催化臭氧氧化技术及其应用

催化臭氧氧化技术作为一种绿色、环保、高效的高级氧化技术被广泛应用于难生物降解废水的深度处理。本文介绍了非均相催化臭氧氧化技术的原理;分析了反应体系pH、载体种类、活性金属种类和负载量、臭氧投加量及反应时间等因素对催化臭氧氧化效果的影响;对比了臭氧和催化臭氧氧化技术对不同废水的处理效果;总结了近年来国内催化臭氧氧化技术的实际应用情况。指出：影响催化臭氧氧化技术工业应用的主要问题是臭氧产生效率和催化剂的催化效率。     

The in situ treatment of TCE and PFAS in groundwater within a silty sand aquifer

Chlorinated ethenes such as trichloroethene (TCE), cis‐1,2‐dichloroethene (cis‐1,2‐DCE), and vinyl chloride along with per‐ and polyfluoroalkyl substances (PFAS) have been identified as chemicals of concern in groundwater; with many of the compounds being confirmed as being carcinogens or suspected carcinogens. While there are a variety of demonstrated in‐situ technologies for the treatment of chlorinated ethenes, there are limited technologies available to treat PFAS in groundwater. At a former industrial site shallow groundwater was impacted with TCE, cis‐1,2‐DCE, and vinyl chloride at concentrations up to 985, 258, and 54 µg/L, respectively. The groundwater also contained maximum concentrations of the following PFAS: 12,800 ng/L of perfluoropentanoic acid, 3,240 ng/L of perfluorohexanoic acid, 795 ng/L of perfluorobutanoic acid, 950 ng/L of perfluorooctanoic acid, and 2,140 ng/L of perfluorooctanesulfonic acid. Using a combination of adsorption, biotic, and abiotic degradation in situ remedial approaches, the chemicals of concern were targeted for removal from the groundwater with adsorption being utilized for PFAS whereas adsorption, chemical reduction, and anaerobic biodegradation were used for the chlorinated ethenes. Sampling of the groundwater over a 24‐month period indicated that the detected PFAS were treated to either their detection, or below the analytical detection limit over the monitoring period. Postinjection results for TCE, cis‐1,2‐DCE, and vinyl chloride indicated that the concentrations of the three compounds decreased by an order of magnitude within 4 months of injection, with TCE decreasing to below the analytical detection limit over the 24‐month monitoring period. Cis‐1,2‐DCE, and vinyl chloride concentrations decreased by over 99% within 8 months of injections, remaining at or below these concentrations during the 24‐month monitoring period. Analyses of Dehalococcoides, ethene, and acetylene over time suggest that microbiological and reductive dechlorination were occurring in conjunction with adsorption to attenuate the chlorinated ethenes and PFAS within the aquifer. Analysis of soil cores collected pre‐ and post‐injection, indicated that the distribution of the colloidal activated carbon was influenced by small scale heterogeneities within the aquifer. However, all aquifer samples collected within the targeted injection zone contained total organic carbon at concentrations at least one order of magnitude greater than the preinjection total organic carbon concentrations.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

