铜铈复合氧化物上石化行业典型VOCs的氧化行为与动力学

采用共沉淀法和等体积浸渍法制备了CuCeO x复合催化剂,对材料的物化性质进行了XRD、低温N2吸脱附、H2-TPR和O2-TPD表征.以石化行业典型VOCs(苯、甲苯和正己烷)为探针污染物,研究了污染物组成与浓度、反应空速、O2浓度、H2O浓度和催化剂种类对其氧化行为的影响,并对反应动力学参数进行了模型拟合.共沉淀得到的催化剂具有均匀的活性相、好的低温可还原性能和较多的活性表面氧物种.甲苯氧化率随着污染物浓度升高而降低,高转化率下苯浓度与其氧化率无相关性,正己烷的氧化率与入口浓度呈正比.苯能够显著抑制甲苯的氧化,而甲苯加入有利于苯的氧化.正己烷对苯氧化的影响较小,但能够促进甲苯的转化,苯系物对正己烷氧化有明显的抑制作用.低空速和高氧浓度都有利于污染物的氧化,氧浓度的变化对正己烷和苯的氧化影响较小.水汽对甲苯的氧化有明显的抑制作用,而对苯和正己烷氧化有明显的促进作用.共沉淀催化剂具有更好的甲苯和苯氧化性能,而无水条件下浸渍催化剂具有更好的正己烷氧化性能.拟一级动力学模型能够很好地模拟不同条件下污染物的氧化行为.     

土壤重金属钝化修复剂生物炭对镉的吸附特性研究

目前以生物炭为代表的生物质对重金属的吸附表现出良好的应用前景.为确定生物炭对溶液中镉的吸附性能,选用由棉花秸秆制备的生物炭,研究吸附等温线、吸附动力学以及温度、pH和离子强度等对生物炭吸附Cd2+的影响.研究表明,生物炭对Cd2+的吸附可以用Freundlich等温线较好地拟合,在不同温度下其饱和吸附量分别为9.738 mg.g-1(288.15 K)、10.14 mg.g-1(298.15 K)、10.40 mg.g-1(308.15 K)和10.71 mg.g-1(318.15 K),热力学参数表明生物炭吸附Cd2+的过程是自发的吸热过程;吸附动力学过程符合二级动力学模型,在40 min即可达到平衡;pH对生物炭吸附Cd2+的影响较大,在pH2～8范围时,生物炭对Cd2+的吸附量随pH的增加先上升后下降;生物炭对Cd2+的吸附量随着溶液离子强度的增大呈降低趋势.该项研究可为生物炭在土壤重金属污染修复中的应用提供一定的理论基础.     

氮氟掺杂二氧化钛(N,F-TiO2)的制备及可见光催化活性的研究

以氨水为氮源,氢氟酸为氟源,采用溶胶-凝胶法制备了氮氟掺杂二氧化钛(N,F-TiO2)光催化剂,并通过X-射线衍射(XRD)和扫描电镜(SEM)技术对其晶型和形态进行表征.最后以酸性红B为模型污染物,探讨了N和F加入量、焙烧温度、焙烧时间、照射时间、催化剂用量、溶液初始浓度和照射功率等因素对N,F-TiO2可见光催化活性的影响.结果表明,制备的N,F-TiO2以锐钛型为主,N和F的掺杂对TiO2的晶相没有明显改变,但可以扩大TiO2的可见光响应范围.当N和F的加入量均为2.0%,且在500℃下焙烧40 min时,得到的N,F-TiO2的可见光催化活性明显高于单N或单F掺杂的TiO2(N-TiO2或F-TiO2).对于50 mL浓度为10.0 mg·L-1的酸性红B溶液,当催化剂加入量为1.5 g·L-1,128W光照3.0 h,溶液pH=5.6时,去除率为85.40%.适当延长光照时间至4.0 h,降解率几乎可达100%.另外,研究还证明了N,F-TiO2催化可见光降解过程中有.OH自由基生成.     

