有机污染土壤原位化学氧化药剂投加方式的综述

原位化学氧化技术是修复有机污染土壤最经济有效的技术之一。药剂的投加与分散技术是原位化学氧化修复技术的核心。药剂投加与分散方式的选择与污染场地的土壤渗透性、特征水平、污染深度、氧化剂性质、修复费用等相关。阐述了直压式注射法、注射井法、土壤置换法和高压-旋喷注射法等药剂投加与分散技术的适用性、控制参数及优缺点等,引用工程实例对药剂投加与分散技术在原位化学氧化修复过程中的应用情况进行了论证。     

Characterizing In Situ Methane‐Enhanced Biostimulation Potential for 1,4‐Dioxane Biodegradation in Groundwater

This study characterizes the 1,4‐dioxane biodegradation potential for an in situ methane‐enhanced biostimulation field pilot study conducted at Air Force Plant 44, located south of the Tucson International Airport in Arizona. In this study, the use of methane as the primary substrate in aerobic cometabolic biodegradation of 1,4‐dioxane is evaluated using environmental molecular diagnostic tools. The findings are compared to an adjacent pilot study, wherein methane was generated via enhanced reductive dechlorination and where methane monooxygenase and methane‐oxidizing bacteria were also found to be abundant. This article also presents the use of ¹³C and ²H isotopic ratio enrichment, a more recent tool, to support the understanding of 1,4‐dioxane biodegradation in situ. This study is the first of its kind, although alkane gas‐enhanced biodegradation of 1,4‐dioxane has been evaluated extensively in microcosm studies and propane‐enhanced biodegradation of 1,4‐dioxane has been previously studied in the field. ©2016 Wiley Periodicals, Inc.     

Selectivity of Nano Zerovalent Iron in In Situ Chemical Reduction: Challenges and Improvements

Nano zerovalent iron (nZVI) is a promising remediation technology utilizing in situ chemical reduction (ISCR) to clean up contaminated groundwater at hazardous waste sites. The small particle size and large surface area of nZVI result in high reactivity and rapid destruction of contaminants. Over the past 20 years, a great deal of research has advanced the nZVI technology from bench‐scale tests to field‐scale applications. However, to date, the overall number of well‐characterized nZVI field deployments is still small compared to other alternative remedies that are more widely applied. Apart from the relatively high material cost of nZVI and questions regarding possible nanotoxicological side effects, one of the major obstacles to the widespread utilization of nZVI in the field is its short persistence in the environment due to natural reductant demand (NRD). The NRD for nZVI is predominantly due to reduction of water, but other reactions with naturally present oxidants (e.g., oxygen) occur, resulting in situ conditions that are reducing (high in ferrous iron phases and H₂) but with little or no Fe(0). This article reviews the main biogeochemical processes that determine the selectivity and longevity of nZVI, summarizes data from prior (laboratory and field) studies on the longevity of various common types of nZVI, and describes modifications of nZVI that could improve its selectivity and longevity for full‐scale applications of ISCR. © 2016 Wiley Periodicals, Inc.     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

Two Pilot Plant Reactors Designed for the In Situ Bioremediation of Chlorobenzene-contaminated Ground Water: Hydrogeological and Chemical Characteristics and Bacterial Consortia

The SAFIRA in situ pilot plant in Bitterfeld, Saxonia-Anhalt, Germany, currently serves as the test site for eight different in situ approaches to remediate anoxic chlorobenzene (CB)-contaminated ground water. Two reactors, both filled with originallignite-containing aquifer material, are designed for themicrobiological in situ remediation of the ground water bythe indigenous microbial consortia. In this study, thehydrogeological, chemical and microbiological conditions of theinflowing ground water and reactor filling material are presented,in order to establish the scientific basis for the start of thebioremediation process itself. The reactors were put intooperation in June 1999. In the following, inflow CB concentrationsin the ground water varied between 22 and 33 mg L^-1; achemical steady state for CB in both reactors was reachedafter 210 till 260 days operation time. The sediments werecolonized by high numbers of aerobic, iron-reducing anddenitrifying bacteria, as determined after 244 and 285 days ofoperation time. Furthermore, aerobic CB-degrading bacteria weredetected in all reactor zones. Comparative sequence analysis of16S rDNA gene clone libraries suggest the dominance of Proteobacteria (Comamonadaceae, Alcaligenaceae, Gallionella group, Acidithiobacillus) and members of theclass of low G+C gram-positive bacteria in the reactorsediments. In the inflowing ground water, sequences withphylogenetic affiliation to sulfate-reducing bacteria andsequences not affiliated with the known phyla of Bacteria, were found.     