Established groundwater contaminants such as chlorinated solvents and hydrocarbons have impacted groundwater at hundreds of thousands of sites around the United States and have been responsible for multibillion dollar remediation expenditures. An important question is whether groundwater remediation for the emerging contaminant class comprised of per‐ and polyfluoroalkyl substances (PFAS) will be a smaller, similar, or a larger‐scale problem than the established groundwater contaminants. A two‐pronged approach was used to evaluate this question in this paper. First, nine quantitative scale‐of‐remediation metrics were used to compare PFAS to four established contaminants: chlorinated solvents, benzene, 1,4‐dioxane, and methyl tert‐butyl ether. These metrics reflected the prevalence of the contaminants in the U.S., attenuation potential, remediation difficulty, and research intensity. Second, several key challenges identified with PFAS remediation were evaluated to see similar situations (qualitative analogs) that have been addressed by the remediation field in the past. The results of the analysis show that four out of nine of the evaluated quantitative metrics (production, number of potential sites, detection frequency, required destruction/removal efficiency) indicate that the scale of PFAS groundwater remediation may be smaller compared to the current scale of remediation for conventional groundwater contaminants. One attenuation metric, median plume length, suggests that overall PFAS remediation could pose a greater challenge compared to hydrocarbon sites, but only slightly larger than chlorinated volatile organic compounds sites. The second attenuation metric, hydrophobic sorption, was not definitive regarding the potential scale of PFAS remediation. The final three metrics (regulatory criteria, in‐situ remediation capability, and research intensity) all indicate that PFAS remediation might end up being a larger scale problem than the established contaminants. An assessment of the evolution of groundwater remediation capabilities for established contaminants identified five qualitative analogs for key PFAS groundwater remediation issues: (a) low‐level detection analytical capabilities; (b) methods to assess the risk of complex chemical mixtures; (c) nonaqueous phase dissolution as an analog for partitioning, precursors, and back diffusion at PFAS sites; (d) predictions of long plume lengths for emerging contaminants; and (e) monitored natural attenuation protocols for other non‐degrading groundwater contaminants. Overall the evaluation of these five analogs provided some comfort that, while remediating the potential universe of PFAS sites will be extremely challenging, the groundwater community has relevant past experience that may prove useful. The quantitative metrics and the qualitative analogs suggest a different combination of remediation approaches may be needed to deal with PFAS sites and may include source control, natural attenuation, in‐situ sequestration, containment, and point‐of‐use treatment. However, as with many chlorinated solvent sites, while complete restoration of PFAS sites may be uncommon, it should be possible to prevent excessive exposure of PFAS to human and ecological receptors.     

Bench-scale testing of a novel soil PFAS treatment train for informed remedial planning and decision-making

Bench-scale batch tests were conducted to assess the potential applicability of a combined separation/concentration/destruction treatment train to address soils and sediments impacted by per- and polyfluoroalkyl substances (PFAS) contamination at Schriever Space Force Base with historic aqueous film-forming foam (AFFF). Specifically, a novel treatment train coupling soil washing (for treatment of impacted soil/sediment) with foam fractionation (for treatment of the wash water [WW] generated during soil washing) and electrochemical oxidation (ECO, for treatment of the foam fractionate generated during foam fractionation) was evaluated at the bench scale using site-specific materials. Results presented herein show that the AFFF-impacted sandy soils with low organic content were amenable to treatment via soil washing. However, the removal of hydrophobic PFAS, such as perfluorooctanesulfonic acid (PFOS), from the organic-rich sediments was challenging. Results from batch desorption experiments were within a factor of 2 of those generated by soil washing bench studies, suggesting that simple batch tests can potentially be used to reasonably predict the treatment efficacy of soil washing. Long-chained perfluoroalkyl acids (PFAAs) within the WW were removed more effectively in the foam fractionation studies as compared to short-chain PFAAs. Addition of a surfactant, such as cetrimonium bromide (CTAB), enhanced foaming but only marginally improved the treatment of short-chained PFAAs and in some cases inhibited PFOS removal. ECO reduced PFAS concentrations in the foam fractionate generated during foam fractionation by several orders of magnitude. However, generation of unwanted byproducts may warrant further treatment and/or disposal. Overall, results from this study provide a novel data set highlighting the site-dependent nature of these PFAS remedial technologies and how simple, low-cost bench tests can be reliably leveraged for informed decision-making during PFAS remedial planning.     

