难降解有机废水处理新技术

介绍了光氧化法、超临界氧化和低温等离子体化学三种废水处理新技术的原理,国内外研究的现状和未来的发展前景,分析了这些新技术在优化污染物废水处理方面得到工业应用所必须解决的主要技术问题.     

废水处理的新趋势与新技术

介绍了我国水污染方面的情况、水污染治理的常用技术及基本工艺流程、水治理技术发展的新趋势和几种水处理的新技术。对这些新技术的基本原理、研究方向与前景作了阐述。     

Pathway of anthracene modification under simulated solar radiation

Exposure of polycyclic aromatic hydrocarbons (PAHs) to sunlight results in rapid structural photomodification generally via oxidation reactions. These PAH modification products are in many cases more toxic than their parent compounds. In this study, anthracene (ANT), a rapidly photooxidized PAH, was irradiated with simulated solar radiation (SSR, 100 μmol m⁻² s⁻¹) in aqueous solution to examine the photomodification pathway. The photoproducts formed were identified by HPLC. The ANT product profile after 9 h in SSR was very complex, with more than 20 compounds detected. The photoproducts formed were anthraquinones, benzoic acids, benzaldehydes and phenols showing the process to be oxidative in nature. Some of the anthraquinones were themselves subject to photooxidation, and were thus intermediates in the product pathway. The kinetics of ANT photooxidation revealed a pseudo first-order reaction with a half-life of 2 h under the SSR source used. The kinetics of product formation allowed deduction of a probable photomodification pathway. This study indicates that PAH photooxidation products are likely to exist as complex, dynamically changing mixtures in PAH contaminated aquatic environments.     

Effect of NOx and RH on the secondary organic aerosol formation from toluene photooxidation

The secondary organic aerosol (SOA) formation mechanism and physicochemical properties can highly be influenced by relative humidity (RH) and NOx concentration. In this study, we performed a laboratory investigation of the SOA formation from toluene/OH photooxidation system in the presence or absence of NOx in dry and wet conditions. The chemical composition of toluene-derived SOA was measured using Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). It was found that the mass concentration of toluene decreased with increasing RH and NOx concentration. However, the change of SOA chemistry composition (f₄₄, O/C) with increased RH was not consistent in the condition with or without NOx. The light absorption and mass absorption coefficient (MAC) of the toluene-derived SOA only increased with RH in the presence of NOx. In contrast, MAC is invariant with RH in the absence of NOx. HR-ToF-AMS results showed that, in the presence of NOx, the increased nitro-aromatic compounds and N/C ratio concurrently caused the increase of SOA light absorption and O/C in wet conditions, respectively. The relative intensity of CHON and CHO_xN family to the total nitrogen-containing organic compounds (NOCs) increased with the increasing RH, and be the major components of NOCs in wet condition. This work revealed a synergy effect of NOx and RH on SOA formation from toluene photooxidation.     

Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber

The gas phase atmospheric degradation of diazinon has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The rate constant for reaction of diazinon with OH radicals was measured using a conventional relative rate method with di-n-buthylether as reference compound being k = (3.5 ± 1.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ at 302 ± 10 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of diazinon is mainly controlled by reaction with OH radicals, and that the tropospheric lifetime with respect to the OH reaction is estimated to be around 4 h whereas its lifetime with respect to the photolysis is higher than 1 d under our conditions. Significant aerosol formation was observed following the reaction of diazinon with OH radicals, and the main carbon-containing products detected in the particle phase were hydroxydiazinon, hydroxydiazoxon and 2-isopropyl-6-methyl-pyrimidinyl-4-ol.     

