Characteristics of size distributions and sources of water-soluble ions in Lhasa during monsoon and non-monsoon seasons

To understand the physical and chemical characteristics, particle size distribution and sources of size-separated aerosols in Lhasa, which is located on the Tibetan Plateau (TP), six sizes of aerosol samples were collected in Lhasa in 2014. Ca²⁺, NH₄⁺, NO₃^?, SO₄^2?and Cl^? were the dominant ions. The ratio of cation equivalents (CE) to anion equivalents (AE) for each particle size segment indicated that the atmospheric aerosols in Lhasa were alkaline. SO₄^2? and NO3^? could be neutralized by Ca²⁺, but could not be neutralized by NH₄⁺, according to the [NH₄⁺]/[NO₃^??+?SO₄^2?] and [Ca²⁺]/[NO₃^??+?SO₄^2?] ratios. Mobile sources were dominant in PM_0.95–1.5, PM_1.5–3 and PM_3–7.2, while stationary sources were dominant in the other three size fractions according to the [NO₃^?]/[SO₄^2?] ratios. The particle size distribution of all water-soluble ions during monsoon and non-monsoon periods was characterized by a bimodal distribution due to the different sources and formation mechanisms, and it was revealed that different ions had different sources in different seasons and different particle size segments by combining particle size distribution with correlation analysis. Source analysis of aerosols in Lhasa was performed using the Principal component analysis (PCA) for the first time, which revealed that combustion sources, motor vehicle exhaust, photochemical reaction sources and various types of dust were the main sources of Lhasa aerosols. Furthermore, Lhasa''s air quality was also affected by long-distance transmission, expressed as pollutants from South Asiaand West Asia, which were transmitted to Lhasa according to backward trajectory analysis.     

天津市典型区域PM2.5中水溶性离子污染特征

为了解天津市不同区域PM_2.5中水溶性离子污染特征,于2015年7月、10月及2016年1月、4月,在天津市南开区（简称“市区”）及武清区采集PM_2.5样品,结合气象因素、气态污染物研究,分析了样品中水溶性离子污染特征及来源.结果表明:①天津市市区及武清区PM_2.5中水溶性离子组分主要为二次离子（SO₄2-、NO₃-、NH₄+）;不同区域PM_2.5中二次离子各季节占比略有不同,市区为夏季（54.0%）>秋季（42.5%）>春季（41.3%）>冬季（40.7%）,武清区为夏季（53.0%）>春季（44.6%）>秋季（43.4%）>冬季（33.2%）.②冬季市区、武清区PM_2.5中水溶性离子组成差异较大,其他季节水溶性离子组成相似;夏季市区及武清区颗粒物呈酸性,其他季节均呈碱性,冬季武清区颗粒物碱性强于市区.③不同季节市区及武清区PM_2.5中SO₄2-均以（NH₄）₂SO₄形式存在,NO₃-冬季以NH₄NO₃形式存在,其他季节NO₃-主要以NH₄NO₃和HNO₃形式共存;市区Cl-主要以NH₄Cl、KCl和NaCl形式存在,武清区Cl-主要以NH₄Cl、KCl形式存在.④对市区及武清区来说,均相反应和非均相反应是SO₄2-重要生成途径,均相反应是生成NO₃-的主要途径.研究显示,代表一次排放的机动车源、燃煤源和二次无机粒子混合源对天津市PM_2.5中水溶性离子贡献率最高,工业源和扬尘源对市区的影响较大,农业源对武清区的影响较大.      