An In Situ Bioreactor for the Treatment of Petroleum Hydrocarbons in Groundwater

Two pilot tests of an aerobic in situ bioreactor (ISBR) have been conducted at field sites contaminated with petroleum hydrocarbons. The two sites differed with respect to hydrocarbon concentrations. At one site, concentrations were low but persistent, and at the other site concentrations were high enough to be inhibitory to biodegradation. The ISBR unit is designed to enhance biodegradation of hydrocarbons by stimulating indigenous microorganisms. This approach builds on existing Bio‐Sep^® bead technology, which provides a matrix that can be rapidly colonized by the active members of the microbial community and serves to concentrate indigenous degraders. Oxygen and nutrients are delivered to the bioreactor to maintain conditions favorable for growth and reproduction, and contaminated groundwater is treated as it is circulated through the bed of Bio‐Sep^® beads. Groundwater moving through the system also transports degraders released from Bio‐Sep^® beads away from the bioreactor, potentially increasing biodegradation rates throughout the aquifer. Groundwater sampling, Bio‐Traps, and molecular biological tools were used to assess ISBR performance during the two pilot tests. Groundwater monitoring indicated that contaminant concentrations decreased at both sites, and the microbial data suggested that these decreases were due to degradation by indigenous microorganisms rather than dilution or dispersion mechanisms. Taken together, these lines of evidence showed that the ISBR system effectively increased the number and activity of indigenous microbial degraders and enhanced bioremediation at the test sites. © 2013 Wiley Periodicals, Inc.     

化学沉淀-臭氧氧化法处理焦化废水

采用臭氧氧化法对焦化废水（简称废水）进行处理,考察臭氧质量流量和废水pH对废水COD和NH3-N去除率的影响。实验结果表明,在臭氧质量流量为3．6g／h、废水pH为12、反应时间为12h的条件下,废水COD和NH3-N去除率分别为93．74％和74．28％。直接采用臭氧氧化法不能使NH3-N得到较好的去除,采用化学沉淀-臭氧氧化法处理焦化废水后,废水COD、NH3-N、挥发酚和色度的去除率均达97％以上。     

强化二氧化钛光催化氧化技术的研究进展

光催化氧化技术被认为是在环境保护领域内一项有前途的新型高级氧化技术,其他污染治理技术强化光催化氧化成为污水处理和废气净化的一个研究热点。介绍了国内外其他污染治理技术——化学法、物理化学法、生物法强化二氧化钛光催化氧化技术的研究和应用现状,分析了这些技术的强化光催化氧化机理,并对其今后的发展前景进行了展望。     

Determination of In Situ Esterification Parameters of Citric Acid-Glycerol Based Polymers for Wood Impregnation

The development of wood treatments is of increasing industrial importance. A novel technique for improving the properties of lodgepole pine and white pine through modification of the microstructure is described. The present investigation is devoted to the synthesis and determination of in situ parameters of citric acid and glycerol based polymers for wood impregnation. This solvent free approach is environmentally friendly and achieved through an esterification condensation reaction under acidic conditions. Crude glycerol and citric acid reactants were cross-linked via a curing process at 160?°C creating a polymer with only water as the byproduct. The ester bonds and crosslinking levels were controlled using different catalysts and citric acid contents and related to the reaction time and temperature. The nature of bonding within the polymers and at the wood cell walls was determined by FT-IR analysis. The thermal properties such as glass transition temperature (T_g) were studied using TGA/DSC and the effect of citric acid content and catalyst type determined. Dimensional stability of impregnated wood samples improved above 50% for each sample with HCl and p-TSA catalysts compared to control samples. FTIR spectra were studied to show the presence of the ester linkages of the polymer in situ at the wood cell walls. Bonding between the polymer and wood macromolecules were observed by scanning electron microscopy and interpreted as evidence of chemical bonds at the wood cells. When prepared using a catalyst, the polymer was intimately incorporated into wood structure significantly improving the substrate dimensional stability. Enhanced stability makes this approach of particular interest for exterior wood products especially as a green renewable option for the wood industry.     

Spreadsheet‐Based Design Tool for In Situ Anaerobic Bioremediation Using Soluble Substrate

A Microsoft Excel spreadsheet‐based design tool has been developed to assist remediation professionals in the design of injection systems for distributing soluble substrate (SS) to enhance in situ anaerobic bioremediation. The user provides site data, design parameters, and unit‐cost information to generate estimates of remediation‐system cost and steady‐state contact efficiency (CE_SS) for various designs. CE_SS is estimated from a nonlinear regression equation that includes terms for the SS injection concentration (C_I), minimum substrate concentration (C_MIN), groundwater travel time between rows of injection wells (T_T), SS half‐life (T_H), substrate reinjection time interval (T_R), and pore volumes of substrate solution injected (PV). With this tool, users can quickly compare the relative costs and performance of different injection alternatives and identify the best design for their specific site conditions. The design process embodied in the tool includes: (1) entering injection‐well configuration and unit costs for well installation, injection, and substrate; (2) determining treatment‐zone dimension; (3) selecting trial injection‐well spacing, time period between substrate reinjection, and injection pore volume; and (4) estimating contact efficiency and capital and life‐cycle costs. This process is then repeated until a final design is selected. In most cases, injection costs increase with increasing CE_SS. However, the best (highest) ratio of CE_SS to injection cost typically occurs for CE_SS in the range of 70 to 80 percent. © 2013 Wiley Periodicals, Inc.     

