氨对甲苯二次有机气溶胶形成和化学组分的影响研究

氨(NH_3)是大气中常见的主要碱性污染气体,能够影响二次有机气溶胶(SOA)的形成和化学组分.本文利用自制的烟雾腔系统开展了NH_3对甲苯SOA形成和化学组分的影响研究,先后采用扫描移动粒径谱仪(SMPS)、气溶胶激光飞行时间质谱仪(ALTOFMS)、紫外-可见分光光度计(UV-Vis)、衰减全反射傅里叶变换红外光谱仪(ATR-FTIR)和荧光光谱仪(MF)测量反应产生的SOA粒子的物理化学性质.结果显示,在光照60 min的时间范围内,有NH_3条件下形成的SOA质量浓度和中心粒径相比于无NH_3条件下分别增加了50%和25%,这说明NH_3能够显著促进甲苯SOA的形成.与无NH_3条件下相比,NH_3存在时甲苯SOA化学组分的紫外可见吸收光谱在270 nm处有明显的吸收峰;红外吸收光谱出现了CN、C—N、N—H键的吸收峰;激光解吸附质谱图中含有m/z=67(C_3H_3N_2~+)、m/z=41(C_2H_2N~+)和m/z=28(CH2N+)碎片峰.这些谱图信息综合表明是NH_3和甲苯SOA中的二醛组分反应形成了咪唑类新产物.这为研究人为源SOA的形成机制提供了实验依据.     

利用酸性水汽提回收氨生产碳酸氢铵

本文将介绍炼油厂酸性水汽提回收的气氨与制氢装置排出的废CO_2碳化生产商品化肥——碳酸氢铵。 1.工艺原理 (1) 炼油厂酸性水汽提回收气,制成20％浓氨水,用浓氨水吸收二氧化碳,生产碳酸铵溶液。其反应式为: 2NH_4OH CO_2—→(NH)_4CO_3 H_2O 116MJ (2) 碳酸铵溶液进一步吸收二氧化碳,得到碳酸氢铵晶体。其反应式为:     

光腔衰荡光谱(CRDS)法观测我国4个本底站大气CO2

利用基于光腔衰荡光谱(CRDS)技术自组装的大气CO2在线观测系统,于2009年在青海瓦里关、浙江临安、北京上甸子和黑龙江龙风山4个世界气象组织全球大气观测网(WMO/GAW)大气本底站对大气CO2进行了在线观测.初步分析结果表明,4站全年大气CO2体积分数最低值出现在7～8月,夏季临安、龙风山和上甸子站CO2平均体积...     

光腔衰荡光谱法走航连续观测海表大气中氧化亚氮

基于最新型Picarro G5101i型光腔衰荡光谱仪,自行设计并集成了适用于海表大气氧化亚氮的船基走航连续观测系统.实验室测试结果显示,该系统准确度优于1.4×10-9mol·mol-1,精密度优于0.2×10-9mol·mol-1.通过搭载2017年春季黄海和东海综合调查航次,首次在我国开展了海表大气中氧化亚氮的船载走航式连续观测研究.实践证明,该系统操作简便,运行稳定可靠,可获取高频率高精度的海表大气氧化亚氮摩尔分数数据.同时,基于实际观测工作,初步优化建立了相应的数据质量控制和处理方法,为获取具有国际可比性的观测数据奠定了基础.观测结果显示,春季黄海和东海海表大气中氧化亚氮的摩尔分数范围为(331.0~345.1)×10-9mol·mol-1,平均值为(333.5±1.4)×10-9mol·mol-1.     

光腔衰荡光谱法走航连续观测海表大气中CH4

以基于高精度光腔衰荡光谱法(Cavity Ring-Down Spectroscopy,CRDS)的Picarro G2301型分析仪为核心,自主设计、组装,建立了适用于船载走航连续观测大气CH4的系统.采用可溯源至世界气象组织全球大气观测网(WMO-GAW)的标准气序列开展多次测试,并建立了外标法线性校正方程.测试表明,该系统对CH4响应精密度优于0.5 ×l0-9,准确度优于0.1％,5个月内漂移小于0.3 ×l0-9.同时,结合船载走航连续观测的特点,优化建立了观测数据处理与质量控制方法,以保证所获数据的高质量和国际可比性.分别于2011年7月和2012年5月,率先在北黄海及渤海海峡区域开展了海表大气CH4的走航连续观测.实践证明,该系统操作简便,运行稳定,适用于船载走航连续海表大气CH4的研究,可获取高精度高时空分辨的观测数据.其中,2011年7月观测到的CH4浓度范围为1823.8×10-9～2020.7×10-9,2012年5月为1887.2×10-9～ 2136.2×10-9,均呈渤海海峡区域浓度高,北黄海中部区域浓度低的分布特征.     

