链长和官能团对全氟有机酸降解路径的影响

考察了碳链长度和官能团对高强UV/SO₃^2-体系降解全氟有机酸的影响,选取典型全氟有机酸PFOA和PFOS,探明其降解机制.结果表明,高强UV/SO₃^2-体系可高效降解5种全氟有机酸.全氟有机酸的降解速率随着碳链长度的增加而增加.官能团对全氟有机酸的降解有重要影响,全氟羧酸在体系中的降解速率显著快于全氟磺酸.全氟羧酸是从与羧基相连的α碳上的氟原子开始,通过逐步脱CF₂单元的形式生成短链全氟羧酸进行降解.全氟磺酸主要有三条降解路径：脱磺酸基、α位脱氟以及中心C—C键断裂.     

O3/UV降解水中的乙酸和硝基苯

利用O3 /UV和O3/H2O2降解了水中的乙酸,结果表明,在相同条件下处理60min后,O3/UV对乙酸的去除率仅比单独臭氧化处理提高了3%,而O3/H2O2在此条件下完全降解乙酸.O3/UV在处理硝基苯过程中却显示较好的氧化降解能力,通过分析表明,硝基苯降解过程中所产生的副产物H2O2对有机物的去除具有很重要的作用.因此,O3/UV氧化降解能力的提高可能有2方面的原因,紫外光对有机物的活化作用;中间产物H2O2催化臭氧分解产生了高活性的羟基自由基. 单独紫外光催化臭氧分解产生羟基自由基的效率极低.     

固定在活性炭聚砜中空纤维膜中的Pseudomonas putida菌对四氯苯酚的共代谢降解

以苯酚-四氯苯酚共代谢体系为对象,研究了中空纤维聚砜膜作为细菌固定化材料对该共代谢过程的强化作用.结果表明,该膜具有内、中、外3层的结构,Pseudomonas putida菌可被固定在膜的表面和中间层;固定化后,细菌对高浓度有毒底物的忍受限度增强,从而得以持续生长,并在29 h内将600　mg/L和120　mg/L的苯酚和四氯苯酚完全降解.在膜的制作过程中添加了一定量的活性炭后,发现膜对苯酚和四氯苯酚的吸附能力增强,同时结构上更疏松,对四氯苯酚的降解效率得到了提高.固定在活性碳中空纤维膜中的Pseudomonas putida可以将1 000　mg/L和200　mg/L的苯酚和四氯苯酚在51 h内完全降解,比不加活性炭的情况缩短了37 h,中空纤维膜可以连续多次使用,对相同浓度的四氯苯酚的降解速度保持稳定.     

正十六烷微生物降解酶的定域和酶促降解性

以正十六烷为研究对象,通过室内实验,利用细胞静息技术提取了2株菌种的胞外酶、膜周酶及膜内酶对石油烃类污染物质的微生物降解酶定域,并研究了菌株受环境影响的产酶条件和酶的一般性质. 结果发现:蜡状芽孢杆菌DQ01能降解正十六烷的关键酶位于膜周和膜内,芽孢杆菌DQ02降解正十六烷的关键酶是胞外酶和膜内酶. 通过GC-MS对代谢产物进行测定发现,关键酶对十六烷的代谢途径是常见的单末端氧化. 2株菌种产酶的最佳环境条件:ρ(正十六烷)为100 mg/L,c(鼠李糖脂)为2 mmol/L. 另外,关键酶在pH为6.5～8.0的环境中活性较高,在pH为7.0左右时的活性最高. 酶促降解性的最适温度为30 ℃.      

新农药硫肟醚在有机溶剂中的光解

以紫外灯为光源,对硫肟醚在甲醇、丙酮、正己烷和二甲苯等有机溶剂中的光解反应动力学及降解机理进行了初步研究.结果表明,硫肟醚在4种有机溶剂中的紫外光解反应符合一级动力学规律,在4种溶剂中反应速率常数分别为1·14×10-1(正己烷)、8·90×10-2(甲醇)、2·46×10-2(二甲苯)和4·51×10-3min-1(丙酮),硫肟醚的降解半衰期分别为6·08,7·79,28·18和153·86min.通过对硫肟醚光解产物进行分离和LC-MS鉴定,初步推出在紫外光辐射下硫肟醚在有机溶剂中的降解主要涉及到硫肟醚分子的肟醚键(CNOC)断裂、甲硫键(C—S—CH3)光氧化、脱氯反应和光异构化作用等途径.     

