基于UV-vis及EEMs解析周村水库夏秋季降雨不同相对分子质量DOM的光谱特征及来源

运用三维荧光光谱(EEMs)技术结合平行因子分析法(PARAFAC)以及紫外-可见光谱技术,对周村水库夏秋季降雨不同相对分子质量雨水的溶解性有机物(DOM)光谱特征和来源进行分析.结果表明,夏秋季降雨不同相对分子质量DOM的紫外-可见吸收光谱并无明显特征峰,吸收系数的变异系数在75%~469%之间,表明其性质在不同季节和相对分子质量上存在差异;a254和E3/E4变化说明DOM的相对浓度和富里酸所占DOM的比例随着季节由夏入秋而增加;三维荧光通过PARAFAC解析出4种组分,分别为类腐殖质(C1、C2)、可见区富里酸(C3)和类蛋白(C4);对4个组分进行相关性分析,结果显示C1与C2、C3以及C4具有显著的相关性(P0.01),C2与C3具有显著的相关性(P0.01);夏秋季降雨DOM总荧光强度以及各组分荧光强度差异明显(P0.05),类腐殖质(C1+C2)是其主要成分、富里酸的荧光强度和所占比例随着季节由夏入秋而增加、类蛋白随着季节由夏入秋而减少;夏秋季降雨有机物来源都呈现以自生源为主的特征,夏季降雨具有自生源特征更强、类蛋白物质含量和占比更多的特点;PCA分析显示夏秋季降雨中不同相对分子质量雨水荧光特征差异明显,并且组分C1、C2和C3与DOM特征参数[HIX、Fn(355)、Fn(280)、E3/E4、a254]以及水质参数(硝氮、氨氮、总氮以及有机碳)显著相关性(P0.01).通过对夏秋季不同降雨相对分子质量的DOM光谱特征研究,可以进一步分析水库大气沉降型外源输入的有机物污染特征,并为水库水质管理提供技术支持.     

Spatiotemporal dynamics of cell abundance, colony size and intracellular toxin concentrations of pelagic and benthic Microcystis in Lake Caohai, China

Lake Caohai has experienced extensive Microcystis blooms in recent years,and to improve its water quality,the local government carried out a series of water control measures.To better understand the dynamics of both pelagic and benthic Microcystis and their characteristics in Lake Caohai,we conducted a 1-year investigation from December 2015to December 2016 to gain a seasonal outlook on the distribution and dynamics of cell abundance,colony size and intracellular microcystins(MCs)of Microcystis.The results indicated that the Microcystis bloom occupied primarily the northeastern region and then moved gradually from lakeshore to lake center.The perennial southwesterly winds and the water inflow from northeast to southwest in Lake Caohai determined the spatiotemporal distribution of pelagic Microcystis.Benthic Microcystis was mainly distributed in the northeastern region in summer,occupied the lake center in autumn and then occupied the southeastern region in winter,determined by the sedimentation of pelagic Microcystis and the death of benthic Microcystis.Small colonies(20-60μm)overwintered more easily in both water column and sediment.The concentrations of intracellular toxin of benthic Microcystis were observed to be significantly higher than those of pelagic Microcystis.This might be because Microcystis synthesized large amount of MCs to acclimate to an unfavorable benthic environment.This knowledge on the dynamics of Microcystis expands our understanding of mechanisms underpinning the formation of Microcystis blooms.     

Influence of COM-peptides/proteins on the properties of flocs formed at different shear rates

Coagulation followed by floc separation is a key process for the removal of algal organic matter(AOM) in water treatment. Besides optimizing coagulation parameters,knowledge of the properties of AOM-flocs is essential to maximizing AOM removal.However, the impact of AOM on the floc properties remains unclear. This study investigated how peptides/proteins derived from the cellular organic matter(COM) of the cyanobacterium Microcystis aeruginosa influenced the size, structure, and shape of flocs formed at different shear rates(G). Flocs formed by kaolinite, COM-peptides/proteins and a mixture of the same were studied, and the effect of intermolecular interactions between floc components on floc properties was assessed. The coagulation experiments were performed in a Taylor–Couette reactor, with aluminum(Al) or ferric sulphate(Fe) utilized as coagulants. Image analysis was performed to gauge floc size and obtain data on fractal dimension. It was found that floc properties were affected by the presence of the COM-peptides/proteins and the coagulant used. COM-peptides/proteins increased floc size and porosity and widened floc size distributions. The Fe coagulant produced larger and less compact flocs than Al coagulant. Moreover, the decrease in floc size that occurred in parallel with increase in shear rate was not smooth in progress. A rapid change for the kaolinite-coagulant suspension and two rapid changes for the suspensions containing COM were observed. These were attributed to various intermolecular interactions between floc components participating in coagulation at different G. Based on the results obtained, shear rates suitable for efficient separation of flocs containing COM were suggested.     