壳聚糖/聚乙二醇/丙烯酸吸附剂对Cu2+、Co2+和Ni2+的吸附选择性和重复利用性

采用扫描电镜(SEM)和红外光谱(FT-IR)对辉光放电电解等离子体(GDEP)技术引发制备的壳聚糖/聚乙二醇/丙烯酸(CS/PEG/AA)聚合物吸附剂的形貌和结构进行了表征.研究了该吸附剂对Cu~(2+)、Co~(2+)和Ni~(2+)的吸附选择性、重复利用性和解吸动力学行为,同时结合X射线光电子能谱(XPS)探讨了可能的吸附机理.结果表明,CS、PEG和AA发生接枝共聚形成聚合物,其表面呈现疏松、多孔的三维网络结构;吸附最佳pH为4.8;在含有Cu~(2+)、Co~(2+)和Ni~(2+)的混合溶液中,CS/PEG/AA对Cu~(2+)有较好的吸附选择性;在EDTA-4Na洗脱液中CS/PEG/AA具有优异的再生和重复利用性,解吸动力学符合解吸准二级模型;Cu~(2+)在CS/PEG/AA上的吸附是由离子交换、配位螯合等共同作用的复杂的物理化学过程.     

Synthesis, characterization and application of Lagerstroemia speciosa embedded magnetic nanoparticle for Cr(VI) adsorption from aqueous solution

Lagerstroemia speciosa bark (LB) embedded magnetic nanoparticles were prepared by co-precipitation of Fe²⁺ and Fe³⁺ salt solution with ammonia and LB for Cr(VI) removal from aqueous solution. The native LB, magnetic nanoparticle (MNP), L. speciosa embedded magnetic nanoparticle (MNPLB) and Cr(VI) adsorbed MNPLB particles were characterized by SEM–EDX, TEM, BET-surface area, FT-IR, XRD and TGA methods. TEM analysis confirmed nearly spherical shape of MNP with an average diameter of 8.76 nm and the surface modification did not result in the phase change of MNP as established by XRD analysis, while led to the formation of secondary particles of MNPLB with diameter of 18.54 nm. Characterization results revealed covalent binding between the hydroxyl group of MNP and carboxyl group of LB particles and further confirmed its physico-chemical nature favorable for Cr(VI) adsorption. The Cr(VI) adsorption on to MNPLB particle as an adsorbent was tested under different contact time, initial Cr(VI) concentration, adsorbent dose, initial pH, temperature and agitation speed. The results of the equilibrium and kinetics of adsorption were well described by Langmuir isotherm and pseudo-second-order model, respectively. The thermodynamic parameters suggest spontaneous and endothermic nature of Cr(VI) adsorption onto MNPLB. The maximum adsorption capacity for MNPLB was calculated to be 434.78 mg/g and these particles even after Cr(VI) adsorption were collected effortlessly from the aqueous solution by a magnet. The desorption of Cr(VI)-adsorbed MNPLB was found to be more than 93.72% with spent MNPLB depicting eleven successive adsorption–desorption cycles.     

烟花爆竹燃放对北京大气污染物和水溶性无机离子的影响

为了解春节期间烟花爆竹燃放对北京大气污染物和PM_2.5中水溶性无机离子贡献的影响,采用浓度特征对比、相关性分析等方法,对2011年2月1日-3月1日期间的PM₁₀、气态污染物、PM_2.5中水溶性无机离子浓度等在线数据进行了分析.结果表明:烟花爆竹的燃放会在短时间内加重PM₁₀颗粒物污染,集中燃放期（含除夕、春节、正月初五、元宵节）ρ（PM₁₀）和φ（SO₂）（分别为232μg/m3和40.2×10-9）是非集中燃放期（63μg/m3和16.0×10-9）的3.7和2.5倍,燃放烟花爆竹对ρ（PM₁₀）和φ（SO₂）的小时贡献率分别达到56.8%和35.6%;但对φ（CO）、φ（NO）、φ（NO₂）无显著影响.而观测期间由其他因素导致的污染期ρ（PM₁₀）和各气态污染物小时体积分数有所增加,分别是非集中燃放期的3.0~8.3倍.燃放烟花爆竹对PM_2.5中ρ（Mg2+）、ρ（K+）、ρ（Cl-）的影响最大,分别为非集中燃放期的65.0、31.6、6.9倍,贡献率分别为88.6%、87.2%、65.8%. ρ（Mg2+）、ρ（K+）与ρ（Cl-）在集中燃放期表现出较高的相关性（R>0.9）.污染期ρ（SO₄2-）、ρ（NO₃-）、ρ（NH₄+）明显升高,分别为非集中燃放期的3.8、16.4、8.3倍,同时高于集中燃放期（分别为2.7、2.5、2.1倍）.集中燃放期PM_2.5中主要以NH₄HSO₄、NH₄NO₃、KNO₃、KCl、NH₄Cl、MgCl₂等形式存在.集中燃放期硫氧化物转化率（SOR）高于非集中燃放期和污染期,而氮氧化物转化率（NOR）则是污染期最高.研究显示,燃放烟花爆竹对ρ（PM₁₀）及PM_2.5中ρ（Mg2+）、ρ（K+）、ρ（Cl-）影响最大,污染期各离子浓度均有大幅升高,NOR在污染期的高值是导致ρ（NO₃-）升高的重要原因.      

