地下水原位修复渗透性反应墙反应介质的改良与展望

渗透性反应墙(PRBs)是倍受关注的地下水原位修复技术之一,具有高效廉价、安装简便、维护简单等优点。详细总结了零价铁、活性炭、无机矿物材料和生物质材料等PRBs反应介质的结构、性能、适用范围、改良方法及增强吸附机制,介绍了PRBs技术在国内外地下水原位修复领域的工程应用实例,指出研发可再生型反应介质、深入研究复杂体系的污染物去除主导机制以及开展多介质混合、多种原位修复技术集成应用研究将是今后PRBs的主要研究方向。     

The horizontal reactive media treatment well (HRX Well®) for passive in situ remediation: Design,implementation, and sustainability considerations

A new in situ remediation concept termed a Horizontal Reactive Media Treatment Well (HRX Well^®) is presented that utilizes a horizontal well filled with reactive media to passively treat contaminated groundwater in situ. The approach involves the use of a large‐diameter directionally drilled horizontal well filled with solid reactive media installed parallel to the direction of groundwater flow. The engineered contrast in hydraulic conductivity between the high in‐well reactive media and the ambient aquifer hydraulic conductivity results in the passive capture, treatment, and discharge back to the aquifer of proportionally large volumes of groundwater. Capture and treatment widths of up to tens of feet can be achieved for many aquifer settings, and reductions in downgradient concentrations and contaminant mass flux are nearly immediate. Many different types of solid‐phase reactive treatment media are already available (zero valent iron, granular activated carbon, biodegradable particulate organic matter, slow‐release oxidants, ion exchange resins, zeolite, apatite, etc.). Therefore, this concept could be used to address a wide range of contaminants. Laboratory and pilot‐scale test results and numerical flow and transport model simulations are presented that validate the concept. The HRX Well can access contaminants not accessible by conventional vertical drilling and requires no aboveground treatment or footprint and requires limited ongoing maintenance. A focused feasibility evaluation and alternatives analysis highlights the potential cost and sustainability advantages of the HRX Well compared to groundwater extraction and treatment systems or funnel and gate permeable reactive barrier technologies for long‐term plume treatment. This paper also presents considerations for design and implementation for a planned upcoming field installation.     

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.     

The in situ treatment of synthetic musk fragrances in groundwater

Synthetic musk fragrances (SMFs) have been shown to be micropollutants in various aquatic and groundwater systems, often occurring at microgram per liter concentrations. Studies have shown that the most commonly detected SMFs in water are nitro musks and polycyclic musks. The SMFs are typically introduced into the environment in continuous streams such as from wastewater and land application of wastewater or sludge generated during wastewater treatment. Various studies for the treatment of SMFs have been undertaken for wastewater but studies for the treatment of SMFs in groundwater are limited, especially for in situ treatment. A pilot‐scale test was conducted to determine if the use of colloidal activated carbon (CAC) could effectively reduce dissolved concentrations of nitro and polycyclic synthetic musk compounds including musk xylene, musk ketone, galaxolide, and tonalide. The pilot test was carried out downgradient of a septic system in Central Canada where a series of nitrification and denitrification reactions are occurring in an unconfined aquifer. A 10‐weight percent CAC solution was injected into a series of temporary direct push injection points to target the synthetic musk plume. The plume contained galaxolide and tonalide concentrations up to 687 and 187 nanograms per liter (ng/L), respectively, while the concentrations of musk ketone and musk xylene were below the method detection limit (20 ng/L). A total of 13,950 liters of CAC solution was injected during one injection event. The pilot test results indicated that the CAC was effectively delivered to the target injection zone resulting in an increase in total organic carbon concentrations within the saturated soil greater than two orders of magnitude compared to the background concentrations. Analyses of the groundwater chemistry before and post‐injection indicated that the CAC had no detrimental impact on the groundwater quality while reducing the concentration of dissolved galaxolide and tonalide within the plume to below the method detection limits within 51 days of injection with the exception of two of the 14 wells monitored which had galaxolide and tonalide concentrations up to 78 and 35 ng/L. Within 6 months of application, the concentrations of galaxolide and tonalide had decreased to below the method detection limits. Subsequent monitoring of the groundwater quality over a one‐year period failed to detect galaxolide and tonalide, suggesting that the CAC was effective in attenuating the galaxolide and tonalide.     

