磁微球负载硝基锌卟啉光催化剂的制备及催化性能研究

以氯化血红素为原料,制备了磁负载的硝基锌卟啉光催化剂.同时,利用热重分析仪(TG)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)和振动磁强计(VSM)对催化剂进行了表征,发现制备的催化剂负载率为32.06%,催化剂为粒径均一的球形壳-核结构,具有良好的磁性.其次,研究了催化剂的催化降解性能.结果表明,磁负载硝基锌卟啉光催化剂在可见光下,对水中的双酚A(BPA)、对硝基苯酚(PNP)等均有90%以上的去除率;对于活性红染料废水的降解也取得了83.67%的降解率.自由基捕获实验证明,电子(e-)、羟基自由基(·OH)、空穴(h+)和氧自由基(O-·2)是降解反应中重要的活性物种.最后通过GC-MS等手段对降解机理进行了研究.     

Growth and alkaline phosphatase activity of Chattonella marina and Heterosigma akashiwo in response to phosphorus limitation

The growth and alkaline phosphatase activity (APA) of two raphidophyceae species Chattonella marina and Heterosigma akashiwo were investigated in response to P-limitation and subsequent addition of dissolved inorganic phosphorus (DIP, NaH₂PO₄) and two dissolved organic phosphorus (DOP) compounds: guanosine 5-monophosphate (GMP) and triethyl phosphate (TEP). APAlevels increased greatly after P-starvation as the decrease of the cellular phosphorus quotes (Q_p). C. marina responded to P-limitation quickly and strongly, with 10-fold increase in APA within 24 hr after P-starvation. The larger difference between maximal and minimal Q_p values in C. marina indicated its high capacity in P storage. APA of H. akashiwo wasmaximally enlarged about 2.5 times at 48 hr of P-starvation. After the addition of nutrients, cell numbers of C. marina increased in all treatments including the P-free culture, demonstrating the higher endurance of C. marina to P-limitation. However, those of H. akashiwo increased only in DIP and GMP cultures. APA increased only after the addition of the monophosphate ester GMP. The results suggest that quick responses of C. marina to P-limitation, high capacity in P storage as well as endurance for P-depletion provide this species an ecological advantage in phytoplankton community competition under DIP-limited conditions.     

有机过氧化物在生产、储运过程中的危险与可操作性分析

有机过氧化物的易燃、受热分解等特殊性质和生产、储运过程要求严格的低温条件与操作程序,使得有机过氧化物潜在的危险性很高。通过基于有机过氧化物危险特性及其在生产、储运过程中物质、能量与信息的分析,依据物-能量-信息的安全要素体系,应用危险与可操作分析方法,研究了有机过氧化物的安全理论,在某种程度上是延伸了HAZOP分析的内容。     

Impact of dissolved organic matter on the photolysis of the ionizable antibiotic norfloxacin

Norfloxacin (NOR), an ionizable antibiotic frequently used in the aquaculture industry, has aroused public concern due to its persistence, bacterial resistance, and environmental ubiquity. Therefore, we investigated the photolysis of different species of NOR and the impact of a ubiquitous component of natural water — dissolved organic matter (DOM), which has a special photochemical activity and normally acts as a sensitizer or inhibiter in the photolysis of diverse organics; furthermore, scavenging experiments combined with electron paramagnetic resonance (EPR) were performed to evaluate the transformation of NOR in water. The results demonstated that NOR underwent direct photolysis and self-sensitized photolysis via hydroxyl radical (·OH) and singlet oxygen (¹O₂) based on the scavenging experiments. In addition, DOM was found to influence the photolysis of different NOR species, and its impact was related to the concentration of DOM and type of NOR species. Photolysis of cationic NOR was photosensitized by DOM at low concentration, while zwitterionic and anionic NOR were photoinhibited by DOM, where quenching of UOH predominated according to EPR experiments, accompanied by possible participation of excited triplet-state NOR and ¹O₂. Photo-intermediate identification of different NOR species in solutions with/without DOM indicated that NOR underwent different photodegradation pathways including dechlorination, cleavage of the piperazine side chain and photooxidation, and DOM had little impact on the distribution but influenced the concentration evolution of photolysis intermediates. The results implied that for accurate ecological risk assessment of emerging ionizable pollutants, the impact of DOM on the environmental photochemical behavior of all dissociated species should not be ignored.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al2O3

High-surface-area mesoprous powders of γ-Al₂O₃ doped with Cu^2 +, Cr^3 +, and V^3 + ions were prepared via a modified sol–gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al₂O₃ and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane (DCE) was studied in the temperature range of 250–400°C. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2 +- and Cr^3 +-containing catalysts showed 100% conversion at 300°C and 350°C, V^3 +-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride (C₂H₃Cl) and hydrogen chloride (HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO₂.     