Six pilot‐scale studies evaluating the in situ treatment of PFAS in groundwater

Per‐ and polyfluoroalkyl substances (PFAS) have been identified by many regulatory agencies as emerging contaminants of concern in a variety of media including groundwater. Currently, there are limited technologies available to treat PFAS in groundwater with the most frequently applied approach being extraction (i.e., pump and treat). While this approach can be effective in containing PFAS plumes, previous studies of pump and treat programs have met with limited remedial success. In situ treatment studies of PFAS have been limited to laboratory and a few field studies. Six pilot‐scale field studies were conducted in an unconfined sand aquifer coimpacted by petroleum hydrocarbon along with PFAS to determine if a variety of reagents could be used to attenuate dissolved phase PFAS in the presence of petroleum hydrocarbons. The six reagents consisted of two chemical oxidants, hydrogen peroxide (H₂O₂) and sodium persulfate (Na₂S₂O₈), and four adsorbents, powdered activated carbon (PAC), colloidal activated carbon (CAC), ion‐exchange resin (IER), and biochar. The reagents were injected using direct push technology in six permeable reactive zone (PRZ) configurations. Groundwater concentrations of various PFAS entering the PRZs ranged up to 24,000 µg/L perfluoropentanoic acid, up to 6,200 µg/L pentafluorobenzoic acid, up to 16,100 µg/L perfluorohexanoic acid, up to 6,080 µg/L perfluoroheptanoic acid, up to 450 µg/L perfluorooctanoic acid, and up to 140 µg/L perfluorononanoic acid. Performance groundwater sampling within and downgradient of the PRZs occurred for up to 18 months using single and multilevel monitoring wells. Results of groundwater sampling indicated that the PFAS were not treated by either the persulfate nor the peroxide and, in some cases, the PFAS increased in concentration immediately following the injection of peroxide and persulfate. Concentrations of PFAS in groundwater sampled within the PAC, CAC, IER, and biochar PRZs immediately after the injection were determined to be less than the method detection limits. Analyses of groundwater samples over the 18‐month monitoring period, indicated that all the PRZs exhibited partial or complete breakthrough of the PFAS over the 18‐month monitoring period, except for the CAC PRZ which showed no PFAS breakthrough. Analysis of cores for the CAC, PAC, and biochar PRZs suggested that the CAC was uniformly distributed within the target injection zone, whereas the PAC and biochar showed preferential injection into a thin coarse‐sand seam. Similarly, analysis of the sand packs of monitoring wells installed before the injection of the CAC, PAC, and biochar indicated that the sand packs of the PAC and biochar preferentially accumulated the reagents compared with the reagent concentrations within the surrounding aquifer by up to 18 times.     

Evaluation of the effects of PFAS soil adsorption and transformation in the presence of divalent cations under ambient conditions

A bench‐scale study was conducted to evaluate the effect of divalent cations on the adsorption of perfluoroalkyl and polyfluoroalkyl substances (PFAS) onto soil particles. The study entailed batch testing of a synthetic soil mixture under a range of Epsom salt (soluble magnesium sulfate heptahydrate) concentrations. The synthetic soil was produced using a mix of sand, silt, clay, and organic matter that then was mixed and saturated with water collected from a PFAS‐impacted water source. The results indicate that variable concentrations of magnesium (divalent cation) had a minor effect on the sorption of perfluorooctane sulfonate with the highest sorption occurring in the strongest solution of Epsom salt. An unanticipated result of the test involved apparent biomediated transformation of polyfluorinated alkylated sulfonates (fluorotelomers or FTS) to perfluorooctanoic acid, perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid. We believe this is the first time the complete transformation of 6:2 FTS to PFHpA has been observed and reported under ambient surface water‐like conditions within 6 months, a relatively short timeframe.     

旋转填充床中臭氧氧化处理兰炭废水生化出水

以旋转填充床（RPB）为反应器,采用臭氧氧化工艺处理实际兰炭废水一级生化池出水。考察了臭氧浓度、RPB转速、气液比、初始废水pH、废水温度和RPB处理级数对废水处理效果和臭氧利用率的影响。实验得到的适宜工艺条件为：保持进气流量90 L/h不变,不调节废水pH和温度,控制臭氧质量浓度50 mg/L、气液比5∶1、RPB转速1 500 r/min,进行二级处理。在上述工艺条件下,处理COD为340.0 mg/L、BOD₅/COD为0.18、pH为7.77、温度为24.7 ℃的废水,处理后出水COD去除率为19.7%,BOD₅/COD为0.34,可生化性大幅提高,可满足后续生化处理要求。     

臭氧氧化-三维电极电解联用技术深度处理造纸废水

采用臭氧氧化-三维电极电解联用技术深度处理造纸废水,通过单因素及正交实验法确定了最优工艺条件,并探讨了反应的动力学和机理。实验结果表明:废水处理的最优工艺条件为电极间距1.5 cm、电流密度9mA/cm~2、臭氧曝气量15 mL/min、活性炭填充量22 g/L、反应时间60 min,该工艺条件下,废水的COD去除率达93.70%;臭氧氧化-三维电极电解联用技术对废水中COD的去除过程符合一级反应动力学方程;臭氧氧化和三维电极电解间存在协同效应。     

