半亲半疏阴极催化电芬顿工艺去除罗丹明B的性能

为解决传统曝气式电芬顿系统中氧气的传质限制和低效利用问题,利用石墨毡疏水化处理与催化剂涂覆的方法制备了一种非对称浸润性的半亲半疏阴极,且对半亲半疏阴极进行了结构表征和电化学性能测试,考察了阴极浸润性、阴极电势和曝气速率对有机污染物去除的影响。结果表明：在−0.4 V (vs. Ag/AgCl)和6 mL·min⁻¹的曝气速率下,半亲半疏阴极在32 min内的罗丹明B去除率高达89.4%,是亲水阴极的8.0倍和疏水阴极的2.2倍,这主要得益于疏水化石墨毡基底的良好O₂储存能力以及亲水催化剂层的较大电化学活性面积。     

The effect of changes in surface wettability on two-phase saturated flow in horizontal replicas of single natural fractures

By using translucent epoxy replicas of natural single fractures, it is possible to optically measure aperture distribution and directly observe NAPL flow. However, detailed characterization of epoxy reveals that it is not a sufficiently good analogue to natural rock for many two-phase flow studies. The surface properties of epoxy, which is hydrophobic, are quite unlike those of natural rock, which is generally assumed to be hydrophilic. Different surface wettabilities result in dramatically different two-phase flow behavior and residual distributions. In hydrophobic replicas, the NAPL flows in well-developed channels, displacing water and filling all of the pore space. In hydrophilic replicas, the invading NAPL is confined to the largest aperture pathways and flow frequently occurs in pulses, with no limited or no stable channel development, resulting in isolated blobs with limited accessible surface area. The pulsing and channel abandonment behaviors described are significantly different from the piston-flow frequently assumed in current modeling practice. In addition, NAPL never achieved total saturation in hydrophilic models, indicating that significantly more than a monolayer of water was bound to the model surface. Despite typically only 60-80% NAPL saturation, there was generally good agreement between theoretically calculated Young-Laplace aperture invasion boundaries and the observed minimum apertures invaded. The key to determining whether surface wettability is negligible, or not, lies in accurate characterization of the contaminant-geologic media system under study. As long as the triple-point contact angle of the system is low (<20 degrees), the assumption of perfect water wettability is not a bad one.     

The effect of changes in surface wettability on two-phase saturated flow in horizontal replicas of single natural fractures

By using translucent epoxy replicas of natural single fractures, it is possible to optically measure aperture distribution and directly observe NAPL flow. However, detailed characterization of epoxy reveals that it is not a sufficiently good analogue to natural rock for many two-phase flow studies. The surface properties of epoxy, which is hydrophobic, are quite unlike those of natural rock, which is generally assumed to be hydrophilic. Different surface wettabilities result in dramatically different two-phase flow behavior and residual distributions. In hydrophobic replicas, the NAPL flows in well-developed channels, displacing water and filling all of the pore space. In hydrophilic replicas, the invading NAPL is confined to the largest aperture pathways and flow frequently occurs in pulses, with no limited or no stable channel development, resulting in isolated blobs with limited accessible surface area. The pulsing and channel abandonment behaviors described are significantly different from the piston-flow frequently assumed in current modeling practice. In addition, NAPL never achieved total saturation in hydrophilic models, indicating that significantly more than a monolayer of water was bound to the model surface. Despite typically only 60–80% NAPL saturation, there was generally good agreement between theoretically calculated Young–Laplace aperture invasion boundaries and the observed minimum apertures invaded. The key to determining whether surface wettability is negligible, or not, lies in accurate characterization of the contaminant-geologic media system under study. As long as the triple-point contact angle of the system is low (< 20°), the assumption of perfect water wettability is not a bad one.     

A new model for humic materials and their interactions with hydrophobic organic chemicals in soil-water or sediment-water systems

A generalized model of humic materials in soils and sediments, which is consistent with their observed properties, is presented. This model provides a means of understanding the interaction of hydrophobic pollutants with humic materials. In this model, it is proposed that the humic materials in soils and sediments consist of a number of different oligomers and simple compounds which result from the partial degradation of plant remains. These degradation products are stabilized by incorporation into humic aggregates bound together by weak bonding mechanisms, such as hydrogen bonding, pi bonding, and hydrophobic interactions. The resulting structures are similar to micelles or membranes, in which the interiors of the structures are hydrophobic and the exteriors are hydrophilic. Hydrophobic compounds will partition into the hydrophobic interiors of the humic micelles or “membrane-like” structures.     

