Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Biosorption mechanisms involved in immobilization of soil Pb by Bacillus subtilis DBM in a multimetal-contaminated soil

Mechanisms of soil Pb immobilization by Bacillus subtilis DBM, a bacterial strain isolated from a heavy-metal-contaminated soil, were investigated. Adsorption and desorption experiments with living bacterial cells as well as dead cells revealed that both extracellular adsorption and intracellular accumulation were involved in the Pb2＋removal from the liquid phase. Of the sequestered Pb（II）, 8.5% was held by physical entrapment within the cell wall, 43.3% was held by ion-exchange, 9.7% was complexed with cell surface functional groups or precipitated on the cell surface, and 38.5% was intracellularly accumulated.Complexation of Pb2＋with carboxyl, hydroxyl, carbonyl, amido, and phosphate groups was demonstrated by Fourier transform infrared spectroscopic analysis. Precipitates of Pb5（PO4）3OH, Pb5（PO4）3Cl and Pb10（PO4）6（OH）2that formed on the cell surface during the biosorption process were identified by X-ray diffraction analysis. Transmission electron microscopy–energy dispersive spectroscopic analysis confirmed the presence of the Pb（II）precipitates and that Pb（II） could be sequestered both extracellularly and intracellularly.Incubation with B. subtilis DBM significantly decreased the amount of the weak-acid-soluble Pb fraction in a heavy-metal-contaminated soil, resulting in a reduction in Pb bioavailability, but increased the amount of its organic-matter-bound fraction by 71%. The ability of B.subtilis DBM to reduce the bioavailability of soil Pb makes it potentially useful for bacteria-assisted phytostabilization of multi-heavy-metal-contaminated soil.     

Inhibitory effects of nisin-coated multi-walled carbon nanotube sheet on biofilm formation from Bacillus anthracis spores

Multi-walled carbon nanotube（MWCNT） sheet was fabricated from a drawable MWCNT forest and then deposited on poly（methyl methacrylate） film. The film was further coated with a natural antimicrobial peptide nisin. We studied the effects of nisin coating on the attachment of Bacillus anthracis spores, the germination of attached spores, and the subsequent biofilm formation from attached spores. It was found that the strong adsorptivity and the super hydrophobicity of MWCNTs provided an ideal platform for nisin coating. Nisin coating on MWCNT sheets decreased surface hydrophobicity, reduced spore attachment, and reduced the germination of attached spores by 3.5 fold, and further inhibited the subsequent biofilm formation by 94.6% compared to that on uncoated MWCNT sheet. Nisin also changed the morphology of vegetative cells in the formed biofilm.The results of this study demonstrated that the anti-adhesion and antimicrobial effect of nisin in combination with the physical properties of carbon nanotubes had the potential in producing effective anti-biofilm formation surfaces.     

Phosphatase activity and culture conditions of the yeast Candida mycoderma sp. and analysis of organic phosphorus hydrolysis ability

Orthophosphate is an essential but limiting macronutrient for plant growth. About 67% cropland in China lacks sufficient phosphorus, especially that with red soil. Extensive soil phosphorus reserves exist in the form of organic phosphorus, which is unavailable for root uptake unless hydrolyzed by secretory acid phosphatases. Thus, many microorganisms with the ability to produce phosphatase have been exploited. In this work, the activity of an extracellular acid phosphatase and yeast biomass from Candida mycoderma was measured under different culture conditions, such as pH, temperature, and carbon source. A maximal phosphatase activity of 8.47 × 10^5±0.11× 10^5 U/g was achieved by C. Mycoderma in 36 hr under the optimal conditions. The extracellular acid phosphatase has high activity over a wide pH tolerance range from 2.5 to S.0 （optimum pH 3.5）. The effects of different phosphorus compounds on the acid phosphatase production were also studied. The presence of phytin, lecithin or calcium phosphate reduced the phosphatase activity and biomass yield significantly. In addition, the pH of the culture medium was reduced significantly by lecithin. The efficiency of the strain in releasing orthophosphate from organic phosphorus was studied in red soil （used in planting trees） and rice soil （originating as red soil）. The available phosphorus content was increased by 230% after inoculating 20 days in rice soil and decreased by 50% after inoculating 10 days in red soil. This work indicates that the yeast strain C. mycoderma has potential application for enhancing phosphorus utilization in plants that grow in rice soil.     

酸性污染物监测浓度降低时酸雨频率增加机理:以阳泉市区为例

通过对比2006-2010年酸雨监测数据和环境空气例行监测数据得出:对于阳泉市区环境空气中SO2、NO2等酸性污染物浓度的变化,酸雨监测间接反映的逐年上升与同期例行环境空气质量监测所反映的逐年明显降低出现矛盾。通过讨论封闭型地貌、静风逆温型气候和资源型城市城矿郊混合结构等因素复合形成的不利大气污染物扩散场,分析高、中、低架点源和特殊污染源煤矸石山和山城机动车酸性污染物源强或排放量变化与空气质量和酸雨监测数据变化的相关性,得出矛盾机理为:2种监测所反映的空气SO2、NOx浓度属于不同高度层面的污染物。最后经相关性分析提出了主要与酸性污染物低空集聚相关的、由特殊地貌、气候、污染源复合形成酸雨的机制及与矸石山、机动车污染物低空排放量逐年增加相关的酸雨频率逐年增加机制。该研究对山区河谷资源型中小城市具有借鉴作用。     