Evaluating the longevity of a PFAS in situ colloidal activated carbon remedy

The remediation of per‐ and polyfluoroalkyl substances by injection of colloidal activated carbon (CAC) at a contaminated site in Central Canada was evaluated using various visualization and modeling methods. Radial diagrams were used to illustrate spatial and temporal trends in perfluoroalkyl acid (PFAA) concentrations, as well as various redox indicators. To assess the CAC adsorption capacity for perfluorooctane sulfonate (PFOS), laboratory Freundlich isotherms were derived for PFOS mixed with CAC in two solutions: (1) PFOS in a pH 7.5 synthetic water that was buffered by 1 millimolar NaHCO₃ (K_f = 142,800 mg^1‐a L^a/kg and a = 0.59); and (2) a groundwater sample (pH = 7.4) containing PFOS among other PFAS from a former fire‐training area in the United States (K_f = 4,900 mg^1‐a L^a/kg and a = 0.24). A mass balance approach was derived to facilitate the numerical modeling of mass redistribution after CAC injection, when mass transitions from a two‐phase system (aqueous and sorbed to organic matter) to a three‐phase system that also includes mass sorbed to CAC. An equilibrium mixing model of mass accumulation over time was developed using a finite‐difference solution and was verified by intermodel comparison for prediction of CAC longevity in the center of a source area. A three‐dimensional reactive transport model (ISR‐MT3DMS) was used to indicate that the CAC remedy implemented at the site is likely to be effective for PFOS remediation for decades. Model results are used to recommend remedial design and monitoring alternatives that account for the uncertainty in long‐term performance predictions.     

Technology review and evaluation of different chemical oxidation conditions on treatability of PFAS

Per‐ and polyfluoroalkyl substances (PFAS) are a class of stable compounds widely used in diverse applications. These emerging contaminants have unique properties due to carbon–fluorine (C–F) bonds, which are some of the strongest bonds in chemistry. High energy is required to break C–F bonds, which results in this class of compounds being recalcitrant to many degradation processes. Many technologies studied that have shown treatment effectiveness for PFAS cannot be implemented in situ. Chemical oxidation is a demonstrated remediation technology for in situ treatment of a wide range of organic environmental contaminants. An overview of relevant literature is presented, summarizing the use of single or combined reagent chemical oxidation processes that offer insight into oxidation–reduction chemistries potentially capable of PFAS degradation. Based on the observations and results of these studies, bench‐scale treatability tests were designed and performed to establish optimal conditions for the formation of specific free radical species, including superoxide and sulfate radicals, via various combinations of oxidants, catalysts, pH buffers, and heat to assess PFAS treatment by chemical oxidants. The study also suggests the possible abiotic transformations of some PFAS when chemical oxidation is or was used for treatment of primary organic contaminants (e.g., petroleum or chlorinated organic compounds) at a site. The bench‐scale tests utilized field‐collected samples from a firefighter training area. Much of the available data related to chemical oxidation of PFAS has only been reported for one or both of the two more commonly discussed PFAS (perfluorooctane sulfonic acid and/or perfluorooctanoic acid). In contrast, this treatability study evaluates oxidation of a diverse list of PFAS analytes. The results of this study and published literature conclude that heat‐activated persulfate is the oxidation method with the best degradation of PFAS. Limited reduction of reported PFAS concentrations in this study was observed in many oxidation reactors; however, unknown mass of PFAS (such as precursors of perfluoroalkyl acids) that cannot be identified in a field collected sample complicated quantification of how much oxidative destruction of PFAS actually occurred.     

