混合形态氮对土壤氮素净转化格局影响较大,含NO₃-形态氮明显促进土壤N₂O的排放,尤其是高氮水平.研究结果可为评价全球气候变化下特别是降雨情况下沉降氮形态对土壤氮素转化的影响提供重要参考.      

光散射法与β射线衰减-光散射联用法颗粒物在线测量方法对比

为考察光散射法和β射线衰减-光散射联用法的适用性,以β射线衰减法颗粒物自动监测仪（BAM）为标准,于2016年2月4日-4月18日,在中国环境科学研究院利用β射线衰减-光散射联用法颗粒物自动监测仪（MP-CPM）与光散射法传感器对ρ（PM₁₀）和ρ（PM_2.5）测量结果进行了对比.结果表明:① MP-CPM与BAM测量ρ（PM₁₀）的结果具有较好的一致性,相关系数为0.92,平均相对偏差为0.04%;ρ（PM_2.5）结果一致性较差,相关系数为0.69,MP-CPM测量ρ（PM_2.5）整体较高于BAM,平均相对偏差为45.8%.② 光散射法传感器与BAM测量ρ（PM_2.5）结果一致性较好,相关系数为0.85,平均相对偏差为11.24%,但ρ（PM₁₀）远低于BAM,平均相对偏差为-44.64%.在特殊污染情景下,光散射法将因受到较大影响而严重错估颗粒物浓度.烟花燃放期间,MP-CPM和光散射法传感器严重低估颗粒物浓度,与BAM测量颗粒物浓度的平均相对偏差均低于-50%;沙尘污染过程中,MP-CPM严重高估ρ（PM_2.5）,与BAM测量ρ（PM_2.5）结果平均相对偏差为79.27%,光散射法传感器严重低估ρ（PM₁₀）,与BAM测量ρ（PM₁₀）结果平均相对偏差为-59.35%.研究显示,不同原理的仪器,在不同的使用场景下应该区别对待.      

北京市郊区夏季臭氧重污染特征及生成效率

为研究北京郊区夏季O₃(臭氧)重污染过程特征及O₃生成的光化学敏感性,基于2016年夏季在北京郊区开展的针对O₃及其相关污染物的强化观测试验(7月23日—8月31日,共计40 d),分析了观测期间O₃浓度[以φ(O₃)计]变化特征、O₃重污染过程主控因素与O₃敏感性化学特征.结果表明:观测期间φ(O₃)超标时有发生,最大小时φ(O₃)为151.1×10-9,其中有15 d的φ(O₃)最大8 h滑动平均值(O₃-max-8h)超过了GB 3095—2012《环境空气质量标准》二级标准限值,占观测天数的37.5%;不同O₃重污染过程成因有所不同,城市烟羽传输的污染物对郊区O₃重污染过程影响显著(观测期间臭氧重污染过程:过程1,7月27—29日;过程3,8月9—11日;过程4,8月16日;过程5,8月21—24日),区域光化学污染对郊区O₃重污染过程也有贡献(观测期间O₃重污染过程2:8月4—6日);结合后向气流轨迹进一步辅助说明了不同重污染过程中O₃的来源不同.研究还发现,观测区域存在反“周末效应”现象,说明观测区域周末受人为影响较为明显;基于观测数据计算的OPE(O₃生成效率)分析了O₃光化学敏感性表明,在有OPE值的22 d内NO_x控制区和VOCs控制区出现的概率(41%)相等,即观测区域O₃对NO_x和VOCs均敏感;此外还发现,在O₃重污染过程中光化学敏感性会随其反应进程发生改变,由NO_x控制区逐渐转变为VOCs控制区.