New insights into disruption of iron homeostasis by environmental pollutants

Among the numerous health conditions environmental pollutants can cause, chronic exposure to pollutants including persistent organic pollutants (POPs) and heavy metals has been shown to disturb a specific biological homeostatic process, the iron metabolism in human body. Disorders of iron metabolism are among the common diseases of humans and encompass a broad spectrum of diseases with different clinical manifestations, ranging from anemia to iron overload, and possibly to neurodegenerative diseases and cancer. Hepcidin–ferroportin (FPN) signaling is one of the key mechanisms responsible for iron supply, utilization, recycling, and storage, and recent studies demonstrated that exposure to environmental pollutants including POPs and heavy metals could lead to disruption of the hepcidin–FPN axis along with disordered systemic iron homeostasis and diseases. This article introduces and highlights the accompanying review article by Drs. Xu and Liu in this journal, which elaborates in detail the adverse effects of environmental pollutants on iron metabolism, and the mechanisms responsible for these toxicological outcomes. It also points out the knowledge gaps still existing in this subject matter. Research that will fill these gaps will improve our understanding of the issue and provide useful information to prevent or treat diseases induced by environmental pollutants.     

Biogenic volatile organic compound analyses by PTR-TOF-MS: Calibration, humidity effect and reduced electric field dependency

Green leaf volatiles(GLVs) emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds(BVOCs). Proton transfer reaction time-of-flight mass spectrometry(PTR-TOF-MS) is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field,etc. In this study the influence of gas humidity and the effect of reduced field(E/N) were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to10 ncps/ppbv(normalized counts per second/parts per billion by volume). The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity(RH) at 21°C, with the exception of(E)-2-hexenol. Product ion branching ratios were also affected by humidity,with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field(E/N) on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.     

Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

桂林市城区大气VOCs污染特征及对O3和SOA的生成潜势

对桂林市城区大气中挥发性有机物(VOCs)的污染特征,以及VOCs对臭氧(O3)和二次有机气溶胶(SOA)的生成潜势进行了研究。结果显示,研究期间,共检出VOCs物种78种,平均体积分数为21.32×10-9,表现为芳香烃(67.82%)烷烃(19.56%)卤代烃(7.50%)烯烃(2.86%)含氧挥发性有机物(1.41%)。VOCs体积分数空间分布呈现市中心和下风向郊区两个高值区。通过苯与甲苯的浓度比值发现,林科所VOCs主要来自交通源和生物源,师专甲山校区VOCs主要是来自交通源,其余测点VOCs主要来自交通源、工业源和外来传输源。分析乙苯和间/对二甲苯的浓度比值发现,电子科大尧山校区气团光化学年龄较大,光化学反应活性相对较强烈;旅游学院、华侨旅游经开区、大埠中心校气团光化学年龄较小,光化学反应活性相对较弱。VOCs对O3生成潜势最大的为芳香烃(93.81%),其次是烷烃(7.22%)和烯烃(4.75%);对SOA生成潜势最大的为芳香烃(97.45%),其次是烷烃(2.55%)。     

The role of agri‐environment schemes in conservation and environmental management

Over half of the European landscape is under agricultural management and has been for millennia. Many species and ecosystems of conservation concern in Europe depend on agricultural management and are showing ongoing declines. Agri‐environment schemes (AES) are designed partly to address this. They are a major source of nature conservation funding within the European Union (EU) and the highest conservation expenditure in Europe. We reviewed the structure of current AES across Europe. Since a 2003 review questioned the overall effectiveness of AES for biodiversity, there has been a plethora of case studies and meta‐analyses examining their effectiveness. Most syntheses demonstrate general increases in farmland biodiversity in response to AES, with the size of the effect depending on the structure and management of the surrounding landscape. This is important in the light of successive EU enlargement and ongoing reforms of AES. We examined the change in effect size over time by merging the data sets of 3 recent meta‐analyses and found that schemes implemented after revision of the EU's agri‐environmental programs in 2007 were not more effective than schemes implemented before revision. Furthermore, schemes aimed at areas out of production (such as field margins and hedgerows) are more effective at enhancing species richness than those aimed at productive areas (such as arable crops or grasslands). Outstanding research questions include whether AES enhance ecosystem services, whether they are more effective in agriculturally marginal areas than in intensively farmed areas, whether they are more or less cost‐effective for farmland biodiversity than protected areas, and how much their effectiveness is influenced by farmer training and advice? The general lesson from the European experience is that AES can be effective for conserving wildlife on farmland, but they are expensive and need to be carefully designed and targeted.