环境治理中光催化剂的失活与再生

催化剂失活是影响光催化过程用于污染治理经济实用的关键因素。对近几年来国内外环境污染控制中光催化剂的失活现象及其原因进行了综述．分析了液相和气相光催化反应体系中催化剂失活后再生的方法．特别是对气相光催化反应中水蒸汽的影响进行了讨论。     

氯化汞对小鼠睾丸生殖细胞的DNA损伤作用

探索氯化汞对雄性小鼠生殖细胞毒性的分子遗传机制。分别以 0 .0 1、0 .10、1.0 0 mmol/L的氯化汞体外处理小鼠睾丸细胞和以 0 .5、1.0、5 .0 μmol/kg的氯化汞体内暴露小鼠 ,应用单细胞凝胶电泳技术检测生殖细胞 DNA的损伤。体外处理 3种剂量组小鼠睾丸生殖细胞 DNA损伤率显著高于阴性对照组 ( 0 mmol/L组 ,P<0 .0 0 1) ;0 .1、1.0 mmol/L剂量组慧星细胞迁移率显著高于阴性对照组 ( P<0 .0 0 1,P<0 .0 5 )。体内暴露 3种浓度氯化汞组小鼠睾丸生殖细胞 DNA损伤率显著高于阴性对照组 ( 0μmol/kg,P<0 .0 0 1) ,5 .0 μmol/kg组慧星迁移率显著高于阴性对照组 ( P<0 .0 5 )。一定剂量的氯化汞处理引起生殖细胞 DNA损伤作用可能是氯化汞细胞毒性的机制之一。     

Investigation on the influence of methanol on adsorption and leaching of pesticides with soil column liquid chromatography

The effect of methanol of low concentration on adsorption and leaching of atrazine and tebuconazole was studied in this paper. The adsorption coefficients and the retardation factors (R^m) of pesticides on EUROSOIL 3# log-linearly decreased as volumetric fraction of methanol (f^c) was increased in the binary solvent mixtures of methanol and water. These data are consistent with solvophobic theory formerly outlined for describing the adsorption and transport of hydrophobic organic chemicals from mixed solvents. Nevertheless, the adsorption of these pesticides in soil–water system slightly increased when the soil was pre-washed with methanol in comparison with that pre-washed with water (pure water system). Furthermore, their adsorption coefficients were still higher in binary solvent systems with methanol of very low concentrations, i.e. f^c<0.03 for atrazine and f^c<0.01 for tebuconazole, than those in pure water system. The adsorption coefficients (logK^w) of atrazine and tebuconazole predicted by solvophobic theory were 0.5792 and 1.6525, respectively, and their experimental logK^w were 0.3701 and 1.6275 in pure water system. Obviously, the predicted logK^w of the two pesticides was higher than the experimental log K^w in pure water system. The predicted K^w and the retardation factor (R^w) in pure water system by solvophobic theory are thus possibly inaccurate.     

Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors

Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.     

Correlation of gas chromatographic properties of chlorobenzenes and polychlorinated biphenyls with the occurrence of reductive dechlorination by untamed microorganisms

To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.     

Effects of butachlor on microbial populations and enzyme activities in paddy soil

This paper reports the influences of the herbicide butachlor (n-butoxymethlchloro -2', 6'-diethylacetnilide) on microbial populations, respiration, nitrogen fixation and nitrification, and on the activities of dehydrogenase and hydrogen peroxidase in paddy soil. The results showed that the number of actinomycetes declined significantly after the application of butachlor at different concentrations ranging from 5.5 microg g(-1) to 22.0 microg g(-1) dried soil, while that of bacteria and fungi increased. Fungi were easily affected by butachlor compared to the bacteria. The growth of fungi was retarded by butachlor at higher concentrations. Butachlor however, stimulated the growth of anaerobic hydrolytic fermentative bacteria, sulfate-reducing bacteria (SRB) and denitrifying bacteria. The increased concentration of butachlor applied resulted in the higher number of SRB. Butachlor inhibited the growth of hydrogen-producing acetogenic bacteria. The effect of butachlor varied on methane-producing bacteria (MPB) at different concentrations. Butachlor at the concentration of 1.0 microg g(-1) dried soil or less than this concentration accelerated the growth of MPB, while at 22.0 microg g(-1) dried soil showed an inhibition. Butachlor enhanced the activity of dehydrogenase at increasing concentrations. The soil dehydrogenase showed the highest activity on the 16th day after application of 22.0 microg g(-1) dried soil of butachlor. The hydrogen peroxidase could be stimulated by butachlor. The soil respiration was depressed during the period from several days to more than 20 days, depending on concentrations of butachlor applied. Both the nitrogen fixation and nitrification were stimulated in the beginning but reduced greatly afterwards in paddy soil.     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

Pollution characterization and diurnal variation of PBDEs in the atmosphere of an E-waste dismantling region

Diurnal air samples were collected from the E-waste dismantling region Guiyu and the underwear industry region Chendian. This was the first report to present the diurnal variation of PBDEs in the atmosphere. The average concentrations of 11 PBDE congeners were 11,742 pg m⁻³ in the daytime, and 4830 pg m⁻³ at night in Guiyu, while the concentrations were lower in Chendian with 376 pg m⁻³ in the daytime, and 237 pg m⁻³ at night. BDE-209 accounted for 22% and 31.3% of the total PBDEs in Guiyu and Chendian, respectively. The diurnal variation trends of BDE-47, -99, -153, -183, and -209 were also analyzed in detail in the two regions.     

Polychlorinated biphenyls and organochlorine pesticides in various bird species from northern China

Little data are available on organochlorine contamination in Chinese terrestrial birds of prey. This study examined the presence of PCBs, DDTs and other organochlorine pesticides in various raptors from northern China. DDE exhibited the highest concentrations among targeted compounds. Greatest levels (23.5-1020 mg/kg lipid weight) were observed in Eurasian sparrowhawks. This may be due to their stopover in southeastern China, where high DDT and dicofol applications have been documented. Residential kestrels exhibited much lower DDE, but similar PCB and HCH concentrations. ΣTEQs and PCB-126/-77 concentration ratios exhibited significant positive correlations with ΣPCB concentrations, respectively. Similar results were also demonstrated by a meta-analysis of previously published data across avian species. Possible hepatic sequestration of coplanar PCB-77, -126, -169 and -118 was observed as liver TEQs increased in Eurasian sparrowhawks. These observations may indicate an induction of CYP1A enzymes, as a result of elevated contamination in some species.