铝钛改性MCM-41材料对污水中铅镉的吸附研究

研究了改性MCM-41材料对污水中重金属铅、镉离子的吸附行为。在MCM-41材料中加入Al、Ti两种诱因金属离子来合成新的Al-Ti-MCM-41及Ti-Al-MCM-41改性材料,通过氮气吸附-脱附等温线对Al-Ti-MCM-41(Al/Ti=1∶1)及Al-Ti-MCM-41(Al/Ti=2∶1)样品进行了表征,并采用改性后的MCM-41材料为吸附剂对含有二价铅、镉离子的溶液进行吸附实验,考察了吸附剂投加量,Pb2+、Cd2+初始质量浓度和吸附温度对吸附的影响。结果表明:改性Al-Ti-MCM-41(Al/Ti=1∶1)材料的最可几孔径和比孔容分别为16.68 nm和0.046 cm3/g,由BJH计算得到的平均孔径为17.02 nm;Al-Ti-MCM-41(Al/Ti=2∶1)的最可几孔径和比孔容分别为16.88 nm和0.083 cm3/g,由BJH计算得到的平均孔径为17.08 nm。Al-Ti-MCM-41(Al/Ti=1∶1)对Cd2+的吸附率为99.8%;Al-Ti-MCM-41(Al/Ti=2∶1)对Pb2+的吸附率为99.96%;Pb2+和Cd2+的吸附容量随吸附剂投加量的增加而降低,随离子初始浓度的增大而增加;温度越高越有利于吸附。该研究重点考察改性MCM-41材料在重金属铅镉离子污染治理中的性能,从而为解决重金属铅镉的污染,加强环境保护提供理论支撑和技术支持,具有明确的现实意义。     

纳米TiO_2纤维的制备及其光催化降解甲醛研究

以胶原纤维为模板制备纳米TiO2纤维用于光助催化降解甲醛气体,用扫描电镜(SEM)、X射线衍射(XRD)和N2吸附-脱附技术对纳米TiO2纤维进行了表征。结果表明,纳米TiO2纤维的比表面积为11.33 m2/g,晶型为锐钛矿型。在相同催化反应条件下纳米TiO2纤维对甲醛气体的催化降解率与商品纳米TiO(2Degussa P25)催化剂相当。纳米TiO2纤维的用量、甲醛气体初始浓度是影响催化效果的两个因素。当甲醛气体初始浓度为0.270 mg/m3,相对湿度为38%,气体流速0.1 L/min,纳米TiO2纤维用量为1.0 g时,甲醛的降解率达到96%。因此,纳米TiO2纤维可用于室内甲醛气体的催化降解。     

钙、镁离子在水流作用下对铜绿微囊藻生长的影响

为了解在"引江济太"过程中大量钙、镁离子的引入对铜绿微囊藻生长的影响,本实验在控制温度和光照条件下,室内模拟不同钙、镁离子浓度在两个特征流速5 cm/s和15 cm/s下微囊藻的生长。实验结果表明,微囊藻藻密度随钙、镁离子浓度的增加而增加,流速在15cm/s下微囊藻最大藻密度(9 236.4×104cell/mL)是流速为5 cm/s下最大藻密度(2 873.72×104cell/mL)的3倍,流速为15 cm/s下微囊藻最大比增长速率均较5 cm/s下的高。这可能是在水流产生的剪切力作用下藻细胞胞外多糖增加,粘附更多的钙、镁离子更利于钙、镁离子迁移到胞内,同时胞外附着的钙、镁离子尤其钙离子形成桥联,使微囊藻细胞形成群体产生微环境利于微囊藻的生长。水流对微囊藻利用钙、镁离子有重要的影响,这为有效调水抑制蓝藻生长提供科学依据。     