Spatial variability and possible sources of acetate and formate in the surface snow of East Antarctica

Spatial trends of acetate(Ac~-) and formate(Fo~-) were determined in surface snow samples along a coastal-inland transect(180 km) in the ice cap region at Princess Elizabeth Land and along a coastal transect in the Amery Ice Shelf(130 km),East Antarctica.Variations in both Ac-and Fo-seem to be unrelated to the acidity of snow.Ionic balance determined for the snow samples indicate the availability of HNO3 that could undergo photolysis to produce hydroxyl radical(UOH),one of the major reactants involved in oxidation reactions with organic matter.The strong positive correlations between Ac~- and NO~-_3 in snow from both regions indicate that NO~-_3 mediatedUOH-oxidation of organic compounds in snow could be an important source of Ac-within the snowpack.On the other hand,negative correlation between Fo~- and NO~-_3 might indicate that sources other thanUOH-oxidation of organic matter may be dominant in the case of Fo~-.Higher Ac~- concentrations in the ice cap compared to the ice shelf correspond with long-range transport of biomass burning emissions to the ice cap region.Interaction of Ac~- and Fo~- with alkaline minerals could lead to their stability in the snowpack and minimize their loss from the snow surface.Resident microbial communities could also influence the budget of the carboxylic acids in snow.     

杭州市PM2.5中水溶性离子的污染特征及其消光贡献

对杭州市2013年大气PM_(2.5)进行采样分析,探讨了其中水溶性离子的污染特征和消光贡献.杭州市PM_(2.5)中总水溶性离子的质量浓度为37.5μg·m~(-3),占PM_(2.5)质量浓度的44.4%,二次离子SNA(SO_4~(2-)、NO_3~-和NH_4~+)是水溶性离子的主要成分,共占到水溶性离子的83.4%.PM_(2.5)和主要水溶性离子的质量浓度都在冬季最大,夏季最低,夏秋季水溶性离子占PM_(2.5)的比值明显高于冬春季,而SNA在总水溶性离子中的比例4个季节非常接近.燃料燃烧和汽车尾气排放导致的二次离子生成,对杭州市PM_(2.5)贡献最大.SOR和NOR的年平均值分别为0.27和0.15,SO_2在大气中的转化率大于NO_x,SOR和NOR与相对湿度都呈现出明显正相关,非均相氧化过程对SO_4~(2-)和NO_3~-的生成具有重要贡献.气溶胶中[NO_3~-]/[SO_4~(2-)]的年平均值为0.63,主要受到燃煤排放的影响.霾天随着霾污染等级的逐渐加重,PM_(2.5)、水溶性离子和SNA的浓度都逐渐增大,SOR和NOR值也不断升高,霾天稳定的天气条件,能有效促进污染物的积累和二次转化.PM_(2.5)和SNA的质量浓度与大气消光系数都呈现出明显正相关,使用IMPROVE公式对不同化学组分消光系数的计算结果能够基本反映出气溶胶对大气散射的变化趋势,其结果显示SNA对大气总消光系数的贡献达60.8%.SNA的消光系数冬季最高,夏季最低,随着霾污染等级的加重,SNA的消光系数和对总消光的贡献比例也逐步增加.     