超声强化高级氧化技术降解水中有机污染物的研究进展

介绍了用于降解水中有机污染物的超声强化技术,分析了超声与臭氧氧化、Fenton试剂氧化和光催化氧化等高级氧化技术联用的机理,综述了这些联用技术在降解有机污染物方面的研究进展,并展望了超声强化高级氧化技术的发展前景。     

Intrinsic and Stimulated In Situ Biodegradation of Hexachlorocyclohexane (HCH)

The feasibility of the biodegradation of HCH and its intermediates has been investigated. A recent characterisation of two sites in The Netherlands has shown intrinsic biodegradation of HCH. At one site, breakdown products (monochlorobenzene, benzene and chlorophenol) were found in the core of the HCH-plume, whereas the HCH-concentration decreased over time and space. Characterisation of a second, industrial site indicated less intrinsic biodegradation and the need to stimulate biodegradation. In the laboratory, enhanced HCH degradation was tested with soil and groundwater material from both sites, and the required conversion to the intermediates benzene and monochlorobenzene was demonstrated. Furthermore, the biodegradation of these intermediates could be initiated by adding low amounts of oxygen (<5%). Adding nitrate enhanced this degradation. We hypothesise that this occurs through anaerobic nitrate reducing conversion of oxidised intermediates.At the non-industrial other site, intrinsic degradation took place, as shown in the laboratory experiments. Interpretation of the field data with computer codes Modflow and RT3D was performed. As a result of the modelling study, it has been proposed to monitor natural attenuation for several years before designing the final approach.At the industrial site, the results of the batch experiments are applied. Anaerobic HCH degradation to monochlorobenzene and benzene is stimulated via the addition of an electron donor.Infiltration facilities have been installed at the site to create an anaerobic infiltration zone in which HCH will be degraded, and these facilities are combined with the redevelopment of the site.     

化学氧化法脱除石油焦中的硫

分别采用硝酸、硝酸-冰醋酸混合液以及王水作氧化剂脱除石油焦中的硫。实验结果表明:石油焦粒径越小,脱硫率越高;随液固比(氧化剂体积与石油焦质量比,mL/g)增大、反应时间延长、反应温度升高,脱硫率先增大,达到极值后保持稳定。王水的脱硫率高于硝酸和硝酸-冰醋酸混合液。王水脱除石油焦中硫的最佳工艺条件为:石油焦粒径0.1mm,液固比20mL/g,反应时间20h,反应温度50℃。在此最佳条件下,脱硫率达42.3%。经王水在最佳脱硫工艺条件下处理后,可有效脱除石油焦中大部分的噻吩类和硫醇类有机硫以及全部的无机硫。     

Experimental Investigation of Cellulose/Silver Nanocomposites Using In Situ Generation Method

Cellulose gel films were prepared by regeneration process using pre-cooled aq.(8 wt% LiOH + 15 wt% urea) mixture as solvent and ethyl alcohol as non solvent. The Terminus cattapa leaf extract diffused wet cellulose films were then dipped in 1–5 mM aq.AgNO₃ solutions to allow in situ generation of silver nanoparticles (AgNPs). Besides the in situ generation, some AgNPs were also formed outside the wet films in the solution. The AgNPs formed outside the films were observed under transmission electron microscope and scanning electron microscope. The nanocomposite films were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis and tensile test. The thermal stability of the composite films was lower than that of the matrix up to a temperature of ~300 °C and afterwards showed a reverse trend. The tensile strength of the nanocomposite films was found to be higher than the matrix but decreased with increasing concentration of aq.AgNO₃. The cellulose/AgNPs composite films showed good antibacterial activity against E. coli (gram positive) and Bacillus sp. (gram negative). Based on the aforementioned properties, the cellulose/AgNPs composite films can be considered for antibacterial packaging and medical applications.     