PFAS Experts Symposium: Statements on regulatory policy,chemistry and analytics,toxicology, transport/fate,and remediation for per‐ and polyfluoroalkyl substances (PFAS) contamination issues

Sixty leading members of the scientific, engineering, regulatory, and legal communities assembled for the PFAS Experts Symposium in Arlington, Virginia on May 20 and 21, 2019 to discuss issues related to per‐ and polyfluoroalkyl substances (PFAS) based on the quickly evolving developments of PFAS regulations, chemistry and analytics, transport and fate concepts, toxicology, and remediation technologies.  The Symposium created a venue for experts with various specialized skills to provide opinions and trade perspectives on existing and new approaches to PFAS assessment and remediation in light of lessons learned managing other contaminants encountered over the past four decades. The following summarizes several consensus points developed as an outcome of the Symposium:

• Regulatory and policy issues: The response by many states and the US Environmental Protection Agency (USEPA) to media exposure and public pressure related to PFAS contamination is to relatively quickly initiate programs to regulate PFAS sites. This includes the USEPA establishing relatively low lifetime health advisory levels for PFAS in drinking water and even more stringent guidance and standards in several states. In addition, if PFAS are designated as hazardous substances at the federal level, as proposed by several Congressional bills, there could be wide‐reaching effects including listing of new Superfund sites solely for PFAS, application of stringent state standards, additional characterization and remediation at existing sites, reopening of closed sites, and cost renegotiation among PRPs.
• Chemistry and analytics: PFAS analysis is confounded by the lack of regulatory‐approved methods for most PFAS in water and all PFAS in solid media and air, interference with current water‐based analytical methods if samples contain high levels of suspended solids, and sample collection and analytical interference due to the presence of PFAS in common consumer products, sampling equipment, and laboratory materials.
• Toxicology and risk: Uncertainties remain related to human health and ecological effects for most PFAS; however, regulatory standards and guidance are being established incorporating safety factors that result in part per trillion (ppt) cleanup objectives. Given the thousands of PFAS that may be present in the environment, a more appropriate paradigm may be to develop toxicity criteria for groups of PFAS rather than individual PFAS.
• Transport and fate: The recalcitrance of many perfluoroalkyl compounds and the capability of some fluorotelomers to transform into perfluoroalkyl compounds complicate conceptual site models at many PFAS sites, particularly those involving complex mixtures, such as firefighting foams. Research is warranted to better understand the physicochemical properties and corresponding transport and fate of most PFAS, of branched and linear isomers of the same compounds, and of the interactions of PFAS with other co‐contaminants such as nonaqueous phase liquids. Many PFAS exhibit complex transport mechanisms, particularly at the air/water interface, and it is uncertain whether traditional transport principles apply to the ppt levels important to PFAS projects. Existing analytical methods are sufficient when combined with the many advances in site characterization techniques to move rapidly forward at selected sites to develop and test process‐based conceptual site models.
• Existing remediation technologies and research: Current technologies largely focus on separation (sorption, ion exchange, or sequestration). Due to diversity in PFAS properties, effective treatment will likely require treatment trains. Monitored natural attenuation will not likely involve destructive reactions, but be driven by processes such as matrix diffusion, sorption, dispersion, and dilution.

The consensus message from the Symposium participants is that PFAS present far more complex challenges to the environmental community than prior contaminants. This is because, in contrast to chlorinated solvents, PFAS are severely complicated by their mobility, persistence, toxicological uncertainties, and technical obstacles to remediation—all under the backdrop of stringent regulatory and policy developments that vary by state and will be further driven by USEPA. Concern was expressed about the time, expense, and complexity required to remediate PFAS sites and whether the challenges of PFAS warrant alternative approaches to site cleanups, including the notion that adaptive management and technical impracticability waivers may be warranted at sites with expansive PFAS plumes. A paradigm shift towards receptor protection rather than broad scale groundwater/aquifer remediation may be appropriate.     

Study of ozonation reaction in phenolic effluents

Chemical interactions between ozone and phenol are studied to obtain more information about the optimum economics of phenol oxidations using ozone gas. Both decomposition of ozone and it's reaction with phenol rate constants are evaluated to be 0.1 and 0.33 min⁻¹, at room temperature. Chemical mass-transfer coefficient is determined from a knowledge of the physical mass-transfer coefficient and effects of the chemical reactions on mass-transfer. A methodology is given for determining the enhancement of mass transfer by the chemical reaction, assuming pseudo first-order reaction rate, in agitated vessels.     

