金属改性碳脱除PH3和H2S动力学及反应机理研究

为综合利用黄磷尾气中的CO,通过计算平均活化能和测定XPS、TG／DTA和氮吸附特性的方法,研究了Cu2＋和某金属离子M^n＋改性碳脱除PH,和H2S的动力学和反应机理问题。结果表明：H2S在金属改性碳上反应时平均活化能为134．4J／mol为-0．76级反应,PH,在金属改性碳上反应时平均活化能为1247．6J／mol为-0．8级反应;减小改性碳粒径增加流量可以显著提高其脱除PH,和H。S的速率;XPS、TG／DTA和孔径分布分析证明,改性碳净化H2S和PH3是一个催化吸附过程,H2S和PH3首先与氧在改性碳表面进行催化氧化反应,然后生成S和P2O5沉积吸附在改性碳表面。     

金属改性碳脱除PH3和H2S动力学及反应机理研究

为综合利用黄磷尾气中的CO,通过计算平均活化能和测定XPS、TG/DTA和氮吸附特性的方法,研究了Cu²⁺和某金属离子Mn⁺改性碳脱除PH₃和H₂S的动力学和反应机理问题。结果表明：H₂S在金属改性碳上反应时平均活化能为134.4 J/mol为-0.76级反应,PH₃在金属改性碳上反应时平均活化能为1 247.6 J/mol为-0.8级反应;减小改性碳粒径增加流量可以显著提高其脱除PH₃和H₂S的速率;XPS、TG/DTA和孔径分布分析证明,改性碳净化H₂S和PH₃是一个催化吸附过程,H₂S和PH₃首先与氧在改性碳表面进行催化氧化反应,然后生成S和P₂O₅沉积吸附在改性碳表面。     

改性透辉石对饮用水中余氯的吸附机理

将透辉石和碳酸钙在高温下反应活化,对透辉石进行改性,探讨了改性透辉石对余氯的吸附性能。利用X射线衍射(XRD)、扫描电镜(SEM)和X射线光电子能谱(XPS)对吸附前后的改性透辉石进行表征。考察了此吸附过程的吸附平衡、动力学和热力学。实验结果表明,吸附后的残渣XRD图谱出现了带羟基的Ca_4(Si_3O_9)(OH)_2,吸附前后的SEM图表面发生明显变化,吸附残渣的XPS图中有+1价的Cl。Freundlich和Langmuir方程都呈现良好的拟合度,改性透辉石的单分子层最大吸附量是6.974 mg·g-1,热力学平衡方程计算的ΔG00,ΔS00,说明吸附是自发进行的、熵增反应;从293 K至303 K时ΔH0值为3.43 k J·mol-1,该阶段的吸附反应是吸热的;温度303 K至313 K阶段,ΔH0值为-9.00 k J·mol-1,吸附反应是放热的。对余氯的吸附机理是斜方硅钙石Ca_4(Si_3O_9)(OH)_2的羟基和Cl O-发生交换作用。     

改性木屑对水中Cr(Ⅵ)的吸附性能

在木屑上接枝季氨基团制备了改性木屑,并用傅里叶红外光谱(FT-IR)对其进行了表征。通过静态实验研究了改性木屑对水溶液中六价铬Cr(Ⅵ)的吸附特性,并探讨了温度、p H、多组分共存离子等对Cr(Ⅵ)吸附效果的影响。结果表明,在30℃时,改性木屑对Cr(Ⅵ)的饱和吸附容量为218.33 mg/g,吸附规律符合Langmuir等温方程式。在p H为3~10时,改性木屑对Cr(Ⅵ)均有显著的吸附效能,吸附过程符合准二级动力学方程,反应活化能为21.71 k J/mol,对吸附热力学参数△G0、△H0和△S0的计算表明,吸附过程是吸热的自发过程。多组分干扰离子共存时,对Cr(Ⅵ)的吸附影响不大。     

过渡金属浸渍改性ACF去除H_2S研究

为探讨活性炭纤维（ACF）去除恶臭气体H2S的性能,采用过渡金属浸渍改性ACF吸附H2S,揭示出改性ACF前后吸附H2S的性能差异及浸渍剂的浓度和种类对ACF吸附性能的影响。结果表明,通过过渡金属改性后的ACF吸附性能有显著提高,对H2S吸附是物理吸附和化学吸附共同作用的结果,改性后的ACF硫容量大小依次为：5%硝酸铜改性ACF〉5%硝酸钴改性ACF〉5%硝酸锰改性ACF。不同浓度浸渍剂改性后的ACF吸附H2S性能有所不同,硫容量呈现出随着浓度升高先增大后减小的趋势。不同浸渍剂改性后的ACF吸附穿透曲线也不同,穿透时间依次为：TCu-ACF〉TCo-ACF〉TMn-ACF。混合金属溶液改性ACF吸附H2S,5%硝酸铜-3%硝酸钴溶液改性ACF吸附性能最佳,硫容量可达166.7 mg/g;而5%硝酸铜-3%硝酸钴-1%硝酸锰溶液改性的ACF效果最差,硫容量仅为83.3 mg/g。     