Scaling of spontaneous imbibition data with wettability included

Wettability is a dominant parameter governing spontaneous imbibition. However less attention has been paid to the effect of wettability on the scaling of spontaneous imbibition data. Actually few models can include wettability in scaling of spontaneous imbibition data. To this end, a scaling model has been developed for NAPL (oil)-saturated porous media with different wettability based on the fluid flow mechanisms in porous media. Relative permeability, capillary pressure, initial water saturation, and wettability are considered in the scaling model. Theoretically this scaling model is suitable for both cocurrent and countercurrent spontaneous imbibition. The experimental data of countercurrent spontaneous water imbibition at different wettability cannot be scaled using the frequently used scaling model but can be scaled satisfactorily using the scaling model developed in this study. An analytical solution to the relationship between recovery and imbibition time for linear spontaneous imbibition has also been derived in the case in which gravity is ignored. The analytical solution predicts a linear correlation between the recovery by spontaneous water imbibition and the square root of imbibition time, which has been verified against experimental data.     

Wettability hysteresis and its implications for DNAPL source zone distribution

Subsurface heterogeneity at sites contaminated with nonaqueous phase liquids (NAPLs) reduces the effectiveness of traditional remediation measures. One cause may be the increased proportion of NAPL that is hydraulically isolated due to capillary trapping in heterogeneously-wetted materials. This study examines the wettability of ten materials, ranging from minerals, such as calcite and dolomite, to carbonaceous materials, such shale and coal, in air and water, NAPL and air, and NAPL and water systems. The wettability differed depending on which phase the solid material was initially immersed in: the less crystalline solids, if initially contacted by water were water-wet, but if initially contacted by NAPL were NAPL-wet. This difference, termed here wettability hysteresis, was observed for a suite of halogenated NAPLs and was independent of equilibration time. The degree of wettability hysteresis was greatest in the NAPL and water systems, with the magnitude of the difference increasing with the carbonaceous materials. Since the degree of capillary trapping in subsurface materials is related to wettability, the phenomenon of wettability hysteresis suggests that system history is a factor that may increase the heterogeneity of NAPL source zones.     

沉积物溶解性有机氮藻类的可利用性

采用DAX-8树脂和732氢型阳离子交换树脂将山口湖沉积物中溶解性有机氮（DON）分成亲水组分和疏水组分,在室内培养条件下,研究了其对羊角月牙藻的可利用性。结果表明：通过DAX-8树脂后,N4和N14沉积物DON回收率分别为98.96%和104.34%。原水和亲水DON组分通过阳离子交换树脂后会吸附类蛋白物质,降低藻类生物量。培养过程中,N4原水和亲水组分DON消耗量分别为0.34 mg·L-1和0.36 mg·L-1,低于N14原水和亲水组分DON消耗量0.94 mg·L-1和0.82 mg·L-1,表明N14亲水组分藻类可利用较N4亲水组分多。由于阳离子交换树脂对N4原水和亲水组中DON去除率较高,其藻类的生物量低于N14原水组和亲水组。N4疏水性组分DON的利用量和藻细胞生物量分别为0.80 mg·L-1和15×104个·mL-1,高于N14组,这是因为N4接收了长水河农场生活污水和周围农田径流中易降解DON。利用PARAFAC模型对培养过程中三维荧光光谱数据解析出1种类蛋白物质和2种类腐殖质物质。培养初期,类蛋白物质先被藻类所利用导致其含量降低,而随着藻类生长进入对数期,释放到水体中类蛋白物质导致其相对荧光强度的增加。在整个培养过程中,类腐殖质物质相对荧光强度的增加主要来源于死亡藻类的释放。     

Kinetic constraints on theIn-situ remediation of soils contaminated with organic chemicals

Cleanup of contaminated soils to comply with soil quality limits currently receives much interest.In-situ remediation of contaminated soils relies on the ability of the techniques employed to enhance the rate of release of contaminants from the soil-sorbed and nonaqueous phase liquid (NAPL) phases into the aqueous or gaseous phases from which they can be more readily removed and treated. Contaminant concentrations in these “environmentally mobile” forms usually decline over time so that the economic efficiency and the overall success of remediation technologies are subject to the “law of diminishing returns”. In this paper we consider the “state of the art” in our understanding of NAPL dissolution and transport, desorption of soilsorbed contaminants and fluid flow in porous media. The extent to which these processes may constrain the success of bioremediation, pump-and-treat remediation and soil venting in relation to established soil quality limits is addressed. Finally, we suggest directions for future research and comment on legislative considerations.     

