Method for predicting photocatalytic oxidation rates of organic compounds

In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2) catalyst in a continuous mixed-batch reactor. It was found that PCO rate constants for alkanes and alkenes vary linearly with gas-phase ionization potential (IP) and with gas-phase hydroxyl radical reaction rate constant. The correlations allow rates of destruction of compounds not tested in this research to be predicted based on physical-chemical characteristics.     

复合人工湿地中低浓度有机物的去除及Monod模型模拟

以复合人工湿地工程实例为研究对象,研究了其在连续5个月内对低浓度有机污染物的深度处理效果,采用简化的Monod动力学模型对研究湿地进行模拟并验证,讨论了污染负荷与去除率的相关性以及BOD/COD比值对有机污染物降解系数的影响。研究湿地总面积为5 000 m2,进水水量为860～1 560 m3/d,水力停留时间为1.48～2.69 d,水力负荷为0.17～0.31 m/d,进水中有机污染物浓度较低(BOD53.0～25.6 mg/L;COD 22.9～89.8 mg/L)。结果表明,复合湿地组合形式对BOD5和COD的去除率分别介于37.9%～79.0%和41.0%～68.7%之间,简化的Monod模型对湿地中BOD5和COD去除的预测值与实验观测值吻合程度较好;BOD5、COD的去除率分别随着进水BOD5和COD浓度的增加而增大,而增长趋势逐渐变缓,当有机污染负荷低时,模型的K值较小;低浓度有机污染物在VSF、FWS和HSF湿地中的去除效率与有机物是否容易或者缓慢被微生物降解的性质相关性较差,这可能与人工湿地中存在的其他因素促进了有机污染物的去除有关。     

潜流人工湿地-生物接触氧化处理低温低浓度生活污水

在低温低浓度生活污水的实验研究中,回流比和气水比是影响潜流人工湿地一生物接触氧化组合工艺污染物去除效果的重要因素,推荐回流比R=1．0,气水比为4：1,在该工况下,进水COD浓度在170．8～221．3mg／L时,平均去除率可达90％;进水NH3-N浓度在17．3～25．9mg／L,平均去除率45％～65％;进水TN浓度在25．1～38．49mg／L时,平均去除率45％～65％;进水TP浓度在2．2～3．1mg／L时,平均去除率65％～80％。污染物沿程浓度分析结果表明,该组合工艺可以在低温季节通过曝气促进氨氮硝化,大幅提高NH3-N和TN去除率,同时可以充分发挥复合潜流湿地功能。     

A new approach to characterize biodegradation of organics by molecular mass distribution in landfill leachate

This study provides biodegradability of organics in leachate according to their molecular mass distributions (<0.5, 0.5 to 1, 1 to 3, 10, and >10 KDa). Organics with molecular mass values lower than 0.5 KDa were the predominant species in the raw leachate filtrate, and the aerated lagoon process was very effective in treating these highly biodegradable organics; the Fenton's oxidation process was very effective in treating not-so-biodegradable organics with molecular mass values higher than 0.5 KDa, but a portion of these organics were converted into organics <0.5 KDa after Fenton's oxidation. An oxygen uptake measurement using a respirometer was more sensitive than a conventional biochemical oxygen demand measurement to evaluate bioactivities, especially when bioactivities were low.     

VOCs in representative canadian residences

Stored extracts of passive samplers exposed in 757 randomly selected Canadian residences provided a unique opportunity for retrospective determination of the occurrence of airborne volatile organic compounds (VOCs). Aliquots of the individual extracts were pooled to form a composite exposure sample and a corresponding blank sample. To identify and quantitate potentially hazardous organics in the samples, GC-MS analyses were conducted by several approaches. The amounts of 52 target compounds in the the composite sample were estimated based on selected ion monitoring (SIM) results, extraction recoveries, average air volume sampled, and 3M OVM 3500 passive sampling rates. Forty of the organics were detected and were present in amounts equivalent to airborne concentrations ranging from <1 to 104 μg m⁻³. Several other compounds were also tentatively identified by full scan analysis. Many of the detected organics have been reported to be associated with activities such as tobacco smoking and the presence of consumer products and plastic materials indoors. The analytical results have been useful in risk assessments and establishment of a new Canadian priority substances list (PSL).     