有机粘土疏水性吸附过程的分子模拟:烷基碳原子数和有机物logK_(ow)的影响

基于从分子尺度上解析改性剂烷基碳原子数和有机物疏水性对有机粘土吸附能力的影响机制,以从头算的量子化学计算方法(MP2/6-31g(d))模拟了有机粘土在水溶液中的吸附过程.通过计算吸附前后几何构型、能量、化学键和电荷分布等参数的变化,分析了影响有机粘土疏水性吸附的关键因素,并对疏水性吸附作用力的化学本质进行了初步探讨.计算结果表明,烷基碳原子数增加对提高有机物吸附能的作用并不显著,长链烷基提高有机粘土吸附容量的真正原因在于其可提供更多的有机物吸附位.有机物的疏水性(以正辛醇-水分配系数logKow表征)是影响疏水性吸附过程的关键因子,水分子的引力作用对疏水性吸附具有决定性影响,理论上解释了普遍存在的有机物吸附量与logKow呈正相关的实验现象.疏水性吸附力的作用前提是有机物为疏水性,即当水分子的引力作用较弱时疏水性作用力才可以表现出来;而对于亲水性有机物,疏水性吸附力会被水分子的引力所抵消,吸附强度减弱.模拟红外光谱和电荷分布结果表明,吸附前后无化学键断裂和电子得失的发生,只有原子电荷密度的微小变化,据此推测疏水性吸附力以分子间弱相互作用力——London色散力为主.     

道南膜技术测定Ca(NO3)2溶液体系中汞的化学形态

虽然道南膜技术(DMT)已经成功用于土壤/溶液中多种重金属自由态离子浓度的测定,但DMT技术测定Hg的形态尚未解决.采用DMT测定Ca(NO3)2溶液体系中Hg化学形态.实验结果表明,Hg在阳离子交换膜内的吸附除静电吸附外还存在结合力更强的化学吸附,Hg在阳离子交换膜内扩散成为Hg跨膜传输受阻的主要因素,限制道南膜技术用于Hg形态测定.Hg2+和Hg(OH)2都表现出在阳离子交换膜上的强烈吸附,供端(Donor)Hg损失达50%以上.缩短试验时间至8h以内,可在一定程度上降低Hg吸附.计算结果表明,由于大量的Hg滞留在阳离子交换膜内,在计算受端(Acceptor)Hg浓度时引入滞留系数补偿供端Hg的损失,较好地预测了Ca(NO3)2溶液体系中Hg的化学形态.     

广州市不同功能区大气二噁英含量和分布特征研究

应用气相色谱-高分辨率质谱仪(GC-HRMS)对广州市秋冬季6个区域环境空气样品中的17种2,3,7,8-氯代二英含量进行了检测.结果表明,广州市各观测区域大气中二英毒性当量浓度范围为0.151～2.230pg.m-3,均值为0.418pg.m-3.各观测区域空气中二英毒性当量浓度分布存在一定的差异,本研究的背景区、居民住宅区和商业区二英毒性当量浓度较低且水平相近,分别为(0.294±0.099)、(0.305±0.115)、(0.308±0.102)pg.m-3.交通枢纽区、郊区和工业区二英毒性当量浓度相对较高,分别为(0.342±0.049)、(0.423±0.113)和(0.838±0.704)pg·m-3.广州市不同功能区二英毒性当量浓度呈现背景区<住宅区<商业区<交通枢纽区<郊区<工业区的分布特点.与2004年相比,广州市城区二英毒性当量浓度有所下降,郊区毒性当量浓度有所上升.     

Characteristics and recent trends of sulfur dioxide at urban, rural, and background sites in North China: Effectiveness of control measures