微气泡催化臭氧化深度处理制药废水的效果及DOM组分特性的变化

采用镁铝层状双氢氧化物(MAL)微气泡催化臭氧化(MAL/MB/O₃)体系深度处理实际制药废水,考察了该体系对溶解性有机物(DOM)的深度去除性能及DOM组分的变化特性,并与普通气泡臭氧化(CB/O₃)、普通气泡催化臭氧化(MAL/CB/O₃)、微气泡臭氧化(MB/O₃)工艺进行了比较。结果表明,MAL/MB/O₃处理性能优于CB/O₃、MAL/CB/O₃和MB/O₃,在臭氧投加总量与处理废水初始COD值之比为0.6、气流量0.5 L·min⁻¹、催化剂投加量0.5 mg·L⁻¹的条件下,整体COD去除率可达49.79%,COD去除量与臭氧消耗量的比值为0.83,废水的可生化性得到了一定改善,生物毒性显著下降。废水DOM中疏水性组分氧化去除率高于亲水性组分。臭氧直接氧化可去除疏水性组分,而亲水性组分去除主要依赖HO·氧化。MAL/MB/O₃对DOM的去除效率最高,可达到52.51%,其中疏水性组分整体去除率56.67%,亲水性组分整体去除率46.93%。废水DOM在氧化处理中存在官能团向酸性基团转化、类腐殖质向类富里酸和类胡敏酸转化、其他组分向亲水性酸(HIA)组分转化的趋势。MAL/MB/O₃强氧化能力对于DOM组分不饱和结构和荧光结构的破坏作用最为显著。以上研究结果可为制药废水深度处理提供参考。     

Pentachlorophenol sorption by variable-charge soils in methanol-water mixture: pH effect at the low solvent volume fraction

Information on how cosolvents affect sorption of ionizable chemicals by soils with heterogeneous variable-charge mineral surface domains is sparse. In this study, the effect of soil-solution pH in methanol/water solutions on sorption of pentachlorophenol (PCP) by variable-charge soils with a range of hydrophilic (f Hphilic) and hydrophobic (f Hphobic) sorption domains was characterized. PCP sorption by 10 variable-charge soils was measured as a function of apparent pH (pH app) and methanol volume fraction (fc8) decreased log-linearly with increasing fc, but the slope of the relationship was less for anionic PCP. The empirical solvent-sorbent interaction term for anionic PCP (alpha i) was inversely correlated with f Hphilic (r2=0.82), which is consistent with methanol-induced increases in anion exchange. For neutral PCP, the empirical term (alpha n) was positively correlated with f Hphobic (r2=0.84), supporting methanol-induced increases in solution and sorbent hydrophobicity. Sorption of PCP by two soils with varying f Hphilic in the pH app range from 3 to 8 at fc相似文献   

亲水性塑料弹性填料生物膜法处理模拟废水的研究

通过比较普通塑料弹性填料与亲水性改进后的塑料弹性填料在污水生化处理中的应用效果发现 :亲水性改进的塑料弹性填料在污水的厌氧生化处理中可提高污水处理效率 15 %— 30 % ,在好氧生化处理中可提高污水处理效率5 %— 10 % ,且亲水性改进大大提高了塑料弹性填料的挂膜速度。     

Evaluation of PPCPs removal in a combined anaerobic digester-constructed wetland pilot plant treating urban wastewater