Changes in character of organics in the receiving environment of effluent from a sulphite pulp mill

Purpose

The characteristics of organics in sulphite pulp mill effluent and in the receiving environment of effluent discharge were investigated to assess the basis for the persistence or attenuation of colour.

Methods

Characterization of organics was conducted through determination of SUVA, specific colour, and molecular weight distribution of organics using high performance size exclusion chromatography and by solid-state ¹³?C cross polarization (CP) NMR. The characteristics of organics from mill wastewater before and after secondary aerobic treatment, followed by lime treatment and from the receiving environment, an enclosed brackish lake were compared. Changes in the character of organics in lake water over a period of 14?years were studied in the context of changes in mill processing and climate impacts.

Results

High colour in mill effluent and in receiving waters correlated with high SUVA and specific colour levels, high molecular weight range and aromatic content. Conversely, lake waters with low colour had UV absorbing compounds of much lower molecular weight range and low relative abundance of aromatic compounds. Attenuation of colour and changes in the character of organics in the receiving environment coincided with increased concentrations of metal cations.

Conclusions

These increased concentrations appear to be due to the effects of climate change, lake management and their presence in mill effluent, with subsequent discharge to the lake. Attenuation of colour was found to be predominantly through removal of high molecular weight aromatic compounds where the removal processes could be through adsorption and co-precipitation with divalent metals, as well as through dilution processes.     

Transport and reduction of nitrate in clayey till underneath forest and arable land

Transport and reduction of nitrate in a typically macroporous clayey till were examined at variable flow rate and nitrate flux. The experiments were carried out using saturated, large diameter (0.5 m), undisturbed soil columns (LUC), from a forest and nearby agricultural sites. Transport of nitrate was controlled by flow along the macropores (fractures and biopores) in the columns. Nitrate reduction (denitrification) determined under active flow mainly followed first order reactions with half-lives (t(1/2)) increasing with depth (1.5-3.5 m) from 7 to 35 days at the forest site and 1-7 h at the agricultural site. Nitrate reduction was likely due to microbial degradation of accumulated organic matter coupled with successive consumption of O2 and NO3- in the macropore water followed by reductive dissolution of Fe and Mn from minerals along the macropores. Concentrations of total organic carbon measured in soil samples were near identical at the two study sites and consequently not useful as indicator for the observed differences in nitrate reduction. Instead the high reduction rates at the agricultural site were positively correlated with elevated concentration of water-soluble organic carbon and nitrate-removing bacteria relative to the forest site. After high concentrations of water-soluble organic carbon in the columns from the agricultural site were leached they lost their elevated reduction rates, which, however, was successfully re-established by infiltration of new reactive organics represented by pesticides. Simulations using a calibrated discrete fracture matrix diffusion (DFMD) model could reasonably reproduce the denitrification and resulting flux of nitrate observed during variable flow rate from the columns.     

Effects of water washing on removing organic residues in bottom ashes of municipal solid waste incinerators

Due to their potential toxicity and odourous nature, the residual organics in municipal solid waste incinerators are recently gaining attention as an important issue of resources recovery apart from their complex mixture of organic counterpart. Studies of the organic fractions in municipal solid waste incinerator residues have been limited. In this study, extended solid-phase extraction of the water-washed bottom ash and liquid-phase extraction of the washing water were carried out with regard to bottom ash samples from three mass-burning incinerators in Taipei County (Taiwan) during four consecutive seasons of year 2008-2009. Supercritical fluid extraction and Soxtec extraction techniques along with GC-MS were successfully used to characterize the residual organics in weathered and washed bottom ashes. Supercritical fluid extraction provided the quantification of aliphatics and aromatic compounds such as hexanoic acid and benzaldehyde, respectively. Soxtec extraction was useful for qualitative analysis of aromatic and aliphatic groups in the ashes and many of which were odourous and toxic compounds. By mixing one unit weight (g) bottom ash with two unit volume (mL) water for 15 min, total organic carbon in the bottom ash was greatly reduced (e.g., from 4.1 to 1.8 wt.%). Among the removed were foul odour-causing compounds such as pyridine and quinoline derivatives, while some aromatic compounds such as 4-hydroxybenzaldehyde and low-molecular-weight aliphatics such as hexanoic acid remained. The results here suggest that washing with water can be an effective pre-treatment step for removing odour-causing and environmental concerned organics.     