高岭石吸附水溶液中铅离子的动力学研究

研究了高岭石吸附水相中铅离子的动力学行为.结果表明:高岭石对水溶液中铅离子的吸附是一个复杂的非均相固液反应,从动力学角度来看,大致可以分为2个阶段:初期阶段反应速度快,动力学过程复杂,有待于深入研究;后期阶段反应速度较慢,并符合一级反应动力学方程.吸附速率常数k与温度T之间的关系符合阿累尼乌斯公式,吸附的活化能为Ea=26.44 J/mol,吸附的频率因子A=603s-1.ln(k/T)与1/T之间的关系符合Eyring公式,其活化焓△H=23.94J/mol,活化熵△S=-200J/K·mol.同时,k与铅离子初始浓度呈负相关性,与高岭石用量、介质pH值呈正相关性.     

活性炭纤维低温脱除模拟烟气中的VOC

采用H2O2浸渍的修饰方法对ACF进行化学改性,并利用氮吸附等温线和XPS（X-ray photoelectron spectroscopy）的方法对ACF样品进行表征。通过在反应床上开展吸附实验,由此测定改性前后ACF脱除VOC（甲苯作为VOC的代表物）的效果,同时考察氧气、温度、水蒸气等因素对ACF脱除甲苯的影响。研究发现,改性使得ACF样品比表面积和孔容略有降低,但表面含氧官能团含量增加,吸附甲苯的能力也因此增强。当模拟烟气中O2浓度为5%时,ACF脱除VOC效果达到最佳,超过5%之后,氧的促进效果不再明显;温度40℃为最佳吸附温度;当烟气中加入水蒸气时,ACF对VOC的脱除效率降低。     

催化超临界水氧化偏二甲肼动力学研究

采用CuO/γ-Al2O3和MnO2/γ-Al2O3为催化剂、H2O2为氧化剂,在一连续流固定床反应器中进行了催化超临界水氧化偏二甲肼实验,得到了COD去除宏观动力学方程.在24 MPa、400～450℃和H2O2过量的情况下,反应对COD分别为1.11级(CuO)和1.26级(MnO2),对氧气分别为0.10级(CuO)和0.12级(MnO2).反应的活化能分别为35.75 kJ/mol(CuO)和37.79 kJ/mol(MnO2),前置因子A分别为9.35×102(CuO)和3.45 ×103(MnO2).     

过渡金属浸渍改性ACF去除H2S研究

为探讨活性炭纤维(ACF)去除恶臭气体H2S的性能,采用过渡金属浸渍改性ACF吸附H2S,揭示出改性ACF前后吸附H2S的性能差异及浸渍剂的浓度和种类对ACF吸附性能的影响。结果表明,通过过渡金属改性后的ACF吸附性能有显著提高,对H2S吸附是物理吸附和化学吸附共同作用的结果,改性后的ACF硫容量大小依次为：5％硝酸铜...     

生物催化氧化法脱除H2S的试验研究

针对H2S污染的严峻形势,构建了包括催化再生装置和生物滴滤器的生物催化氧化装置.该装置以沸石为填料,以氧化亚铁硫杆菌为脱硫菌种,通过微生物和Fe3 的双重氧化作用高效脱除H2S.试验确定了装置的适宜喷淋量和沸石的最佳粒径.在温度为30 ℃,进气量为0.25 m3/h,进气H2S浓度为2500 mg/m3,喷淋量为1000 mL/h,喷淋液的pH值为1.97、Fe3 浓度为0.05 mol/L的条件下,出气H2S浓度足以达到GB14554-93规定的一级厂界标准值.试验证明,生物催化氧化法是一种新型高效的脱硫技术,应进一步开展中试研究.     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

Kinetic and structural relationships of transition monomeric and oligomeric carboxyl- and choline-esterases