The removal efficiency of 16 pharmaceuticals and personal care products (PPCPs) from urban wastewater (dissolved and particulate phases) was evaluated for the first time in a hybrid pilot plant consisting of an upflow anaerobic sludge blanket reactor followed by two sequentially connected horizontal flow constructed wetlands: a surface flow wetland (SF CW) and a subsurface flow wetland (SSF CW). Whereas the PPCP removal associated with the dissolved phase exhibited a seasonal pattern, the fraction associated with the suspended solids showed less seasonality. In the dissolved phase, the overall removal efficiency in summer ranged from 70% to 85% for salicylic acid (SAL), methyl dihydrojasmonate, caffeine (CAF), ketoprofen and triclosan, whereas in winter it declined for most of the PPCPs to between 30% and 50%, except for CAF and SAL (>80%) and carbamazepine and butylated hydroxyl toluene (11-18%). In the suspended solids, the removal exceeded 80% for most of the target PPCPs. The efficiency of the different treatment steps was also compound-dependent, but the SF CW generally exhibited the highest removal efficiency for most of the contaminants analyzed. The characterization of the organic matter retained in the wetland gravel beds revealed the occurrence of hydrophobic contaminants such as phthalate esters and fragrances at moderate concentrations (i.e., up to 3.5 μg kg⁻¹), which declined strongly over the course of the different treatment steps. In the SF CW, the net mass accumulation rates of tonalide and galaxolide were 4 and 23 g y⁻¹ respectively, whereas in the SSF CW they were 0.3 and 1.8 g y⁻¹ respectively.     

Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.     

Nontargeted evaluation of the fate of steroids during wastewater treatment by comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry

Emerging organic contaminants in wastewater are usually analyzed by targeted approaches, and especially estrogens have been the focus of environmental research due to their high hormonal activity. The selection of specific target compounds means, however, that most of the sample components, including transformation products and potential new contaminants, are neglected. In this study, the fate of steroidal compounds in wastewater treatment processes was evaluated by a nontargeted approach based on comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry. The potential of the nontargeted approach to generate comprehensive information about sample constituents was demonstrated with use of statistical tools. Transformation pathways of the tentatively identified compounds with steroidal four-ring structure were proposed. The purification efficiency of the wastewater treatment plants was studied, and the distribution of the compounds of interest in the suspended solids, effluent water, and sludge was measured. The results showed that, owing to strong adsorption of hydrophobic compounds onto the solid matter, the steroids were mostly bound to the suspended solids of the effluent water and the sewage sludge at the end of the treatment process. The most abundant steroid class was androstanes in the aqueous phase and cholestanes in the solid phase. 17β-estradiol was the most abundant estrogen in the aqueous phase, but it was only detected in the influent samples indicating efficient removal during the treatment process. In the sludge samples, however, high concentrations of an oxidation product of 17β-estradiol, estrone, were measured.     

Nutrient losses by surface run-off following the application of organic manures to arable land. 1. Nitrogen

Research was conducted on nitrogen (N) surface run-off losses following organic manure applications to land, utilising a purpose-built facility on a sloping site in Herefordshire under arable tillage. Different rates and timing of cattle slurry, farmyard manure and inorganic N and phosphorus (P) fertiliser were compared, over a 4-year period (1993-97). P losses from the same studies are reported in a separate paper. The application of cattle slurries to the silty clay loam soil increased the loss of solids and NH4(+)-N in surface water flow compared to control plots receiving inorganic fertiliser only, or no treatment, but had little effect on NO3(-)-N losses by this route. Results were consistent with other observations that rainfall events immediately after manure applications are particularly likely to be associated with nutrient run-off losses. Losses via subsurface flow (30 cm interflow) were consistently much lower than via surface water movement and were generally unaffected by treatment. Increasing slurry application rate and, in particular, slurry solids loading, increased solids and NH4(-)-N losses via surface run-off. The threshold, above which the risk of losses via surface run-off appeared to be greatly increased, was ca. 2.5-3.0 t/ha slurry solids, which approximates to the 50 m3/ha limit suggested for slurry within UK 'good agricultural practice'. Sealing of the soil surface by slurry solids appears to be a possible mechanism by which polluting surface run-off may occur following slurry application on susceptible soils. Total losses of NH4(+)-N and NO3(-)-N during the 4-year monitoring period were insignificant in agronomic terms, but average soluble N concentrations (NH4(+)-N + NO3(-)-N) in run-off, ranging from ca. 2.0 mg/l, up to 14.0 mg/l for the higher rate slurry treatments. Peak concentrations of NH4(+)-N > 30 mg/l, are such as to be of concern in sensitive catchments, in terms of the potential for contribution to accelerated eutrophication and adverse effects on freshwater biota.     