Field analyses of RDX and TCE in groundwater during a GCW pilot study

Contaminant concentrations in groundwater are typically analyzed using traditional laboratory analytical procedures approved by the Environmental Protection Agency (EPA) or state regulatory agencies. The use of off‐site laboratories provides very high‐quality water quality data at a relatively high cost in terms of time and money. Yet there are many instances when it is desirable to have water quality data measured in the field. The field methods for measuring water quality typically cost much less than the corresponding laboratory methods. However, the usability of the field data may be uncertain when the results are qualitatively compared to duplicate laboratory results. Groundwater samples collected during a groundwater circulation well pilot study were analyzed using field kits to measure concentrations of trichloroethylene (TCE) and the explosive compound known as RDX. A subset of the samples was split for duplicate laboratory analysis. Linear regression analysis and relative percent difference analysis were performed on the duplicate results to evaluate the comparability of the field and laboratory data. The data analyses were also used to evaluate the concept that the field kits were more accurate for specific concentration ranges, as well as the concept the field kit results would improve as field personnel gained experience with the field analysis procedures. © 2002 Wiley Periodicals, Inc.     

In situ treatment of a dilute chlorinated solvent plume in an acidic aerobic aquifer

In situ bioremediation was selected in the Record of Decision (ROD) as the remedial technology for a 29‐acre dilute, acidic and aerobic, chlorinated solvent plume (principally trichloroethylene [TCE] and 1,1‐dichloroethylene) for a Superfund site located in central New Jersey. Implementation of the remedy at full‐scale began in late 2010, using reductive dechlorination and bioaugmentation, and treatment has continued steadily over the last 9 years. The amendments injected include electron donor and alkaline (bicarbonate) buffer solution and, once anaerobic aquifer conditions became established, a bioaugmentation culture. Amendment injections occurred in multilevel injection wells (IWs), to maintain control over the vertical interval of amendment delivery. The areal coverage of the plume has been reduced by 59% based on the 10 µg/L TCE isocontour and the contaminant mass has been reduced by 79% through the 9 years of treatment. Lessons learned from this project include the need for bioaugmentation in the acidic aquifer and an efficient and effective manner of well construction and amendment injection using multiscreen single casing IWs and packer systems. Additional lessons learned include differences in longevity of the electron donor amendment versus the bicarbonate neutralization additive, and the need for varied amendment delivery techniques (IWs, direct injection, horizontal well installation) in selected lower permeable zones to attain treatment.     

The in situ treatment of BTEX,MTBE, and TBA in saline groundwater

A pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na₂S₂O₈) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (³⁴S and ¹⁸O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (¹³C and ²H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.     

Chemical Changes in Sediment Pore-Waters of an Acidic Mining Lake After Addition of Organic Substrate and Lime for Stimulating Lake Remediation

In the past five years, enclosures have beeninstalled in an acidic mining lake in Lusatia to investigate insitu remediation processes. They were treated with straw, withstraw and Carbokalk, or with Carbokalk alone, where Carbokalkis a by-product of the sugar industry (solid precipitate ofnon-sugars after lime clarification of extracted sugar beetjuice). Sediment samples were taken as cores to get informationabout the behaviour of organic and inorganic components insediment pore-water with depth. Vertical distributions of pH,soluble reactive phosphate, nitrate, ammonium, silica,aluminium, iron, manganese, calcium, magnesium, sodium,potassium, sulphate, and DOC were measured. The resultingprofiles, each consisting of 15 data points at differentdepths, were compared by cluster analysis. The similarities ofsediment cores from different treated enclosures relating toprofiles of chemical components were discussed. Increasedconcentrations of potassium and sulphate were found in pore-water after substrate treatment. The data imply dissolution ofpotassium iron sulphate hydroxide minerals (jarosite) after anincrease of pH caused by dissolution of lime and by sulphatereducing processes which were stimulated by organic substrateaddition.     

Bioremediation of Chlorobenzene-Contaminated Groundwater on Granular Activated Carbon Barriers

During the past decade, various promising technologies have been developed for the decontamination of groundwater insitu which do not require long-term pumping or high energy consumption. One approach is to use funnel and gate technology. In the case described here, the combination of adsorption of contaminants on granular activated carbon (GAC) and its biodegradation is applied to considerably extend the operating time of the filling material in the barrier system. Monochlorobenzene (MCB), a recalcitrant groundwater contaminant under anaerobic conditions, undergoes high-capacity adsorption on GAC up to about 450 mg per gram. Aerobic enrichment cultures, obtained from a contaminated aquifer, were able to mineralize initially adsorbed MCB. In respirometer experiments the rate of carbon dioxide formation was dependent on the equilibrium concentration of MCB. The oxygen consumption of activated carbon by means of autoxidative reactions may delay aerobic biodegradation in GAC filters. The oxygen uptake of pristine activated carbon amounted to 5.6 mg per gram GAC in laboratory column experiments. When GAC was pre-loaded with MCB, autoxidation rates were considerably reduced. Hence, it is advisable not to stimulate the biodegradation of MCB by oxygen supply in GAC biobarriers until after an initial period of solely sorptive MCB removal from the groundwater flow.     