The kinetic and structural relationships of eight electrophoretically pure mammalian serum and liver serine carboxylesterases (CE) and cholinesterases (ChE) have been studied. Eight CE's and ChE's, which were fully resolved but only partially purified, provided additional information. Five of the electrophoretically pure esterases were monomeric, and of these, four belonged to a new and widely distributed class. These four monomeric esterases hydrolyzed choline esters, but at widely differing rates. Thus two were termed monomeric butyrylcholinesterases, mBuChE I and II, and two were monomeric CE's (mCE). The rabbit liver mCE was not a subunit of the oligomeric CE (oCE), although the oCE also hydrolyzed choline esters at a very low rate. The complex kinetics of the mCE's, mBuChE's, oCE's, and of the oligomeric BuChE's of horse and human serum could be interpreted according to a single reaction scheme involving an allosteric site and the equation derived from it. Thus activation and inhibition at high substrate concentrations, together with sigmoidal activity versus substrate concentration plots, all of which characterize the reactions of these esterases, could be interpreted by a single scheme and equation. Structural and kinetic comparisons showed a progressive transition of properties from the oCE's through the mCE's to the oBuChE's. One of the purified mCE's was from horse serum, and it exhibited physical and kinetic properties unlike those of the liver mCE's or oCE's.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Bacterial and archaeal diversity in oil fields and reservoirs and their potential role in hydrocarbon recovery and bioprospecting

Environmental Science and Pollution Research - Hydrocarbon is a primary source of energy in the current urbanized society. Considering the increasing demand, worldwide oil productions are declining...     

畜禽养殖业污染与循环经济

解决畜禽养殖业的污染问题要以充分利用资源为根本出发点，通过对污染全过程控制及废物综合利用，达到畜禽粪便的减量化、无害化、资源化，走循环经济的发展道路。     

Isocyanatocyclohexane and isothiocyanatocyclohexane levels in urban and industrial areas and possible emission-related activities

Isocyanatocyclohexane and isothiocyanatocyclohexane are becoming relevant compounds in urban and industrial air, as they are used in important amounts in automobile industry and building insulation, as well as in the manufacture of foams, rubber, paints and varnishes. Glass multi-sorbent tubes (Carbotrap, Carbopack, Carboxen) were connected to LCMA-UPC pump samplers for the retention of iso- and isothiocyanatocyclohexanes. The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detector (MSD). TD-GC/MS was chosen as analytical method due to its versatility and the possibility of analysis of a wide range of volatility and polarity VOC in air samples. The method was satisfactory sensitive, selective and reproducible for the studied compounds. The concentrations of iso- and isothioisocyanatocyclohexanes were evaluated in different urban, residential and industrial locations from extensive VOC air quality and odour episode studies in several cities in the Northeastern edge of Spain. Around 200–300 VOC were determined qualitatively in each sample. Higher values of iso- and isothiocyanatocyclohexane were found in industrial areas than in urban or residential locations. The concentrations ranged between n.d.−246 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively, for industrial areas. On the other hand, urban and residential locations showed concentrations ranging between n.d.−164 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively. The site location (urban or industrial), the kind and nearness of possible iso- and isothiocyanatocyclohexane emission activities (industrial or building construction) and the changes of wind regimes throughout the year have been found the most important factors influencing the concentrations of these compounds in the different places.     

Degradation in soil and water and ecotoxicity of rimsulfuron and its metabolites.

The degradation and ecotoxicity of sulfonylurea herbicide rimsulfuron and its major metabolites were examined in batch samples of an alluvial sandy loam and in freshwater. An HPLC-DAD method was adapted to simultaneously identify and quantify rimsulfuron and its metabolites, which was successfully validated by GC-MS analysis. In aqueous solutions, pure rimsulfuron was rapidly hydrolyzed into metabolite 1 (N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinylurea)), which itself was transformed into the more stable metabolite 2 (N-((3-(ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine)), with half-life (t(1/2)) values of 2 and 2.5 days, respectively. Hydrolysis was instantaneous under alkaline conditions (pH = 10). In aqueous suspensions of the alluvial soil (pH = 8), formulated rimsulfuron had a half-life of 7 days, whereas that of metabolite 1 was similar to that in water (about 3.5 days). The degradation of the two major metabolites was also studied in soil suspensions with the pure compounds at concentrations ranging from 1 to 10 mg l(-1). The half-life of metabolite 1 ranged from 3.9 to 5 days, close to the previous values. Metabolite 2 was more persistent and its degradation is strongly dependent on the initial concentration (C0): half-life values ranged from 8.1 to 55 days at 2-10 mg l(-1), respectively. These values are higher than those determined from the kinetics of metabolite 1 transformation into metabolite 2 (t(1/2) = 8-19 days). The ecotoxicity of the three chemicals was evaluated through their effect on Daphnia magna and Vibrio fischeri (Microtox bioassay). No effect was observed on D. magna with 24 and 48 h acute toxicity tests. Similarly, no toxic effect was observed with the Microtox test for the three chemicals in the range of concentrations tested that included the field application dose. Thus, being of low persistence and lacking acute toxicity, these chemicals present a low environmental risk. However, chronic effects should be studied in order to confirm the safety of rimsulfuron and its major metabolites.