Microbially Mediated In Situ Desorption Accelerates Remediation of Large Gasoline Product Plume

Remediation of a large separate‐phase hydrocarbon product and associated dissolved‐phase gasoline plume was accelerated by coupling multiphase extraction with in situ microbial stimulation. At the beginning of remediation activities, the separate‐phase hydrocarbon plume extended an estimated seven acres with product thickness measuring up to 2.1 feet thick. Within 18 months after beginning extraction, reduction of gasoline constituents in groundwater became asymptotic and measureable product disappeared from the upgradient source area. At that time, the remediation team initiated a program of limited in situ anaerobic bioremediation with the goal of stimulating production of natural surfactants from native microbes to release petroleum from the soil matrix. Groundwater concentrations of gasoline constituents increased gradually over the next three years, improving recovery without biofouling the pump‐and‐treat infrastructure. Using this approach, the groundwater component of the remedy was completed in less than five years, substantially less than the 10 years to 15 years predicted by modeling. This strategy demonstrated a more sustainable approach to remediation, reducing electrical usage by an estimated 800 megawatt hours, reducing infrastructure requirements, and preserving an estimated 150 million gallons of groundwater for this arid agricultural area. © 2014 Wiley Periodicals, Inc.     

In Situ treatment of PFAS‐impacted groundwater using colloidal activated Carbon

Poly‐ and perfluoroalkyl substances (PFASs) have been identified by many regulatory agencies as contaminants of concern within the environment. In recent years, regulatory authorities have established a number of health‐based regulatory and evaluation criteria with groundwater PFAS concentrations typically being less than 50 nanograms per liter (ng/L). Subsurface studies suggest that PFAS compounds are recalcitrant and widespread in the environment. Traditionally, impacted groundwater is extracted and treated on the surface using media such as activated carbon and exchange resins. These treatment technologies are generally expensive, inefficient, and can take decades to reach treatment objectives. The application of in situ remedial technologies is common for a wide variety of contaminants of concern such as petroleum hydrocarbons and volatile organic compounds; however, for PFASs, the technology is currently emerging. This study involved the application of colloidal activated carbon at a site in Canada where the PFASs perfluorooctanoate (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in groundwater at concentrations up to 3,260 ng/L and 1,450 ng/L, respectively. The shallow silty‐sand aquifer was anaerobic with an average linear groundwater velocity of approximately 2.6 meters per day. The colloidal activated carbon was applied using direct‐push technology and PFOA and PFOS concentrations below 30 ng/L were subsequently measured in groundwater samples over an 18‐month period. With the exception of perfluoroundecanoic acid, which was detected at 20 ng/L and perfluorooctanesulfonate which was detected at 40 ng/L after 18 months, all PFASs were below their respective method detection limits in all postinjection samples. Colloidal activated carbon was successfully distributed within the target zone of the impacted aquifer with the activated carbon being measured in cores up to 5 meters from the injection point. This case study suggests that colloidal activated carbon can be successfully applied to address low to moderate concentrations of PFASs within similar shallow anaerobic aquifers.     

In Situ Remediation of 1,4‐Dioxane Using Electrical Resistance Heating

Recent regulatory changes need more challenging treatment goals for 1,4‐dioxane. However, significant treatment limitations exist in part due to the high solubility and low Henry's law constant of 1,4‐dioxane. Two case studies are reported with substantial 1,4‐dioxane concentration reductions through in situ thermal remediation via electrical resistance heating (ERH). Concentration reductions greater than 99.8 percent of 1,4‐dioxane have been observed in the field using ERH. Concentrations of 1,4‐dioxane in air and steam extracted by an ERH vapor recovery system have also been evaluated. Laboratory studies were conducted to further understand the mechanisms that enable ERH remediation of 1,4‐dioxane. Vapor liquid equilibrium studies in water and soil were conducted and utilized to develop an ERH treatment cost model for 1,4‐dioxane. Existing field data were correlated to the 1,4‐dioxane treatment cost model. Field observations and laboratory testing indicate steam stripping that occurs through ERH remediation is an effective treatment method for 1,4‐dioxane. ©2015 Wiley Periodicals, Inc.     

Use of an In Situ Erosion Flume for Measuring Stability of Sediment Deposits in Hamilton Harbour,Canada

An in situ erosion flume was used to measure the stability of sediment deposits in Hamilton Harbour, Ontario, Canada. The flume consists of a rectangular duct with an opening at the bottom. A submerged pump attached to the downstream end of the flume circulates the ambient water through the flume, thereby generating turbulent shear flows inside the flume. When the flume rests on a sediment deposit, the exposed part of the sediment deposit is subjected to the flow shear stress. By applying a continually increasing flow shear stress on the sediment deposit and by measuring the amount of sediment erosion, it is possible to assess the erosional stability of the sediment deposits. An under water video camera was mounted on the flume to get visual images of the sediment erosion process. The flume was used at two sites in the Harbour. The erosional resistances measured by the flume for the two sites were different. Measurement of dry density of the sediment deposits using an ultrasonic device was carried out to explain the differences in the stability of sediment deposits from the two sites.