磺胺二甲基嘧啶(SM2)高效降解菌J2的分离筛选及降解特性研究

从城市污水处理厂活性污泥中分离得到一株能以磺胺二甲基嘧啶(SM2)为唯一碳源的菌株,经生理生化鉴定和16S rRNA基因序列同源性分析,将此菌鉴定为蜡样芽孢杆菌(Bacillus cereus),命名为J2.不同条件下的降解特性研究结果表明,J2菌株具有极高的SM2耐受性(100 mg·L~(-1))、较广的温度(20～30℃)和pH(6～8)适用范围;在温度30℃、pH=8.0、初始OD_(600)=0.1、SM2起始浓度为50 mg·L~(-1)的条件下,J2菌株在36 h内对SM2的降解率可达100%,降解效率远超目前已报道的其他SM2降解菌株,展现出了良好的应用潜力.J2菌株降解SM2过程中产生了5种主要中间代谢产物,分析推断其降解SM2的途径分为两条:①磺胺二甲基嘧啶分子首先在酶促反应作用下脱除SO_2,生成嘧啶环和苯胺环自由基,这两种自由基再经过环间耦合生成N-(4,6-二甲基嘧啶-2基)-1,4-二苯胺,该分子中的C—N键在活性氧物种的作用下断开生成苯胺和2-氨基-4,6-二甲基嘧啶;②在漆酶的作用下N~4键断裂,产生N-(3,5-二甲基嘧啶)-苯磺酰胺,之后N-(3,5-二甲基嘧啶)-苯磺酰胺的N—S键断裂,进一步形成2-氨基-4,6-二甲基嘧啶和苯亚砜.     

PFOS前体物质(PreFOSs)降解菌的分离鉴定及其降解特性

从氟化工厂附近土壤中分离出1株能以全氟辛烷磺酸前体物质(Pre FOSs)为唯一碳源和能源生长的降解菌PF1,经形态观察及16S r DNA基因序列分析,初步鉴定该菌为生丝微菌属(Hyphomicrobium sp.).在温度为30℃、p H为7.0~7.2条件下,菌株PF1对全氟辛基磺酰胺(PFOSA)和N-乙基全氟辛基磺酰胺(N-Et FOSA)48 h降解率分别为14.6%和8.2%,对PFOS无降解能力.对降解产物进行检测和分析,结果表明PFOSA的降解产物为PFOS;N-Et FOSA能被降解生成PFOSA和PFOS,同时也产生少量的全氟辛基磺酰胺乙酸(FOSAA).由此推断Pre FOSs降解途径,在菌株PF1的作用下,PFOSA脱去氨基直接转化成PFOS.NEt FOSA主要有2种降解途径:(1)N-Et FOSA脱乙基产生PFOSA,PFOSA再进一步脱氨基生成PFOS,此为主要途径;(2)NEt FOSA中的N-乙基被氧化成乙酸基生成FOSAA,FOSAA进一步脱去乙酸基生成PFOSA,并最终脱氨基生成PFOS.     

低温硝基苯降解菌的筛选及降解特性研究

从被硝基苯污染的某河流底泥中分离到能在低温下生长并能以硝基苯为唯一碳源的7株细菌,其中菌株NB1在温度从2.5～35 ℃范围内时都可以生长并矿化20 mg/L的硝基苯,最适宜的生长温度为25 ℃左右;当培养温度为5 ℃时,该菌株在pH为6～9范围内可以快速降解20 mg/L硝基苯,偏碱性的条件比酸性条件更适合其生长;不超过100 mg/L的硝基苯可以被该细菌完全降解.通过生理生化反应特性、菌体形态以及16S rDNA序列测定结果,确定NB1为恶臭假单胞菌(Pseudomonas putida).不同温度条件,特别是低温下该菌株对硝基苯的快速降解特性为低温环境硝基苯污染的生物修复提供了可能.     

