Concurrent catalytic removal of typical volatile organic compound mixtures over Au-Pd/α-MnO2 nanotubes

α-MnO_2 nanotubes and their supported Au-Pd alloy nanocatalysts were prepared using hydrothermal and polyvinyl alcohol-protected reduction methods, respectively. Their catalytic activity for the oxidation of toluene/m-xylene, acetone/ethyl acetate, acetone/m-xylene and ethyl acetate/m-xylene mixtures was evaluated. It was found that the interaction between Au-Pd alloy nanoparticles and α-MnO_2 nanotubes significantly improved the reactivity of lattice oxygen, and the 0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst outperformed the α-MnO_2 nanotube catalyst in the oxidation of toluene, m-xylene, ethyl acetate and acetone. Over the0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst,(i) toluene oxidation was greatly inhibited in the toluene/m-xylene mixture, while m-xylene oxidation was not influenced;(ii) acetone and ethyl acetate oxidation suffered a minor impact in the acetone/ethyl acetate mixture; and(iii) m-xylene oxidation was enhanced whereas the oxidation of the oxygenated VOCs(volatile organic compounds) was suppressed in the acetone/m-xylene or ethyl acetate/m-xylene mixtures. The competitive adsorption of these typical VOCs on the catalyst surface induced an inhibitive effect on their oxidation, and increasing the temperature favored the oxidation of the VOCs. The mixed VOCs could be completely oxidized into CO_2 and H_2 O below 320°C at a space velocity of 40,000 m L/(g·hr). The 0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst exhibited high catalytic stability as well as good tolerance to water vapor and CO_2 in the oxidation of the VOC mixtures. Thus, the α-MnO_2 nanotube-supported noble metal alloy catalysts hold promise for the efficient elimination of VOC mixtures.     

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai

To investigate formation mechanisms of secondary organic carbon(SOC) in Eastern China,measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O_3 concentrations(daily peak 120 ppb) was observed, during which daily maximum SOC concentrations exceeding 9.0 μg/(C·m~3). Diurnal variations of SOC concentration and SOC/organic carbon(OC) ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with O_x(= O_3+ NO_2) and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon(EC) particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250–2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe(III) complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.     

金属软管爆裂失效分析

某厂压缩机出口管线处金属软管的设计压力为6.3 MPa,试压时金属软管接头与接头套处发生爆裂,爆裂压力为4.2 MPa。通过对金属软管爆裂处进行宏观检查与测厚、化学成分分析、断口分析、X射线能谱分析以及焊接形式分析,判定金属软管爆裂的主要原因是活套法兰侧接头与波纹管连接焊缝结构不合理导致焊缝承载能力不足,焊缝存在严重未焊透、焊材选用不合理,进一步导致了焊缝承载能力的下降。最后,提出了针对性预防措施。     

基于SARIMA模型和普通Kriging法对杭州市主城区PM2.5短期预测和制图

基于SARIMA模型对杭州市主城区内的7个站点和周边3个站点的PM_(2.5)浓度进行4 h平均的短期预报,并利用普通Kriging法对杭州市主城区PM_(2.5)进行空间插值和制图.在建立SARIMA模型时,用批量自动化的方法,使用R语言编程对夏季和冬季各360期的数据进行SARIMA(p,d,q)×(P,D,Q)6模型的参数的确定和拟合,来预测下一期的值.在10个站点分别进行120期的预测,做出真实与预测的时间序列图,在精度分析中,夏季和冬季PM_(2.5)浓度总体的平均绝对误差(MAE)分别为8.4μg·m~(-3)和14.8μg·m~(-3).在Arc GIS中,对每期的数据使用普通Kriging法,用球面模型拟合半变异函数,决定各个站点的权重,来对杭州市区内未知空间样点进行插值,最后生成完整的杭州市主城区PM_(2.5)短期预测图.本研究创新性地将SARIMA模型广义化运用到小尺度时间序列中,预报效果较好,并且批量自动化预测和制图的方法,可为今后的预测制图产品化提供技术支持.     

浑河流域底质类型对硅藻群落分布特征的影响

河流底质可以为硅藻提供附着的基质,不同的底质类型对硅藻群落结构有一定的影响.本研究对浑河流域上23个采样点位进行调查研究,并运用多响应置换过程、典范对应性分析、线性回归分析等,分析河流底质类型对硅藻群落的影响.多响应置换过程结果显示,苏子河、红河和英额河、浑河中游及浑河下游水系之间硅藻群落空间差异显著;香农多样性指数、均匀度指数与物种丰富度的平均值分别为2.57、0.69和15;典范对应性分析结果显示,IOS指数、电导率、总氮和总磷是显著影响硅藻群落结构的环境因子;相关分析结果显示,香农多样性指数、均匀度指数和物种丰富度与IOS指数呈正相关.本研究中,河流底质类型为大石块、鹅卵石等类型时,硅藻多样性较高;而底质类型为淤泥和细沙时,硅藻多样性较低.     