三氯生对土壤酶活性的影响

为了明确三氯生对土壤生态环境的安全性,以3种土壤酶为指标,采用室内培养试验,研究了不同浓度的三氯生对土壤脲酶、酸性磷酸酶和过氧化氢酶活性的影响。研究结果表明,不同浓度水平的三氯生对3种土壤酶活性的影响效果不同。低浓度(≤50 mg/kg)三氯生作用下,脲酶活性先降低后增加,最后恢复到对照水平,高浓度(100 mg/kg)三氯生胁迫下脲酶活性先降低后恢复最后又被抑制。而对酸性磷酸酶活性来说,三氯生在低浓度时(≤50 mg/kg)先刺激后抑制酶活性,最后磷酸酶活性恢复到对照水平,高浓度下(100 mg/kg)三氯生先抑制后刺激再抑制磷酸酶活性,最后磷酸酶活性恢复到对照水平。各浓度水平的三氯生在培养的初期(21 d)对土壤过氧化氢酶活性没有影响,随着培养时间延长(≥28 d),低浓度(≤50 mg/kg)三氯生刺激了酶活性,高浓度(100 mg/kg)的三氯生抑制了过氧化氢酶活性。总体来说,高浓度的三氯生对土壤环境存在不利影响。     

煤矿酸性矿井水的治理方法与探讨

煤矿酸性矿井水具有强腐蚀性,并含有多种重金属离子,直排对生态环境破坏严重。本文主要介绍了人工湿地法、微生物法与中和法处理酸性矿井水治理方法,并对目前国内技术最成熟、应用最广泛的石灰乳中和法进行了重点阐述和探讨。     

对硝基苯胺耐盐降解菌S8的筛选及特性研究

从江苏农药厂活性污泥中筛选出1株能以对硝基苯胺为唯一碳源和氮源生长代谢的耐盐降解菌S8.通过对其形态特征、生理生化特性以及16S rDNA序列分析,确定为枯草芽孢杆菌(Bacillus subtilis).研究表明,该菌株具有较强的对硝基苯胺降解能力.当温度31℃和pH 6.0时,S8在72 h内对60 mg·L-1和120 mg·L-1对硝基苯胺的降解率分别为65.6%和55.8%.在高盐条件下,S8仍有较强的降解能力,当盐含量为7%时,对硝基苯胺降解率为49.5%(72 h);当盐含量为10%时,对硝基苯胺降解率为27.4%(72 h).利用LC-MS法分析降解产物时,共发现6种分子量不同的化合物,其中两种为苯酚及对苯二酚.此为首次关于对硝基苯胺耐盐菌株的研究报道,菌株S8可用于含有对硝基苯胺的高盐工业废水的微生物修复.     

高效聚磷菌Alcaligenes sp. ED-12菌株的分离鉴定及其除磷特性

利用经典的微生物筛选方法,从福州市闽侯县上街镇高岐村某排污口淤泥中分离出1株高效聚磷菌,并结合16S rRNA基因序列分析进行了菌株鉴定.结果表明,该菌株为产碱杆菌,将其命名为Alcaligenes sp.ZGED-12.理化因素实验显示,在以乙酸钠为碳源、NH4Cl为氮源,当C/N为3∶1,pH为8.0,温度和摇床转速分别为35℃和100 r·min-1时,该菌株的生长状态最好,对磷的去除能力也最强,最高除磷率可达80%.此外,该菌株能够耐受较高浓度的磷,当磷浓度超过45 mg·L-1时会产生抑制效应.同时,以聚乙烯醇(PVA)和海藻酸盐(SA)制备了聚磷微生物固定化小球,并考察了菌球对氮磷废水的净化效果.结果表明,氮磷的去除包括固定化材料的吸附作用及微生物的生长利用和/或贮存,显示出了良好的应用前景.     

东莞市大气亚微米粒子PM1及其中水溶性无机离子的污染特征

2011年8月—2012年7月期间,利用中流量(100 L·min-1)大气采样器对东莞市A和B两点(A:生活区,B:工业区)进行PM1、PM1~2.5、PM2.5~10采样,并定量分析颗粒物上F-、Cl-、NO-3、SO2-4、NH+4、Na+、K+、Ca2+、Mg2+等9种水溶性无机离子.分析结果显示,工业区B点的细粒子污染较生活区A点严重,B点PM1质量浓度年均值为48μg·m-3,其浓度是A点的1.2倍.A、B两点PM1对PM2.5和PM10的质量贡献率无明显差异,平均贡献率分别高达69%和45%.二次离子SO2-4、NO-3、NH+4及与燃烧行为有关的K+、Cl-等5种离子在细粒子PM1上富集,这5种离子对PM1质量的贡献率分别为18.82%~19.76%、4.98%~5.47%、3.98%~4.12%、2.03%~2.27%和3.39%~3.78%.而其他4种离子,Ca2+、Mg2+、F-和Na+积聚在粗粒子PM2.5~10上.PM10/PM2.5/PM1三种粒子中,PM1粒子酸性值AE/CE(阴离子当量浓度/阳离子当量浓度)比值和硫转化率SOR、氮转化率NOR值均是最高.