堆肥过程中木质素的降解机理及影响因素研究进展

农作物秸秆中的木质素作为自然界中含量丰富的高分子芳香族化合物,结构复杂,微生物难以降解,因此农业废弃物堆肥技术中,木质素的降解利用备受关注。研究表明:木质素是由结构单元通过碳碳键和醚键联接聚合而成,结构稳定。已有堆肥实验证明,木质素的微生物降解过程中真菌占主导地位,其分泌的漆酶、锰过氧化物酶和木质素过氧化物酶等以H₂O₂或O₂作为电子受体,能够使联接键断裂,使芳香烃结构去甲基化。多酚或酚类衍生物产物与氨基酸聚合,并进一步缩聚为腐殖质,用作土壤改良质还田。在实验室及自然条件下,大多数真菌对木质素的降解周期较长为30~60 d,降解率为20%~50%,其降解过程依赖于培养条件,特别在中温35~45℃和偏酸性条件下更利于木质素的降解。微生物代谢过程中存在最佳碳氮补充量,并且可以利用微量Mn2+、Cu2+诱导剂等提高木质素降解酶活性,这为调控堆肥过程木质素的降解和人工腐质化提供了重要的研究方向。     

Burkholderia sp.FDS-1降解硝基苯酚类化合物的特性研究

从长期受农药污染的土壤中分离到1株高效杀螟硫磷降解菌株Burkholderia sp.FDS^-1,它能以3-甲基-4-硝基苯酚(MNP)为唯一碳源和氮源进行生长.该菌能在9h内将0.6mmol.L-1MNP完全转化成邻甲基对苯二酚(MHQ),并能继续降解MHQ.该菌降解MNP的最适温度和pH分别为30℃和7.0,菌株降解MNP的速率和起始接种量呈正相关.降解MNP的酶为诱导酶.     

自来水中强致突变物MX的测定

MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]是饮用水氯化消毒过程中产生的具有强致突变作用的副产物.实验利用XAD-8吸附树脂对江苏省癌症高发区自来水中的MX进行了富集,饱和BF₃-CH₃OH溶液衍生化,并用GC/MS测定.结果发现,除个别点MX含量较高外,其余浓度在0.58～20.0ng·L^-范围之内.同一采样点枯水期浓度要高于平水期.     

舟山群岛降水中阴离子及pH值的特征分析

通过对舟山站点降水中的4种阴离子(F^-、Cl^-、NO^3-和SO4₄^2-)及pH值近2a的连续观测,对阴离子和pH值的范围及变化趋势进行了描述;利用本征矢量投影技术对实验数据进行降维处理,并对造成异常样品点的影响因素进行了分析.进一步因子分析结果显示,舟山站点降水样本点在阴离子及pH值方面的分布特征可基本确定为2个因子,SO₄^2--NO₃^-因子(FA1)及Cl^-因子(FA2),可将其概括为“人类活动因子”与“海洋因子”,因子分析结果得到的主要因子FA1、FA2与本征矢量投影得到的主成分PC1、PC2基本对应,因子分析的结果对解释影响样品点差异的实际变量方面更具实际意义,即舟山站点样本点的异常值可归为2类,受SO4₄^2---NO₃^-因子(FA1)影响及受Cl^-因子(FA2)影响.     

Effect of oxide nanoparticles on the morphology and fluidity of phospholipid membranes and the role of hydrogen bonds

Engineered oxide nanoparticles (NPs) are widely applied in insulators, catalyzers, paints, cosmetic products, textiles and semiconductors. Their attachment on cell membrane may lead to cytotoxicity. The effects of Al₂O₃, Fe₂O₃, SiO₂, TiO₂ and ZnO NPs on membrane integrity and fluidity were studied using giant or small unilamellar vesicles in this study. Al₂O₃ and SiO₂ NPs disrupted the oppositely charged membrane, indicating the important role of electrostatic attraction. However, Fe₂O₃, TiO₂ and ZnO NPs did not cause serious membrane disruption as Al₂O₃ and SiO₂ NPs. Membrane fluidity was evaluated by the generalized polarity (GP) values of Laurdan fluorescent emission. SiO₂ NPs induce the membrane gelation of both positively and negatively charged membrane. Al₂O₃ and ZnO NPs induced the gelation of the oppositely charged membrane, but did not cause obvious membrane gelation to the like charged membrane. The phospholipid molecular structural changes after NP exposure were analyzed by Fourier transform infrared (FT-IR) spectroscopy. FT-IR spectra revealed the hydrogen bond formation between NPs and the carbonyl/phosphate groups of phospholipids. Al₂O₃ and SiO₂ NPs showed strongest evidence of hydrogen bonding on their FT-IR spectra. It was consistent with the microscopic observation and fluorescent data that Al₂O₃ and SiO₂ NPs caused more serious membrane disruption and gelation. This study on membrane damage provides further knowledge on the cytotoxicity of nanomaterials and the safety of NP application.     