一种复合菌剂在生物除臭滤池中的试验研究

文章构建了复合型除臭菌剂——YDEM-1,考察YDEM-1对生物滤池除臭反应器的启动及NH_3、H_2S等恶臭物质的去除效果。结果发现:YDEM-1对生物除臭反应器初次启动和二次启动速度快;相比之下,YDEM-1对NH_3去除效率高于H_2S,如NH_3进气浓度为58.9、100.9、165.3、230.3 mg/m~3时,去除率达到100%所需空床停留时间分别为12.6、29.6、63.0、100.8 s,而H_2S进气浓度为15.7 mg/m~3条件下,实现98%以上的去除率,所需停留时间为29.6 s;该反应器适宜含水率范围在25%～50%。该复合型生物滤池反应器具有良好的应用前景。     

激光拉曼光谱法测定生物燃气的气体组分

文章提出了一种基于激光拉曼光谱仪的生物燃气气体组分含量的快速分析方法,实现了生物燃气中C_1~C_3、H_2、O_2、N_2、CO、CO_2共11种气体成分的同时测定。通过实验测定、计算CH_4主峰处其他气体相对于CH_4的折算系数,解决了拉曼光谱中存在的重叠峰使CH4测量不准确的问题。同时通过实验和分析确定了合理的积分时间和气体压力。实验表明,所有组分都能被测量出来,并且测量的绝对误差小于1%,基本满足生物燃气组分含量的现场分析的精度和稳定性要求。     

三种小分子对光电子还原铀的影响及机理研究

光电子具有较强的还原性,但在溶液中其还原性受到多种因素的影响。该研究通过在反应体系中添加不同的有机小分子并利用循环伏安(CV)、电化学交流阻抗(EIS)、恒电位I-t曲线和红外光谱(FTIR)等方法考察小分子对光电子还原铀的影响及其作用机理。结果表明:CV分析证实在半导体矿物-U(Ⅵ)体系中U(Ⅵ)经历两步单电子还原为U(Ⅳ),扩散系数D_(Ⅵ)=1.9×10~(-8)cm~2/s。加入Na_3C_6H_5O_7、CH_3COONa、C_2H_5OH 3种小分子后溶液体系具有更高的电活性;随着小分子浓度不断增加,电子转移的能力先升高后降低;体系存在最优条件,即U(Ⅵ)与小分子的摩尔浓度为1∶1时,电子转移能力最强。相较于半导体矿物-U(Ⅵ)体系,3种小分子加入后其还原率分别提高了27.4%、16.4%、14.6%。EIS表明加入小分子的溶液体系具有更低的传荷内阻,更有利于电子的快速传递;I-t曲线证实还原过程中添加小分子可以加快U(Ⅵ)还原反应动力学速度;FTIR表明作用后603.34 cm~(-1)处有一U(Ⅳ)的较强吸收峰,表明光电子可将U(Ⅵ)还原成低价铀。研究结果表明通过加入合适的小分子可提高光电子对铀的还原效率。     

地下水中222Rn的液体闪烁测量法

本文介绍的测量地下水中~(222)Rn的液体闪烁法,具有简便、快速、灵敏、可靠等优点。该方法仅需水样10ml,制样时间不超过1min,探测限可达0.82Bq/L,能实现样品测量的自动化。它不需要特殊的测量装置,普通的商品液体闪烁计数器即可满足要求。是一种进行大规模地下水样中~(222)Rn浓度调查的,较为理想的方法。     

本底大气CO2观测分析过程中QA/QC方法的建立与评估

建立科学规范的本底大气CO2采样观测分析过程中的质量保证与质量控制方法,是实现该数据资源同化和共享的基础.本研究以中国气象局温室气体网络化采样观测经验为基础,以便携式采样观测、波长扫描-光腔衰荡(WS-CRDS)分析技术为例,系统介绍了我国青海瓦里关全球本底站大气中CO2采样观测过程中的质量保证措施,样品分析过程中的玻璃瓶质量保证措施和样品分析过程中的系统质量控制方法、数据处理过程中的校正方法、数据分级质量标记和数据拟合插补方法等;并重点对该方法中几个关键步骤进行了评估验证;最后,应用本研究方法,对我国3个区域大气本底站CO2的采样观测数据进行了处理和浓度变化特征分析,说明本研究方法也可以较好地捕捉区域和局地环境因素影响对观测结果的影响,并客观、准确地反映该区域的自然和人为活动特征.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.