活性炭材料在火电厂烟气脱硫脱硝中的应用

概述了传统活性炭和活性炭纤维材料独特的吸附性,介绍了活性炭材料在烟气脱硫脱硝中的应用原理.同时建议今后应在表面改性、脱硫脱硝反应机理等方面进行深入研究.     

Evidence for biodegradation and volatilisation of dissolved petroleum hydrocarbons during in situ air sparging in large laboratory columns

Laboratory column experiments run for up to 13 days compared air sparging of groundwater contaminated by dissolved petroleum hydrocarbons in sterile and non-sterile aquifer sediments as well as uncontaminated sediments and groundwater. Loss of dissolved BTEX compounds in the contaminated columns was very rapid, occurring through volatilisation. The majority of the dissolved total organic carbon (TOC) persisted for much longer periods however. A direct comparison between losses from sterile and non-sterile columns suggested a negligible contribution of biodegradation to the removal of TOC. This was difficult to confirm through examination of O₂ utilisation because oxidation of a small amount of reduced sulphur in the aquifer materials was the dominant sink for O₂. Despite this, it was possible to conclude that less than 22% of the removal of TOC was through biodegradation during the first three days of air sparging.     

CuO/CSAC催化剂的制备及酸性大红GR废水的处理

以椰壳活性炭(CSAC)为载体负载CuO制备了CuO/CSAC催化剂。采用正交实验优化了CuO/CSAC催化剂的制备工艺条件,采用单因素实验和响应面实验优化了CuO/CSAC催化剂处理模拟酸性大红GR废水的工艺参数。结果表明:在CSAC加入量5 g、煅烧时间2.5 h、煅烧温度300 ℃、0.5 mol/L的硝酸铜溶液用量15 mL的最佳工艺条件下,CuO/CSAC催化剂微孔结构丰富,CuO特征峰明显;CuO/CSAC催化剂处理酸性大红GR废水的最佳工艺参数为pH 5.0,曝气时间4.10 h,催化剂加入量0.57 g,可将100 mL初始COD 962 mg/L、初始色度32 700倍的废水分别处理至残余COD 41.5 mg/L,残余色度28.4倍。建立了以残余COD和残余色度为响应值的工艺模型,计算值与实验值的相对误差均在±10%以内。     

阳离子嫩黄染料与苯酚在活性炭上竞争吸附的研究

用阳离子嫩黄染料和苯酚作为分子量差异悬殊的两种机吸附质，研究它们在两种国产活性炭上的吸附性能。在双组分竞争吸附中，阳离子嫩黄染吸附占明显优势，而 酚的吸附量则比在单组分系统时要小。本文还用理想吸附溶液（ＩＡＳ）模型对双组分竞争吸附作了预测。     

吸附-催化氧化法深度去除采油废水中COD的研究

采用载铜活性炭和废水中溶解氧体系,用催化氧化法深度去除采油废水中的COD.活性炭用质量分数为7.5%的Cu(NO3)2溶液浸渍,在260℃下还原固化,制得催化剂.采用固定床式水处理柱,对混凝沉降处理后COD难以达标的采油废水进行了深度处理研究.pH为7.5±0.5、经曝气处理后的采油废水,在25～35℃条件下与催化体系接触2h,可将45倍于催化剂体积的采油废水中的COD由400mg/L以上降至100mg/L以下.催化剂可以再生.     

活性炭固定床吸附分离溶液中表面活性剂和多环芳烃

利用活性炭固定床吸附分离表面活性剂和多环芳烃(PAH)的混合溶液,选取了具代表性的表面活性剂(TX100)和PAH(菲(PHE)等)。实验结果表明,流量越低、活性炭填充量越多、表面活性剂浓度越高、PAH浓度越低,越有利于表面活性剂的回收和PAH的去除。定义了有效回收时间,该时间是指PAH穿透10%的时间与表面活性剂穿透90%的时间之差,该时间越长,越有利于表面活性剂的回收。采用BDST和Thomas模型对TX100和PHE进行了吸附模拟,效果均较好;BDST模型拟合结果表明,当活性炭对TX100的吸附接近饱和时仍对PHE有较强的吸附能力。活性炭固定床吸附分离法可节约运行成本0.06元/L。     