Reaction of monoterpenes with ozone,sulphur dioxide and nitrogen dioxide—gas-phase oxidation of SO2 and formation of sulphuric acid

Teflon bag experiments were carried out in the dark in order to study the gas-phase reactions of selected monoterpenes with O₃ in the presence of SO₂ (β-pinene) as well as in the presence of SO₂/NO₂ (α-pinene, β-pinene, limonene). Emphasis was given in identifying the main reaction products and in quantifying the H₂SO₄ aerosol formed. Apart from the H₂SO₄ aerosol no other S containing compounds could be detected.It was found that the reaction of β-pinene with O₃, SO₂ and NO₂ leads mainly to 6,6-dimethyl-bicyclo [3.1.1] heptan-2-one (nopinone), the α-pinene-O₃-SO₂-NO₂-reaction produced 2′,2′-dimethyl-3-acetyl cyclobutyl ethanal (pinonaldehyde). The reaction of limonene with O₃-SO₂-NO₂ leads mainly to an unidentified product with a molecular weight M⁺ 134. In addition to the above-mentioned volatile products, the formation of organic nitrates could be established by means of gas chromatography-mass spectrometry.The yield of H₂SO₄ in the system β-pinene/O₃/SO₂ varies between 0.13 and 0.44 depending on the initial conditions, e.g. humidity. In the system terpene/O₃/SO₂/NO₂ the yield of H₂SO₄ for α-pinene (after 1 h reaction time) was 0.01–0.03, for β-pinene (2 or 4 h reaction time) 0.07–0.13 and for limonene (1 h reaction time) 0.02–0.09.     

光催化体系中噻虫胺降解动力学及机制

利用光催化技术探讨了烟碱类杀虫剂噻虫胺在水体环境中降解的可行性,不同催化剂浓度、反应温度、底物浓度、溶液初始p H值和不同阴阳离子等因素对其光催化降解动力学的影响,及其初步的光催化降解机制.结果表明噻虫胺的光催化降解符合L-H动力模型,其降解假一级动力学速率常数为0.050 6 min-1.当催化剂用量(TiO_2)为3.0 g·L~(-1)时,噻虫胺的光催化降解速率最大;高温和较低的底物浓度有利于噻虫胺的光催化降解;溶液的初始p H值为5时噻虫胺的降解速率最大,强酸和强碱均不利于其光催化降解.而无机阴、阳离子对噻虫胺降解均有明显的抑制作用.最后,通过GC/MS对噻虫胺光催化降解中间产物进行了初步鉴定,研究发现在活性氧物种的作用下噻虫胺降解途径主要有母体化合物的羟基化,硝基胍基团中N—N的断裂,以及连接硝基胍和噻唑环的C—N键的裂解等.     

酸性红B染料的阴极氧化降解机理

以Pt/C气体扩散电极为阴极,对pH=3的60mg/L酸性红B溶液进行双室电解,8V下电解80min后,酸性红B溶液在阴极室的脱色率和COD去除率分别为94.2%和66.8%,而酸性红B溶液在阳极室的脱色率和COD去除率分别为73.3%和56.6%,表明O2能在阴极室还原为H₂O₂和.OH来氧化降解酸性红B.通过红外光谱和GC-MS对酸性红B在阴极室的降解中间产物进行了分析,检测出20种中间产物,包括14种酯、3种酸和3种含—NO₂或N—OH基团的物质,给出了酸性红B染料在阴极室的可能降解路径.     