Predicting surfactant modified soil/water distribution coefficients using micellar HPLC

Soil water/distribution coefficients (Kd) have been measured for the partitioning of naphthalene, phenanthrene and pyrene between aqueous surfactant solutions and a clean soil. The surfactants used are ABA block copolymers constructed from ethylene oxide (the monomer used to synthesise the hydrophilic A blocks) and propylene oxide (used for the manufacture of the hydrophobic B block). Three of these surfactants comprising the same size propylene oxide block but different ethylene oxide/propylene oxide ratios were investigated. Increasing amounts of surfactant in the system result in a progressive decrease in the Kd values signifying an increasing tendency for the hydrophobic solutes to be dispersed in aqueous solution due to the action of the surfactant. More significantly for equal surfactant doses the most hydrophobic surfactant possessing the lowest ethylene oxide/propylene oxide ratio reduces Kd by the greatest amount whereas the most hydrophilic surfactant reduces Kd the least. Finally micellar HPLC using the above surfactants and hydrophobic solutes was undertaken. Interpolated capacity factors evaluated for particular surfactant doses correlated well with Kd values calculated for the same surfactant doses. The relationship between Kd and capacity was found to be log-linear and the correlation line could be fitted to the data obtained for all three surfactants. It is therefore concluded that micellar HPLC may be used for preliminary evaluations of the effectiveness of particular surfactants proposed for contaminated soils restoration schemes.     

生物过滤塔处理实验室废气

研究了生物过滤塔处理实验室排放的模拟混合废气,考察了反应器对苯、甲苯、二甲苯、乙醇、丙酮、乙酸乙酯和甲烷等废气的去除效果。运行结果表明,在设备稳定运行期间,进气中总挥发性有机物(TVOCs)的浓度为124～380 mg/m3,而出气浓度在10～40 mg/m3,去除效率保持在85%以上。实验室废气中的多种污染物在生物过滤塔中去除机理不同,亲水性污染物的去除效率高于疏水性污染物。通过系统关停后重启,污染物的去除效果在第2天就能恢复,这为生物过滤塔处理实验室废气过程的停运检修或者系统闲置提供了可行性。     

亲疏水性溶解性有机物对聚偏氟乙烯超滤膜污染行为

选用模拟亲疏水性有机物及实际二级处理水中的亲疏水性有机物,分别进行了聚偏氟乙烯(PVDF)超滤膜污染实验.并测定了不同污染物与膜及污染物间的作用力,分析亲/疏水性有机物对PVDF超滤膜的污染行为.结果表明,膜-污染物及污染物间相互作用力是控制膜污染行为的主导因素.亲水性有机物与PVDF超滤膜之间的相互亲和力较强,致使运行初期膜通量的大幅度下降,是PVDF膜的优势污染物.但是,针对实际污染物,运行后期,疏水性有机物之间较强的相互作用力使得其取代了亲水性有机物,成为膜的优势污染物.此外,模拟亲疏水性有机物的膜污染变化规律与实际亲疏水性有机物相似,表明使用模拟污染物可一定程度上预测实际废水中相应性能污染物的膜污染行为.     

Sorption of isoxaflutole diketonitrile degradate (DKN) and dicamba in unsaturated soil

When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with 14C-labeled chemical.The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, Kd, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN Kd values were approximately 2-3 times (average Kd = 0.71 L kg-1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (Kd = 0.33 L kg-1), but similar for the two methods in sand (0.12 vs 0.09 L kg-1) soils. Dicamba Kd values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg-1), however, the Kd values were the same for the two methods in the sand (approximately 0.06 L kg-1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.     

Volatilisation of o-xylene from sandy soil

The diffusive release of o-xylene from two soils with different contents of organic carbon (1.1 % and 0.11 % TOC) and with two different water contents (app. 5 % w/w and 15 % w/w was studied in the laboratory. The soils were spiked with o-xylene in the laboratory. The fluxes were measured over a period of 24 hours. The measured fluxes were compared to predictions by two models. Model I, which is an analytical model, assumed instant local equilibrium between soil air, water and solids. The distribution coefficients were measured for the two soils, and Henry's constant and the diffusion coefficient in air were taken from the literature. This model overestimated the flux for o-xylene for all the tested combinations. The ratios between estimated and observed fluxes at 1 h were between 1.7 and 7.3. Model II assumed that the mass transfer of o-xylene between the solids and the water phase was kinetically controlled and was solved numerically. However, the predictions by the more advanced model were not significantly better than the prediction by the simple analytical model. The results indicate that prediction of o-xylene volatilisation from unsaturated soil is associated with substantial uncertainty.