水体悬浮颗粒物对斜生栅藻生理生化及光合活性的影响

通过研究不同浓度(30、40、50、60、70 mg·L-1)和不同粒径(0～75μm、75 ～ 96μm、96 ～150 μm、150～ 250 μm)水体悬浮颗粒物对斜生栅藻(Scenedesmus obliquus)叶绿素a含量、抗氧化系酶活性、脂质过氧化物丙二醛(MDA)含量、可溶性蛋白含量及光合参数变化的影响,探讨了水体悬浮颗粒物对斜生栅藻生理生化及光合活性影响的机制.结果表明,预处理与未处理悬浮颗粒物在一定浓度范围内会促进藻类生长,超过各自临界浓度(预处理为40 mg·L-1、未处理为50 mg·L-1)后,随着颗粒物浓度的增加会对藻类生长产生抑制现象未经处理的相同浓度不同粒径颗粒物对斜生栅藻都表现出抑制作用,0～75μm粒径组颗粒物作用下藻体内超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、MDA和可溶性蛋白质含量等均显著区别于其他粒径组的作用(p＜0.05).经过预处理的相同浓度不同粒径颗粒物中,96～150μm粒径组对藻类的生长抑制较其他粒径组明显,且小粒径组颗粒物对藻类体内SOD、CAT、MDA和可溶性蛋白质含量等影响较大.受不同浓度悬浮颗粒物胁迫的斜生栅藻相对电子传递速率随着时间延长在一定程度上降低,但这种抑制作用在藻细胞的耐受范围,藻细胞可以通过自身调节将电子传递速率恢复到正常水平甚至更高以抵抗逆境环境.     

北京夏季灰霾天臭氧近地层垂直分布与边界层结构分析

后奥运时期首都北京的空气质量被更加关注,尤其是对于灰霾天与光化学复合污染的状况,而近地层数百米高度内的大气污染物与大气物理参数垂直分布观测对于空气质量变化过程评估至关重要.因此,本研究于2009年8月1-16日,在北京市325 m气象塔进行了相应的立体观测,观测平台垂直分布在距离地面高度8、47、120和280 m四层中.同时,在近地面320 m高度以内,分15层分别观测了大气温度、湿度、风速、风向.另外,使用气溶胶后向散射云高仪观测了边界层2.5 km内气溶胶后向散射系数.利用垂直分层的O3数据与边界层物理观测数据并结合天气形势、后向轨迹模式等方法,综合分析了本次观测数据之间的相互关系和内在联系.结果表明:夏季西北部低压槽控制的北京区域不利于低空大气扩散,容易形成光化学污染叠加灰霾污染,污染形成时白天地面小时最大φ(O3)可达120×10-9,280 m高度处可达155×10-9;来自西北偏西的气流一般较为干净,有利于北京污染物的清除,而来自西南和偏南的气流使北京的O3污染加重,导致区域性高浓度O3污染;在稳定天气条件下,夜间残留层与地面的φ(O3)差别越大,次日光化学生成的φ(O3)起点越高,表明残留层O3在次日混合层抬升过程中卷夹到地面,影响地面空气质量;300 m以内的近地层,在50 m高度左右存在φ(O3)变化程度剧烈层,这是城市冠层界面与大气化学反应共同作用的结果.     

太湖春季和秋季蓝藻光合作用活性研究

采用Phyto-PAM浮游植物分析仪测定太湖蓝藻光合作用活性的时空间分布.结果表明,太湖蓝藻光合活性具有显著的时空差异:春季蓝藻的最大光量子产量F_v/F_m (可变荧光和最大荧光之比)和实际光量子产量F_v'/F_m'分别在0.35~0.49和0.16~0.29之间,秋季蓝藻分别在 0.33~0.53和0.21~0.43之间,太湖秋季蓝藻的最大光合作用能力和实际光合作用能力大于春季蓝藻.春季和秋季蓝藻的非光化学淬灭NPQ(non-photochemical quenching)分别在0.012~0.17和0.035~0.26之间,秋季蓝藻的NPQ高于春季蓝藻,说明秋季蓝藻的自我保护能力高于春季蓝藻.快速光响应曲线(Rapid light curve, RLC)的特征参数表明春季蓝藻的光能利用效率、最大电子传递速率和光饱和强度点高于秋季蓝藻;从空间分布来看,蓝藻的最大光合作用能力、实际光合作用能力和光合作用效率在营养水平低和有水草分布的湖区相对较低,富营养化水平高的湖区则相对较高.因此,降低太湖营养盐浓度,恢复水生植物,能够抑制蓝藻的光合作用活性和生长,从而降低蓝藻水华强度.     