Interactive response of photosynthetic characteristics in Haloxylon ammodendron and Hedysarum scoparium exposed to soil water and air vapor pressure deficits

C₄ plants possess better drought tolerance than C₃ plants. However, Hedysarum scoparium, a C₃ species, is dominant and widely distributed in the desert areas of northwestern China due to its strong drought tolerance. This study compared it with Haloxylon ammodendron, a C₄ species, regarding the interactive effects of drought stress and different leaf–air vapor pressure deficits. Variables of interest included gas exchange, the activity levels of key C₄ photosynthetic enzymes, and cellular anatomy. In both species, gas exchange parameters were more sensitive to high vapor pressure deficit than to strong water stress, and the net CO₂ assimilation rate (A_n) was enhanced as vapor pressure deficits increased. A close relationship between A_n and stomatal conductance (g_s) suggested that the species shared a similar response mechanism. In H. ammodendron, the activity levels of key C₄ enzymes were higher, including those of phosphoenolpyruvate carboxylase (PEPC) and nicotinamide adenine dinucleotide phosphate-malate enzyme (NADP-ME), whereas in H. scoparium, the activity level of nicotinamide adenine dinucleotide-malate enzyme (NAD-ME) was higher. Meanwhile, H. scoparium utilized adaptive structural features, including a larger relative vessel area and a shorter distance from vein to stomata, which facilitated the movement of water. These findings implied that some C₄ biochemical pathways were present in H. scoparium to respond to environmental challenges.     

生物炭添加对半干旱地区土壤温室气体排放的影响

为确定生物炭添加对半干旱地区农田土壤温室气体释放的影响,采用小区定位试验,利用锯末(J)和槐树皮(H)及3种添加比例(1%、3%、5%,质量百分比),研究了生物炭添加6个月内表层土壤CO2、CH4和N2O等3种温室气体排放的动态变化.结果表明,与对照相比,各处理土壤CO2排放通量随生物炭的添加呈现增加的趋势,锯末和槐树皮等两种生物炭处理的土壤CO2平均排放通量分别增加了1.89%和3.34%,但差异不显著.CH4排放随着生物炭添加量的增加而降低,各生物炭处理的土壤表层CH4排放量平均降幅分别为:J1:1.17%、J3:2.55%、J5:4.32%、H1:2.35%、H3:5.83%、H5:7.32%.其中,锯末生物炭仅在5%添加量时较对照差异显著(P0.05),而槐树皮生物炭处理在3%和5%的添加量与对照差异均达显著水平(P0.05).生物炭对N2O的排放影响没有明显规律性.研究表明,生物炭在短期内对半干旱地区农田土壤CO2和N2O的排放没有显著影响,而对CH4排放则影响显著(P0.05).就生物炭类型而言,槐树皮生物炭在抑制CH4排放方面优于锯末生物炭,差异显著(P=0.048).     

石羊河流域降水化学特征时空变化及来源浅析

运用相关分析、因子分析、富集因子和HYSPLIT模型对石羊河流域从2013年7月到2014年7月连续收集降水样品的主要离子浓度特征及来源进行了探讨分析,结果表明,Ca~(2+)和Na~+是主要的阳离子,SO_4~(2-)和NO_3~-是主要的阴离子,石羊河流域的主要降水类型为SO_4~(2-)-NO_3~--Ca~(2+);石羊河流域的总离子浓度的季节大小变化顺序为冬季春季秋季夏季,石羊河流域的降水水化学主要受地壳源和人为源的影响;石羊河流域的降水类型分为季风降水、西风降水和混合降水,而混合降水是石羊河流域的主要降水类型,其次为西风降水,最后为季风降水。     

Degradation of 4-aminophenol by hydrogen peroxide oxidation using enzyme from Serratia marcescens as catalyst

This paper reports on the degradation of 4-aminophenol using hydrogen peroxide as oxidizer and the enzyme from Serratia marcescens AB 90027 as catalyst. The effecting factors during degradation and the degrading mechanism were studied. Also, the location of the enzyme in the cell, which could catalyze the degradation of 4-aminophenol, was analyzed. The results showed that to degrade 50 mL of 4-aminophenol whose concentration was 500 mg/L, the optimal conditions were: volume of H₂O₂ = 3 mL, temperature = 40–60°C and pH = 9–10. In the degradation process, 4-aminophenol was first converted to benzoquinone and NH₃, then organic acids including maleic acid, fumaleic acid, and oxalic acid were formed, and then finally CO₂ and H₂O were generated as final products. The enzyme that could catalyze the degradation of 4-aminophenol was mainly extracellular enzyme. Translated from Environmental Chemistry, 2006, 25(2): 141–144 [译自: 环境化学]