Methods and results of characterization of organic emissions from an indoor material

The method and example results for the determination of organic air emissions from a common indoor material are presented. A well instrumented and characterized 0.166-m³ stainless steel test chamber is used to ventilate sample materials at controlled air change rates, temperature and relative humidity. The test chamber outlet air stream is sampled using Tenax^® (1.6g) filled glass cartridges. The Tenax^® sample cartridges are then thermally desorbed for further concentration onto a Nutech^® model 8528 purge and trap system and desorption to a packed column gas Chromatograph for analysis. Organic emissions are quantified on a species specific basis and total organics basis. Test chamber concentrations of total organics for a waterbased adhesive are observed to diminish with time. Calculated emission rates for the floor adhesive were determined to be 95μg g⁻¹ h⁻¹ after ventilation at 1.77 air changes per hour for 10 h and 259 μg g⁻¹ h⁻¹ after 24-h ventilation at 3.6 air changes per hour.     

Modeling of gas-phase photodegradation of chloroform and carbon tetrachloride

The relationship between the irradiance in a photoreactor and the rate of photodegradation of organics is essential in the scaling-up of photoreactors to treat large volumes of air contaminated with organic pollutants. In this study, the analysis is adopted to compare results obtained from two different photoreactors. Initially, the applicability of two light models in calculating the irradiance in two photoreactors was evaluated. Thereafter, kinetic models of ultraviolet (UV) photooxidation of chloroform (CHCl3) and carbon tetrachloride (CCl4) from the archived literature were tested using experimental data under various operating conditions and different irradiances. Sensitivity analyses were conducted using different values of model parameters to determine the significance of each parameter on the photodegradation of the two chlorinated organics. For compounds that undergo photolysis as a primary mode of degradation, the rate of photodegradation at low initial concentrations can be predicted easily by the following equation: d[C]/dt = -2.303Iave, lambdaepsilonlambdaphilambda[C]. Although the photodegradation of chlorinated organic compounds in dry and humid air can be predicted well, it is difficult to predict the Cl* sensitized oxidation occurring at high initial concentrations. A good agreement between the simulated and experimental data provides a sound basis for the design of large-scale reactors.     

Improved computational model (AQUIFAS) for activated sludge, integrated fixed-film activated sludge, and moving-bed biofilm reactor systems, part III: analysis and verification

Research was undertaken to analyze and verify a model that can be applied to activated sludge, integrated fixed-film activated sludge (IFAS), and moving-bed biofilm reactor (MBBR) systems. The model embeds a biofilm model into a multicell activated sludge model. The advantage of such a model is that it eliminates the need to run separate computations for a plant being retrofitted from activated sludge to IFAS or MBBR. The biofilm flux rates for organics, nutrients, and biomass can be computed by two methods-a semi-empirical model of the biofilm that is relatively simpler, or a diffusional model of the biofilm that is computationally intensive. Biofilm support media can be incorporated to the anoxic and aerobic cells, but not the anaerobic cells. The model can be run for steady-state and dynamic simulations. The model was able to predict the changes in nitrification and denitrification at both pilot- and full-scale facilities. The semi-empirical and diffusional models of the biofilm were both used to evaluate the biofilm flux rates for media at different locations. The biofilm diffusional model was used to compute the biofilm thickness and growth, substrate concentrations, volatile suspended solids (VSS) concentration, and fraction of nitrifiers in each layer inside the biofilm. Following calibration, both models provided similar effluent results for reactor mixed liquor VSS and mixed liquor suspended solids and for the effluent organics, nitrogen forms, and phosphorus concentrations. While the semi-empirical model was quicker to run, the diffusional model provided additional information on biofilm thickness, quantity of growth in the biofilm, and substrate profiles inside the biofilm.     