二氧化钛-活性炭光催化复合膜的制备及对若丹明染料降解的研究

采用以粉状活性炭为主要载体、少量聚四氟乙烯为粘结剂、金属网为城撑基体的TiO2导电光催化复合膜，在不同条件下对若丹明B染料进行了光催化氧化研究。研究结果表明，该膜具有较强而稳定的光催化活性；在此光催化体系中光催化与吸附之间存在一定的协同作用，使光催化效率得以提高。     

负载型金属催化剂的制备及印染废水的催化氧化处理

采用浸渍沉淀法制备负载型金属催化剂,考察了载体种类、活性组分种类、活性组分配比（n（Fe2+）∶n（Mn2+））、浸渍液浓度（以Mn2+计）、煅烧温度和煅烧时间对催化剂性能的影响。实验结果表明：活性炭负载FexOy-MnOx型催化剂具有较高的活性;将在浸渍液浓度0.5 mol/L（以Mn2+计）、n（Fe2+）∶n（Mn2+）=1∶2、煅烧温度250 ℃,煅烧时间8 h条件下制备的催化剂用于印染废水（COD=584 mg/L、色度500倍）的处理,在臭氧流量0.8 L/min、废水pH 7、催化剂加入量40 g/L、反应时间60 min的条件下,印染废水COD的去除率为83.2%;该催化剂具有良好的稳定性,连续使用6次后的COD去除率仍可达到61.1%。     

生物膜反应器脱氮性能及其硝化细菌的研究

采用模拟含氮废水对自行设计制作的A/O生物膜反应器进行脱氮性能研究。研究结果表明：在水温为20～23℃、水力停留时间为18h、进水总氮质量浓度为61～78m g/L、曝气量为25L/min、进水COD分别为110～165m g/L和205～272m g/L的条件下,废水的COD去除率均在90%以上,硝化率分别为98%和95%,总氮去除率分别为50%和78%。采用荧光原位杂交技术对反应器各区域中的硝化细菌进行了检测。结果表明,反应器中的硝化菌主要为亚硝化螺菌属和硝化螺菌属,有少量亚硝化单胞菌属和硝化杆菌属存在。亚硝化菌和硝化菌在好氧区数量相对较多,在缺氧区数量相对较少。     

微波强化CWPO工艺CuO_x-CeO_2/GAC催化剂的制备及其对二甲亚砜的降解

以颗粒活性炭(GAC)为载体、铜为活性组分、铈为助剂组分、草酸钠为沉淀剂,采用浸渍焙烧法制得CuO_x-CeO_2/GAC催化剂。以H_2O_2为氧化剂,微波强化催化湿式过氧化氢氧化(CWPO)处理二甲亚砜(DMSO)初始质量浓度为1 000 mg/L的废水,处理3 min后DMSO去除率达93.8%。催化剂第7次使用时DMSO去除率仍保持在75%以上。初始废水pH在3~9范围内,DMSO去除率均在85%以上。助剂Ce的加入提高了催化剂表面活性组分的分散性和稳定性,使催化剂的活性稳定性和使用寿命显著提高。     

Inventory and treatment of compost maturation emissions in a municipal solid waste treatment facility

Emissions of volatile organic compounds (VOCs) from the compost maturation building in a municipal solid waste treatment facility were inventoried by solid phase microextraction and gas chromatography–mass spectrometry. A large diversity of chemical classes and compounds were found. The highest concentrations were found for n-butanol, methyl ethyl ketone and limonene (ppm_v level). Also, a range of compounds exceeded their odor threshold evidencing that treatment was needed. Performance of a chemical scrubber followed by two parallel biofilters packed with an advanced packing material and treating an average airflow of 99,300 m³ h^?1 was assessed in the treatment of the VOCs inventoried. Performance of the odor abatement system was evaluated in terms of removal efficiency by comparing inlet and outlet abundances. Outlet concentrations of selected VOCs permitted to identify critical odorants emitted to the atmosphere. In particular, limonene was found as the most critical VOC in the present study. Only six compounds from the odorant group were removed with efficiencies higher than 90%. Low removal efficiencies were found for most of the compounds present in the emission showing a significant relation with their chemical properties (functionality and solubility) and operational parameters (temperature, pH and inlet concentration). Interestingly, benzaldehyde and benzyl alcohol were found to be produced in the treatment system.