Woody species Rhus chinensis Mill. seedlings tolerance to Pb: Physiological and biochemical response

Screening potential plant species is a crucial consideration in phytoremediation technology. Our previous study demonstrated that Rhus chinensis Mill. seedlings had potentials for phytoremediation of Pb contaminated soil. However, its bioaccumulation and tolerance characteristics remain unclear. Seedling growth, LMWOAs secreted by roots, Pb subcellular distribution and chemical forms, and mineral elements in R. chinensis tissues were evaluated under different Pb concentrations (0, 25, 50, 100, 200 and 400?mg/L) in culture solution at 14?days after planting. R. chinensis did not show visual symptoms of Pb toxicity under lower Pb treatments; however, Pb significantly declined the growth of seedlings under higher Pb treatments. Higher Pb stress also decreased the concentrations of nitrogen in leaves, but increased the concentrations of P and K in roots. Pb stress also decreased Mn concentrations in leaves. A great quantity of Pb was uptake and mostly retained in R. chinensis roots. Nonetheless, R. chinensis can still concentrate 459.3 and 1102.7?mg/kg Pb in leaves and stems, respectively. Most of Pb in R. chinensis tissues was stored in the cell wall with HAc-, HCl-, and NaCl-extractable form. LMWOAs secreted by R. chinensis roots showed a strong positive correlation with Pb concentrations in all plant tissues and with P in roots. Our results suggested that Pb deposited in the cell wall and integration with phosphate or oxalate might be responsible for the tolerance of R. chinensis under Pb stress in short period.     

具有不同粒径和相同表面结构纳米银颗粒的制备及表征

具有不同粒径相同表面结构AgNPs（nano-silver,纳米银）的可控合成是开展AgNPs毒性研究和风险评估的基础,也是材料制备领域的难点之一.采取化学还原的方法,使用AgNO₃（硝酸银）作为反应前体,使用TSC（trisodium citrate,柠檬酸三钠）和NaBH₄（sodium borohydride,硼氢化钠）作为稳定剂及还原剂,通过优化剂量比和反应条件等合成参数,一步式原位反应生成不同粒径的AgNPs.利用TEM（透射电子显微镜）、UV-Vis（紫外可见分光光谱）、ICP-MS（电感耦合等离子体质谱）、FT-IR（傅里叶转换红外光谱）和DLS（动态光散射）等技术综合表征了合成纳米颗粒的形貌和结构性质.结果表明:①TEM结果显示,3种AgNPs均为球形且粒径分别为12、25和33 nm.②UV-Vis表征结果显示,所得产物在391~408 nm之间有较强吸收,说明合成产物为AgNPs.③利用ICP-MS测试样品中未反应的ρ（Ag+）,得出该制备方法具有高产率（>99%）.④DLS结果证实了合成的AgNPs在水溶液中带负电荷且具有较窄的粒度分布.⑤FT-IR结果显示,所制备的AgNPs表面结构一致,具有碳碳双键、酯基、羧基和羟基等官能团,在材料制备的过程中,溶液的初始配比、反应时间及环境条件都会对反应结果产生很大影响.研究显示,通过化学还原方法制备的AgNPs具有方法简便、重现性好、产率高和单分散性的特点,所制备的系列AgNPs颗粒表面结构一致,具有良好的化学稳定性.      

Toxicity and mechanisms of action of titanium dioxide nanoparticles in living organisms

Titanium dioxide nanoparticles(TiO_2 NPs) are one of the most widely used nanomaterials in the consumer products, agriculture, and energy sectors. Their large demand and widespread applications will inevitably cause damage to organisms and ecosystems. A better understanding of TiO_2 NP toxicity in living organisms may promote risk assessment and safe use practices of these nanomaterials. This review summarizes the toxic effects of TiO_2 NPs on multiple taxa of microorganisms, algae, plants, invertebrates, and vertebrates. The mechanism of TiO_2 NP toxicity to organisms can be outlined in three aspects: The Reactive Oxygen Species(ROS)produced by TiO_2 NPs following the induction of electron–hole pairs; cell wall damage and lipid peroxidation of the cell membrane caused by NP-cell attachment by electrostatic force owing to the large surface area of TiO_2 NPs; and TiO_2 NP attachment to intracellular organelles and biological macromolecules following damage to the cell membranes.     

腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

广州地区不同粒径段大气颗粒物中水溶性有机碳的吸光贡献

对广州地区春季（2015年3~4月）、夏季（2015年6~7月）、秋季（2015年9~10月）、冬季（2015年12月~2016年1月）四个季节6个粒径段（<0.49、0.49~0.95、0.95~1.5、1.5~3.0、3.0~7.2以及7.2~10.0μm）的大气颗粒物样品中水溶性有机碳（WSOC）的浓度和光学性质等变化特征进行了研究.结果表明,WSOC的浓度水平呈现冬季[（5.07±2.80）μg/m³]>秋季[（3.87±1.51）μg/m³]>春季[（3.60±1.16）μg/m³]>夏季[（2.42±0.51）μg/m³]的季节变化特征;WSOC的质量平均直径（MMD）为0.57μm （春）、0.42μm （夏）、0.49μm （秋）和0.56μm （冬）.WSOC的质量吸收效率MAE₃₆₅差异较大,分布在0.18~1.42m²/g之间,冬季最高;吸收波长指数AAE值分布在3.6~9.8之间.细颗粒物（<3μm）中WSOC对PM₁₀WSOC总吸光的贡献达到了90%以上,其中<0.49μm颗粒物的贡献超过50%.在300~500nm之间,春季、夏季、秋季和冬季WSOC对颗粒物总吸光比例平均值分别为5.23%、2.95%、3.04%和6.92%;其中<0.49μm粒径段的贡献最高,分别为3.11%、1.79%、1.65%和3.45%.进一步通过特征紫外吸光度SUVA值的分析表明芳香性和分子量可能是影响WSOC吸光能力的重要因素.粒径越小颗粒物含有越多的不饱和键,使得MAE₃₆₅值较高.     

重庆市不同粒径颗粒物中水溶性离子污染特征

于2010年3月~2011年2月和2017年1~12月在重庆主城区连续采集PM_1.0、PM_1.0~2.5和PM_2.5~10样品,采用离子色谱测定了样品中9种水溶性无机离子（WSIIs）含量,研究了近年来不同粒径颗粒物中主要离子的污染特征.结果表明,2017年重庆市PM_1.0、PM_1.0~2.5和PM_2.5~10中WSIIs年均浓度和占比分别为24.10,32.89,39.11μg/m³和41.8%、40.3%、38.6%,较2010年均有所下降（39.85,47.84,57.12μg/m³和49.2%、46.6%、36.2%）,但NO₃^-浓度和占比呈上升趋势（分别上升12.3%~27.8%和53.1%~78.2%）,且成为2017年冬季首要离子.SO₄^2-、NO₃^-、NH₄⁺、Cl^-、K⁺和Na⁺主要分布在细粒子中,F^-、Mg²⁺和Ca²⁺主要分布在粗粒子中.重庆颗粒物呈弱碱性,其中粗粒子碱性强于细粒子,NH₄⁺主要以（NH₄）₂SO₄和NH₄NO₃的形式存在.与2010年不同,2017年细粒子中SO₄^2-和NO₃^-浓度均随相对湿度增大而快速上升,非均相反应已成为2017年SO₄^2-和NO₃^-形成的重要途径,且在PM_1.0中尤为突出.随污染加重,不同粒径下各类WSIIs演化特征各异,其中2017年细粒子中NO₃^-浓度及其对WSIIs贡献大幅升高,并成为重污染形成的主因,而SO₄^2-和扬尘源示踪物（Mg²⁺、Ca²⁺）贡献呈下降趋势.与2010年相比,2017年各粒径中NO₃^-/SO₄^2-比值随污染加重大幅升高,且重污染日比值均大于1.0.细粒子中WSIIs主要来源于二次转化,粗粒子主要来源于扬尘.2017年扬尘污染较2010年有所减缓,但二次源对WSIIs贡献上升明显,尤其是NO₃^-的二次生成,因此对NOx排放源的管控是WSIIs减排的重要途径.研究结果对了解近年来重庆市大气颗粒物污染来源及形成机制研究具有重要参考价值.     

微介复合固体酸β分子筛催化芳烃硝化合成研究

研究了多级孔道β分子筛催化剂对芳烃(氯苯)的硝化反应,显示具有优异的催化作用。在以硝酸为硝化剂,氯苯∶催化剂=3∶1,60℃反应2 h条件下,对比传统β分子筛,自制多级孔道β分子筛的催化活性较高,且氯苯的对位选择性均有所提高,对位/邻位比分别从0.5提高到1.2。多级孔道β分子筛催化剂重复使用5次,催化活性保持稳定,且随着孔道比表面积增加,催化剂稳定性更好。