Membrane Bioreactor Model for Removal of Organics from Wastewater

Abstract

The persistence of trace organics in wastewater effluent is a major environmental concern. Possible use of fixed microbial films in wastewater treatment processes is currently an active area of research that may be able to address many of these problems. In the waste effluent, the persistence of trace organics is attributed, in part, to the inability of microbial populations to extract energy from dilute environments at a rate fast enough to sustain themselves. To address this problem, a novel wastewater treatment scheme is considered. On the basis of previous hollow fiber biomass growth studies, we believe that an anaerobic biofilm supported by hollow fibers could achieve greater biomass density than a film grown on traditional impermeable supports. This in turn could lead to improved substrate removal efficiency in a reactor of a given volume. Using this concept, we developed a mathematical model to test the potential of hollow fiber membrane reactors for biodegradation of acetate solution. A computer simulation has shown that it would be possible to remove about 90% from feed solutions containing 0.1 mg-cm^-3 acetate with biomass density 25 mg-cm^-3 in the hollow fiber supported biofilm. More concentrated feeds could be effectively treated if sufficiently high biomass density could be attained. This process, therefore, shows promise in wastewater treatment. The advantages of hollow fiber membrane bioreactors are their high surface-to-volume ratio, separation of cells from flow, and high cell concentration. All of these are essential requirements for optimum utilization of biomass in wastewater treatment. The hollow fiber membrane bioreactor concept, therefore, may provide a new and unique approach to treating organics.     

Abiotic reductive dechlorination of chlorinated ethylenes by soil

Abiotic reductive dechlorination of chlorinated ethylenes by soil in anaerobic environments was characterized to improve knowledge of the behavior of chlorinated ethylenes in natural systems, including systems modified to promote attenuation of contaminants. Target organics in the soil suspension reached sorption equilibrium in 2 days and the sorption isotherm of target organics was properly described by the linear sorption model. A modified Langmuir-Hinshelwood model was developed to describe the kinetics of reductive dechlorination of target organics by soil. The rate constants for the reductive dechlorination of chlorinated ethylenes at the reactive surfaces of reduced soils were found in the range between 0.055 (+/- 8.9%) and 2.60 (+/- 3.2%) day(-1). The main transformation products in reduced soil suspensions were C2 hydrocarbons. No chlorinated intermediates were observed at concentrations above detection limits. Five cycles of reduction of the soil followed by oxidation of the soil with trichloroethylene (TCE) did not affect the removal of TCE. The removal was affected by the reductants used and increased in the order: Fe(II) < dithionite < Fe(II) + dithionite.     

改性TiO_2/浮石光催化去除二级出水中有机物

为了实现城市污水厂二级出水的回用,将La3＋、Fe3＋共掺杂TiO2/浮石光催化用于二级出水中有机物的去除。在优化工艺条件下,该方法对TOC的去除率为49.0%,对UV254的去除率为76.5%;出水BDOC/DOC值大幅度提高,由最初的0.21提高到0.56,增加了出水的可生化性;二级出水中存在着影响光催化去除有机物的因素,其中阴离子对有机物的去除有一定的抑制作用;光催化反应在通过O3强化后对有机物的去除率得到提高,TOC的去除率达到75.0%,光催化和O3氧化对有机物的去除具有协同效应;随着光催化反应次数的增加,催化剂活性有下降趋势,使用10次后TOC去除率下降到第一次使用时的16.7%,再生能够使催化活性恢复到使用前的95%,催化剂在使用15次以内稳定性较好。     

O_3/BAF工艺系统中有机物生物降解数学模型

研究臭氧预氧化/曝气生物滤池（O3/BAF）联合工艺深度处理实际城市污水二级出水过程中,后续BAF系统中有机物的生物降解数学模型。以有机底物浓度、填料层高度两个基本变量为控制条件,研究BAF的总体运行常数和填料特性常数,得出BAF有机物生物降解动力学方程为（Se/S0）=exp（（-Kn/qSh0））。出水与进水COD浓度比值（Se/S0）的对数与反应器填料高度（h）之间可表达成一次函数关系。在不同的进水浓度（S0）下,根据ln（Se/S0）~h和关系式m=（K/qS0n）,得到方程ln（qm）=-nln（S0）＋lnK。BAF总体运行常数K和填料特性常数n分别为1.708和0.5063。该模型对BAF工艺有如下指导意义：可以根据设计流量、进水有机物浓度和出水浓度,初步确定BAF的尺寸（如横截面积、高度等）。     