Alkaline Degradation of Cellulose: Mechanisms and Kinetics

Cellulose powder and softwood sawdust were subjected to alkaline degradation under conditions representative of a cementitious environment for periods of 7 and 3 years, respectively. During the first 3 years, sampling was frequent, and data on the degradation of cellulose and production of isosaccharinic acid was used for establishing long-term prediction models. Samples after an additional period of 4 years were compared to the predicted values. The total rate of degradation was measured as the increase in total organic carbon (TOC) in corresponding solutions. A previously published theoretical model of degradation kinetics gave a good approximation of the present experimental data. Peeling-off, stopping, and alkaline hydrolysis reaction rate constants were obtained as model parameters, and the results suggested that the transformation of the glucose end group is the rate-limiting step in the cellulose peeling-off reaction and also determines the pH dependence of that reaction. After 3 years, isosaccharinic (ISA) acid represented 70–85% of all degradation products as quantified by capillary zone electrophoresis. The long-term prediction model indicated that all of the cellulose would be degraded after only 150–550 years. The control sampling after 7 years points toward a lower degradation of cellulose and production of ISA than predicted by the model, reflecting either a degradation of ISA that was faster than the production or a termination of the ISA production.     

活性炭催化臭氧氧化水中诺氟沙星

以椰壳基活性炭为催化剂,采用催化臭氧氧化工艺降解诺氟沙星(NF),优化了工艺条件,评价了催化活性,并对反应机理进行了探讨。实验结果表明:活性炭催化臭氧氧化工艺的优化条件为臭氧通量80 mg/h、初始NF质量浓度15.0 mg/L、反应温度25℃、初始NF溶液p H 5.0;在该优化条件下反应60 min时,TOC去除率达51.5%,较单独臭氧氧化的32.5%和单独活性炭吸附的11.5%有明显改善;在活性炭催化臭氧氧化工艺中臭氧氧化与活性炭吸附之间存在一定的协同作用,活性炭具有较好的催化活性;活性炭催化臭氧氧化工艺对NF的去除主要是基于臭氧的直接氧化作用。     

挥发性有机物控制技术评价指标体系初探

阐述了挥发性有机物(VOCs)控制技术的评价原则、评价步骤和影响 VOCs 控制技术评价的因素,从技术、经济、社会和其他方面初步构建了 VOCs 控制技术的评价指标体系.进一步介绍了评价指标的量化方法.VOCs控制技术评价指标体系的建立,为科学、全面、客观地评价和筛选 VOCs 控制技术奠定坚实的基础.     

Membrane bioreactor technology: A novel approach to the treatment of compost leachate

Compost leachate forms during the composting process of organic material. It is rich in oxidizable organics, ammonia and metals, which pose a risk to the environment if released without proper treatment. An innovative method based on the membrane bioreactor (MBR) technology was developed to treat compost leachate over 39 days. Water quality parameters, such as pH, dissolved oxygen, ammonia, nitrate, nitrite and chemical oxygen demand (COD) were measured daily. Concentrations of caffeine and metals were measured over the course of the experiment using gas chromatography – mass spectrometry (GC/MS) and inductively coupled plasma – mass spectrometry (ICP–MS) respectively. A decrease of more than 99% was achieved for a COD of 116 g/L in the initial leachate. Ammonia was decreased from 2720 mg/L to 0.046 mg/L, while the nitrate concentration in the effluent rose to 710 mg/L. The bacteria in the MBR system adjusted to the presence of the leachate, and increased 4 orders of magnitude. Heavy metals were removed by at least 82.7% except copper. These successful results demonstrated the membrane bioreactor technology is feasible, efficient method for the treatment of compost leachate.     

电化学水处理技术的研究和应用

介绍了电化学技术的分类,总结了电化学技术在处理有机废水、重金属离子废水和氨氮废水方面的研究及应用现状,并指出了该技术在目前的应用中所存在的一些问题,探讨了今后的发展方向。     

湿热处理技术工艺发展现状与趋势展望

湿热处理技术近年来在国内外受到广泛的关注,此项技术主要应用于淀粉、餐厨垃圾的湿热水解均质化处理等方面.对此,研究人员开展了大量的研究工作,研究内容涉及湿热处理工艺影响因素研究、湿热处理工艺条件优化分析、湿热处理工艺对底物结构与性质的影响.总结前人的研究成果,沉淀目前湿热处理工艺成果应用与成果转化相关信息,并对湿热处理工艺的潜在应用领域做出初步展望.