羧基化碳纳米管载铂催化剂对微生物燃料电池阴极氧还原性能的影响

阴极催化剂是影响微生物燃料电池(microbial fuel cell,MFC)性能的关键要素.为了考察不同羧基化方法改性的碳纳米管(carbon nanotube,CNT)负载Pt的催化氧还原效率,分别在80℃和95℃条件下对CNT进行了羧基化,采用浸渍-沉淀法制备了Pt/CNT催化剂(Pt/CNT-80和Pt/CNT-95),并在空气阴极MFC体系中验证了其催化氧还原效果(MFC-80、MFC-95和MFC-C).结果表明,MFC-95和MFC-80的最大功率密度分别为568.8 mW.m-2和412.8 mW.m-2,内阻分别为204.7Ω和207.7Ω,开路电压分别为0.719 V和0.651 V.而对照MFC-C的最大功率密度仅为5.4 mW.m-2,内阻为826.2Ω.XPS和XRD分析结果显示,Pt/CNT-95催化氧还原效果优于Pt/CNT-80,原因可能是95℃羧基化过程在CNT表面引入了丰富的含氧基团.     

Investigation of low-molecular weight organic acids and their spatiotemporal variation characteristics in Hongfeng Lake, China

The identities and concentrations of low-molecular-weight organic acids (LMWOAs) were determined by ion chromatography throughout a 20-m water column in Hongfeng Lake, China. The spatiotemporal variations of LMWOAs and their contributions to dissolved organic matter (DOM) in a research period of 24 hr were also investigated. The results demonstrated that five LMWOAs (lactic, acetic, pyruvic, sorbic, oxalic acid) were detected, and their total concentration and proportion in DOC were 6.55 μmol/L and 7.47%. Their average levels were 2.50, 0.65, 2.35, 0.96 and 0.09 μmol/L, respectively. LMWOAs were higher during daytime (10:00-18:00 on Jun 13, 2008) than nighttime (21:00-6:00 the next morning), in particular 4.99 μmol/L high in the epilimnion ( 1 m water depth), reflecting the fact that direct import from terrigenous sources and photochemical production from humic materials were dominant during LMWOAs’ origin and accumulation. The same factors caused LMWOAs to be 0.63 μmol/L in the epilimnion higher than in the hypolimnion. The rapid decrease of total organic acid (TOA) up until 18:00 mainly resulted from bio-uptake and mineralization in the hypolimnion (>1 m water depth). Pyruvic acid increased with time in the epilimnion and decreased in the hypolimnion, largely related to the two contrary processes of continuous degradation and synthesis of macromolecular organic matter during life materials’ cycle mediated by organisms. Simultaneously, plankton behavior and thermal stratification played a pivotal role in LMWOAs’ behavior in the water column, causing decreasing and increasing profiles. The distribution of LMWOAs represents an interesting resource for biogeochemical research of DOM in aquatic ecosystems.     

Quantitative analysis of microbial biomass yield in aerobic bioreactor

We have studied the integrated model of reaction rate equations with thermal energy balance in aerobic bioreactor for food waste decomposition and showed that the integrated model has the capability both of monitoring microbial activity in real time and of analyzing biodegradation kinetics and thermal-hydrodynamic properties. On the other hand, concerning microbial metabolism, it was known that balancing catabolic reactions with anabolic reactions in terms of energy and electron flow provides stoichiometric metabolic reactions and enables the estimation of microbial biomass yield (stoichiometric reaction model). We have studied a method for estimating real-time microbial biomass yield in the bioreactor during food waste decomposition by combining the integrated model with the stoichiometric reaction model. As a result, it was found that the time course of microbial biomass yield in the bioreactor during decomposition can be evaluated using the operational data of the bioreactor (weight of input food waste and bed temperature) by the combined model. The combined model can be applied to manage a food waste decomposition not only for controlling system operation to keep microbial activity stable, but also for producing value–added products such as compost on optimum condition.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.