改性TiO2/浮石光催化去除二级出水中有机物

为了实现城市污水厂二级出水的回用,将La3+、Fe3+共掺杂TiO2/浮石光催化用于二级出水中有机物的去除。在优化工艺条件下,该方法对TOC的去除率为49.0%,对UV254的去除率为76.5%;出水BDOC/DOC值大幅度提高,由最初的0.21提高到0.56,增加了出水的可生化性;二级出水中存在着影响光催化去除有机物的因素,其中阴离子对有机物的去除有一定的抑制作用;光催化反应在通过O3强化后对有机物的去除率得到提高,TOC的去除率达到75.0%,光催化和O3氧化对有机物的去除具有协同效应;随着光催化反应次数的增加,催化剂活性有下降趋势,使用10次后TOC去除率下降到第一次使用时的16.7%,再生能够使催化活性恢复到使用前的95%,催化剂在使用15次以内稳定性较好。     

A New Audit Technique for EPA Method 25

A simple, inexpensive, and accurate technique for evaluating or auditing the sampling, recovery, and analytical phases of EPA Source Reference Method 25 has been developed. The technique involves spiking a U-shaped stainless steel cartridge containing Tenax® with known quantities of selected organic compounds and thermally desorbing them at temperatures from 160°C to 180°C to generate organic vapors quantitatively. The major advantages of this technique are that no other measurement methods can be used to determine the generated organic concentrations in lieu of Method 25; and that the cartridge can easily be taken to the field for evaluation. The organic compounds generated in test runs are collected and analyzed using the Method 25 procedure. The generation of organics is quantitative and recoveries were found to be 100 ± 10%. The time required for desorption of the majority of organics is generally less than forty-five minutes at a flow rate of 100 mL/min; however, based on laboratory experience the recommended sampling time is sixty minutes. These spiked cartridges are stable at room temperature over a two-month period. Results of interlaboratory studies showed close agreement with the expected concentrations based on calculations from the mass loadings and sample volumes.     

Desorption of chlorinated hydrocarbons from spiked and anthropogenically contaminated sediments

The desorption of 20 chlorinated organics from sediments has been studied using a nitrogen purge/Tenax trap system for separating the “dissolved” and “sorbed” fractions in sediment/water slurries. The desorption partition coefficient, K_D, was found to decrease with increasing temperature and suspended sediment concentration. While some differences in K_D and desorption rates were observed for the study chemicals, considering their wide range of physical/chemical properties such as K_OW, these changes were small. Desorption half-lives averaged about 60d at 4°C, 40d at 20°C and 10d at 40°C under continuous gaseous purging. Estimates of the loadings of chemicals via desorption from bottom sediments in Lake Ontario are compared to loadings of these chemicals to the lake from the Niagara River.     

Trace organic and heavy metal pollutants in the Mississippi River

A study was conducted to characterize and measure organic and heavy metal pollutants in the Mississippi River. Water samples were collected along the entire length of the river, and were screened for semivolatile organics by capillary GC and for heavy metals by atomic absorption spectrophotometry. Four water samples were further examined for semivolatile organics by capillary GC/MS. Eight heavy metals and more than sixty distinct organic chemicals were identified including alkylbenzenes, various halogenated organics, five herbicides or derivatives, plasticizers, polynuclear aromatic hydrocarbons (PAHs), saturated hydrocarbons, and three miscellaneous organics. All organic compounds were detected at the parts-per-trillion (pptr) level. In spite of the limited nature of the sampling effort, the large number of data derived from this study suggests the need for a more rigorous monitoring of the river for a wide spectrum of chemical pollutants.     

难降解氯代有机物污染环境的生物修复技术研究进展

氯代有机物是一类在生产和生活中广泛应用并被大量排放到环境中的难降解有机污染物质,一旦进入生态环境,就会在水体、土壤和底质中长期残留,并在食物链中不断积累、富集,从而对生物体产生危害。因此,对受这类难降解有机物污染的环境修复是目前所迫切需要解决的环境问题之一。基于物理和化学修复方法成本较高易造成二次污染,文中探讨了国内外生物修复技术的研究进展,并对难降解氯代有机物污染环境修复的研究方向进行了展望,由于环境中的污染物质复杂多变,联合生物修复技术将成为未来的研究热点。