SO₂ measurements made in recent years at sites in Beijing and its surrounding areas are performed to study the variations and trends of surface SO₂ at different types of sites in Northern China. The overall average concentrations of SO₂ are (16.8 ± 13.1) ppb, (14.8 ± 9.4) ppb, and (7.5 ± 4.0) ppb at China Meteorological Administration (CMA, Beijing urban area), Gucheng (GCH, relatively polluted rural area, 110 km to the southwest of Beijing urban area), and Shangdianzi (SDZ, clean background area, 100 km to the northeast of Beijing urban area), respectively. The SO₂ levels in winter (heating season) are 4-6 folds higher than those in summer. There are highly significant correlations among the daily means of SO₂ at different sites, indicating regional characteristics of SO₂ pollution. Diurnal patterns of surface SO₂ at all sites have a common feature with a daytime peak, which is probably caused by the downward mixing and/or the advection transport of SO₂-richer air over the North China Plain. The concentrations of SO₂ at CMA and GCH show highly significant downward trends (-4.4 ppb/yr for CMA and -2.4 ppb/yr for GCH), while a less significant trend (-0.3 ppb/yr) is identified in the data from SDZ, reflecting the character of SDZ as a regional atmospheric background site in North China. The SO₂ concentrations of all three sites show a significant decrease from period before to after the control measures for the 2008 Olympic Games, suggesting that the SO₂ pollution control has long-term effectiveness and benefits. In the post-Olympics period, the mean concentrations of SO₂ at CMA, GCH, and SDZ are (14.3 ± 11.0) ppb, (12.1 ± 7.7) ppb, and (7.5 ± 4.0) ppb, respectively, with reductions of 26%, 36%, and 13%, respectively, compared to the levels before. Detailed analysis shows that the differences of temperature, relative humidity, wind speed, and wind direction were not the dominant factors for the significant differences of SO₂ between the pre-Olympics and post-Olympics periods. By extracting the data being more representative of local or regional characteristics, a reduction of up to 40% for SO₂ in polluted areas and a reduction of 20% for regional SO₂ are obtained for the effect of control measures implemented for the Olympic Games.     

Synthesis, characterization and experimental investigation of Cu-BTC as CO2 adsorbent from flue gas

Porous Cu-BTC material was synthesized by the solvothermal method. Powder X-ray diffraction (PXRD) was used to test the phase purity of the synthesized material and investigate its structural stability under the influence of flue gas components. The thermal stability of the material was determined through thermal gravimetric (TG) analysis. Scanning electron microscopy (SEM) was employed to study the microstructure of the material. Cu-BTC was demonstrated not only to have high CO₂ adsorption capacity but also good selectivity of CO₂ over N₂ by means of packed bed tests. The adsorption capacity of Cu-BTC for CO₂ was about 69 mL/g at 22°C. The influence of the main flue gas components on the CO₂ capacity of the material were discussed as well.     

Absorption characteristics of new solvent based on a blend of AMP and 1,8-diamino-p-menthane for CO2 absorption

Aqueous 1,8-diamino-p-menthane (KIER-C3) and commercially available amine solutions were tested for CO₂ absorption. A 2-amino- 2-methyl-1-propanol (AMP) solution with an addition of KIER-C3 showed 9.3% and 31.6% higher absorption rate for CO₂ than the AMP solution with an addition of monoethanolamine (MEA) and ammonia (NH₃), respectively. The reaction rate constant for CO₂ absorption by the AMP/KIER-C3 solution was determined by the following equation: k_2,AMP/C3 = 7.702×10⁶ exp (-2248.03/T). A CO₂ loading ratio of the AMP/KIER-C3 solution was also 2 and 3.4-times higher than that of the AMP/NH3 solution and the AMP/MEA solution, respectively. Based on the experimental results, KIER-C3 may be used as an excellent additive to increase CO₂ absorption capability of AMP.     

A GFP-based bacterial biosensor with chromosomally integrated sensing cassette for quantitative detection of Hg(II) in environment

A mercury biosensor was constructed by integrating biosensor genetic elements into E. coli JM109 chromosome in a single copy number, using the attP/attB recombination mechanism of λphage. The genetic elements used include a regulatory protein gene (merR) along with operator/promoter (O/P) derived from the mercury resistance operon from pDU1358 plasmid of Serratia marcescens. The expression of reporter gene gfp is also controlled by merR/O/P. Integration of the construct into the chromosome was done to increase the stability and precision of the biosensor. This biosensor could detect Hg(II) ions in the concentration range of 100-1700 nmol/L, and manifest the result as the expression of GFP. The GFP expression was significantly different (P ≤ 0.05) for each concentration of inducing Hg(II) ions in the detection range, which reduces the chances of misinterpretation of results. A model using regression method was also derived for the quantification of the concentration of Hg(II) in water samples.