典型绿洲不同土壤类型有机碳含量及其稳定碳同位素分布特征

土壤有机碳及其稳定同位素组成反映了生态系统碳循环的关键信息,对研究全球变化下陆地生态系统碳动态及碳资源的可持续发展具有重要意义.本研究以阿拉尔绿洲4种土壤类型为研究对象,测定不同深度土壤有机碳(SOC)含量和δ~(13)C值,探讨不同土壤类型有机碳分布、δ~(13)C_(SOC)丰度差异及其与土壤环境因子的关系.结果表明:(1)土壤整体有机碳含量由高到低依次为灌漠土、棕漠土、盐土、风沙土,且在表层(0~20 cm层)具有较大值;δ~(13)C_(SOC)变化范围在-26‰~-23‰,表层(0~20 cm)由正趋负为盐土风沙土灌漠土棕漠土.(2)土壤有机碳含量受土壤类型、深度及其交互作用极显著影响,δ~(13)C_(SOC)受土壤类型、交互作用显著影响;进一步交互效应检验中土壤有机碳受因素水平影响极强,同位素相对较弱.(3)冗余分析发现土壤有机碳与土壤无机碳、全氮、土壤含水量、容重均存在显著或极显著正相关关系,与C/N具有显著负相关关系;δ13CSOC与电导率存在显著正相关关系,与土壤无机碳、土壤含水量均存在极显著负相关关系.土壤环境因子的重要性排序为土壤含水量土壤无机碳容重全氮C/N电导率pH.分析得出土壤有机碳及其同位素在不同土壤类型中呈现出不同变化规律,其土壤类型的效应强于土壤深度,受土壤含水量影响最甚.     

施用生物炭对土壤Cd形态转化及烤烟吸收Cd的影响

采用盆栽试验模拟Cd污染土壤,研究施用烟秆炭(0、10、20 g·kg~(-1))对土壤pH、有机质含量、土壤Cd形态分布及烤烟Cd含量和Cd累积量的影响.结果表明:随着生育期的延长,土壤pH和有机质含量均呈现升高的趋势.在同一Cd污染水平下,土壤pH和有机质含量均随生物炭施用量的增加而升高.随生物炭施用量的增加,土壤有效态Cd和可交换态Cd含量显著降低,土壤碳酸盐结合态Cd、铁锰氧化物结合态Cd、有机结合态Cd和残渣态Cd含量升高.移栽后30 d,处理G2T2和G2T1的土壤有效态Cd含量的降幅分别达到45.59%和24.56%.外源添加Cd的土壤中,土壤pH和有机质含量均与土壤有效态Cd和可交换态Cd含量呈显著负相关关系(p0.01),与土壤碳酸盐结合态Cd、铁锰氧化物结合态Cd和有机结合态Cd含量呈显著正相关关系(p0.01).在Cd污染土壤上,施用生物炭能明显降低烟株各部位Cd含量,烟株各部位干物质积累量随生物炭施用量的增加显著升高,烟株各部位Cd累积量和总Cd累积量随生物炭施用量的增加呈降低的趋势.由此说明,在Cd污染的土壤上施用生物炭能够使土壤中可被植物吸收利用的有效态Cd转化为潜在的无效态Cd,从而达到修复土壤并减轻作物受Cd毒害的目的.     

典型可溶有机质与磺胺二甲嘧啶的络合作用研究

以藻源有机质(AOM)和腐殖酸(HA)作为典型生物大分子可溶有机质(DOM)和腐殖化DOM,采用荧光猝灭滴定和光谱分析考察磺胺二甲嘧啶(SMZ)与DOM的络合作用.三维荧光光谱结合平行因子分析显示AOM荧光组分主要由类酪氨酸和类色氨酸物质组成,而类富里酸和类腐殖酸物质是HA荧光组分的主要构成.4种荧光组分可与SMZ发生不同程度的静态猝灭,且猝灭过程中DOM分子构象改变.同步荧光光谱结合二维相关图谱进一步发现类酪氨酸优先于类色氨酸组分与SMZ发生络合作用.Ryan-Weber非线性模拟拟合表明AOM中各荧光组分与SMZ的络合稳定常数(logK)大小为:类富里酸(3.33)类酪氨酸(3.12)类色氨酸(2.15)类腐殖酸(1.57);而HA中大小为:类富里酸(3.06)类腐殖酸(2.02).总体上生物大分子DOM对SMZ的亲和力高于腐殖化DOM.DOM与SMZ的相互作用可改变水环境中抗生素的形态和归趋,影响其生物有效性和生态毒性.     

基于时空指示克里格的PM2.5不确定性分布

以山东省2014年PM_2.5浓度监测数据为对象,利用时空指示克里格理论和方法,实现对PM_2.5时空分布的不确定性分析.结果表明,山东省境内PM_2.5的空间自相关范围大于100km,时间自相关范围为3d左右.此外,山东省境内各空间位置全年空气质量以大于0.8的概率达到空气质量"优"级别的时空占比为7%,以大于0.8的概率达到轻度污染级别的时空占比为34%,以大于0.8的概率超过严重污染级别的时空占比为1%;东部沿海地域空气质量达到轻度污染的概率明显高于中西部,夏季空气质量也明显优于其它季节.     

全球增温1.5℃和2.0℃对淮河中上游径流影响预估

论文应用第5次耦合模式比较计划(Coupled Model Intercomparison Project Phase 5,CMIP5)中5个全球气候模式(Global Climate Models,GCMs)和3种典型浓度路径(Representative Concentration Pathways,RCPs)在全球增温1.5℃和2.0℃下的预估结果,分析了淮河中上游地区未来的气候变化特征。进一步基于SWAT(Soil and Water Assessment Tool)水文模型定量预估了气候变化对该区域径流量的影响,并量化了预估结果的不确定性。结果表明:SWAT模型在淮河中上游对月径流量具有较好的模拟能力。在全球增温1.5℃和2.0℃下,淮河中上游年平均气温分别较基准期(1986—2005年)增加1.1℃和1.7℃;年降水量较基准期分别相应增加4%和7%;基于SWAT模型预估的年径流量较基准期分别增加5%和8%。未来气候变化不会改变月径流分布特征,年内径流仍集中在盛夏和初秋(6—9月)。预估的月丰水流量明显增加,尤其当全球增温达到2.0℃后,出现洪涝的风险明显增大。未来降水量和径流量预估都存在较大的不确定性,不确定性主要来源于GCMs,在全球增温2.0℃下预估的不确定性更大。