葡萄藻生物膜贴壁培养处理含钴工业废水与烃类生产的耦合

工业废水污染日趋严重,水体中重金属钴污染因难处理、高危害等问题成为废水净化的关键.传统治理重金属工业废水的方法难以应用.为寻求处理工业废水"绿色生态"可行性路径,本文以葡萄藻Botryococcus braunii SAG 807-1为研究对象,应用贴壁培养技术对含钴工业废水进行处理研究.结果表明,葡萄藻贴壁培养可处理工业废水,4.5 mg·L~(-1)Co~(2+)对葡萄藻生长影响不大,却可以促进长链烃类的合成,提高烃产量.葡萄藻贴壁培养去除Co2+的能力为1 473.9μmol·g~(-1),远高于报道的微藻P.littoralis.本研究为绿色高能燃料烃类的生产与工业废水处理耦合提供理论基础.     

外源Ca2+和K+作用下河口区碱蓬水质净化效果和耐盐碱提高机制

入海河流中较高的氮、磷污染负荷严重影响近岸海域水质,必须加强陆海统筹.但河口区受海水倒灌影响,水体盐碱浓度高且变化范围大,植物生长困难,去除氮磷能力低,提高植物生存能力是亟需解决的难题.本文通过添加适当浓度的Ca~(2+)和K~+,研究提高植物耐盐碱能力以及降低富营养化风险的可能性.结果表明,在pH 8、盐度20‰条件下,外源Ca~(2+)和K~+浓度分别为8 mmol·L~(-1)和10 mmol·L~(-1)的水培实验中,碱蓬对总氮及总磷的去除效率均最高,为对照组的1. 53～1. 87倍,生长最好,相对生长速率(RGR)为对照组的2. 4倍和2. 0倍,同浓度Ca~(2+)的缓解作用大于K~+.外源Ca~(2+)和K~+提高耐盐碱能力的机制体现在碱蓬渗透调节功能的提升:无机渗透调节机制为平衡Na~+/K~+,提高碱蓬持水能力,叶片与根系中无机离子含量与含水量相关性均在0. 966以上;有机渗透调节机制为促进甜菜碱等小分子有机物积累,降低细胞膜脂过氧化作用,Ca~(2+)和K~+缓解作用下叶片丙二醛含量最大降幅达72. 9%和61. 7%.外源Ca~(2+)和K~+能够增强碱蓬渗透调节能力,提升耐盐碱能力,促进碱蓬生长,提高碱蓬对氮磷的去除率.     

新型钛酸钠填料对Cu2+、Pb2+、Zn2+和Cd2+的竞争吸附研究

以钛酸钠纳米纤维为原材料制备新型钛酸钠填料,对水体中常见的重金属(Cu~(2+)、Pb~(2+)、Zn~(2+)和Cd~(2+))进行竞争吸附实验研究,分析了四元、三元及双组分竞争吸附的选择性吸附特性,并探讨了4种金属离子在钛酸钠填料上的相互作用关系.结果显示,初始浓度较低时,4种离子之间的相互影响差异性不明显;随着初始浓度的升高,4种离子的竞争吸附分配系数都呈下降的趋势,竞争吸附系数大小顺序为:Pb~(2+)Cu~(2+)Zn~(2+)Cd~(2+),这与重金属离子的第一水解常数大小顺序一致.竞争吸附结果表明,水中存在Pb~(2+)时,其余3种离子的吸附都会被抑制,尤其对Zn~(2+)和Cd~(2+)的抑制更显著,即在钛酸钠填料上Pb~(2+)的竞争吸附能力最强,Cu~(2+)次之,而Zn~(2+)和Cd~(2+)的竞争吸附能力较弱,其吸附过程容易受到其他二价金属离子的抑制.