Heterogeneous photocatalytic oxidation of cyprodinil and fludioxonil in leaching water under solar irradiation

The efficiency of ZnO and TiO₂ suspensions in the photocatalytic degradation of two fungicides (cyprodinil and fludioxonil) in leaching water was investigated. The experiments were carried out at pilot plant scale using compound parabolic collectors under natural sunlight. The blank experiments for both irradiated compounds solutions showed that both oxides strongly enhanced the removal of the fungicides. The addition of an oxidant (Na₂S₂O₈) to the ZnO or TiO₂ increased the rate of photooxidation. The degradation of cyprodinil and fludioxonil followed first order kinetics according to the Langmuir-Hinshelwood model. Complete degradation of both fungicides was achieved within 4 h (t_30W = 18 min) when treated with illuminated ZnO. The disappearance time (DT₇₅), when referred to the normalized illumination time (t_30W), was lower than 40 and 550 min (t_30W = 2 and 40 min) for both fungicides using ZnO or TiO₂, respectively. ZnO appeared to be more effective in cyprodinil and fludioxonil oxidation than TiO₂ probably due to its nonstoichiometry.     

Mercury photoreduction and photooxidation in lakes: Effects of filtration and dissolved organic carbon concentration

Mercury is a globally distributed, environmental contaminant. Quantifying the retention and loss of mercury is integral for predicting mercury-sensitive ecosystems. There is little information on how dissolved organic carbon(DOC) concentrations and particulates affect mercury photoreaction kinetics in freshwater lakes. To address this knowledge gap,samples were collected from ten lakes in Kejimkujik National Park, Nova Scotia(DOC: 2.6–15.4 mg/L). Filtered(0.2 μm) and unfiltered samples were analysed for gross photoreduction, gross photooxidation, and net reduction rates of mercury using pseudo first-order curves. Unfiltered samples had higher concentrations(p = 0.04) of photoreducible divalent mercury(Hg(II)RED)(mean of 754 ± 253 pg/L) than filtered samples(mean of 482 ± 206 pg/L);however, gross photoreduction and photooxidation rate constants were not significantly different in filtered or unfiltered samples in early summer. DOC was not significantly related to gross photoreduction rate constants in filtered(R~2= 0.43; p = 0.08) and unfiltered(R~2= 0.02; p = 0.71) samples; DOC was also not significantly related to gross photooxidation rate constants in filtered or unfiltered samples. However, DOC was significantly negatively related with Hg(Ⅱ)_(RED) in unfiltered(R2= 0.53; p = 0.04), but not in filtered samples(R~2= 0.04;p = 0.60). These trends indicate that DOC is a factor in determining dissolved mercury photoreduction rates and particles partially control available Hg(Ⅱ)_(RED) in lake water. This research also demonstrates that within these lakes gross photoreduction and photooxidation processes are close to being in balance. Changes to catchment inputs of particulate matter and DOC may alter mercury retention in these lakes and could partially explain observed increases of mercury accumulation in biota.     

Photochemical alteration of the molecular weight of dissolved organic matter

Molecular weight (MW) is a key control on the physical, chemical, and biological characteristics of dissolved organic mater (DOM). This study investigated the effect of photooxidation on the average MW of DOM by exposing DOM of diverse origins to simulated solar radiation at varying levels of dissolved oxygen and under different incident light wavelength regimes. During irradiation, high-molecular-weight fractions were destroyed and low-molecular-weight constituents were formed. The average MW decreased with irradiation time in all treatments in a manner that can be described by a quasi-exponential function, which suggests that solar radiation is incapable of completely mineralizing DOM even after prolonged exposure. Increasing the oxygen concentration accelerated the MW reduction while the removal of oxygen strongly suppressed this process. The fractional contributions from UV-B, UV-A, and visible radiations to full-spectrum photoinduced MW reduction varied considerably among the DOM samples examined, ranging from 19% to 60%, 17% to 36%, and 15% to 46%, respectively. The MW changes in time-series irradiations were inversely correlated with the ratio of the absorbance at 250 nm to that at 365 nm (i.e., the E₂/E₃ quotient). Photoinduced MW reduction was accompanied by a decrease of polydispersity, which is indicative of a reduced DOM heterogeneity.     

Photochemical transformations of selected organic chemicals in two phase system

The photodegradation of some aromatic sulfur compounds dissolved in n‐hexane and spread as a thin liquid film on water was investigated. Dibenzothiophene and diphenylsulfide were found to be the most reactive towards photooxidation process among the compounds studied. The degraded compounds were investigated by HPLC and GC/MS.