土壤电阻加热技术原位修复有机污染土壤的关键问题与展望

为解决我国近年来重污染企业搬迁遗留的有机污染土壤问题,土壤电阻加热修复技术(electrical resistance heating,ERH)等热处置技术日益受到重视。ERH是目前修复挥发性、半挥发性有机污染土壤最具有潜力的原位热修复技术之一,其污染物去除率及土壤性质变化是用以评估该土壤修复技术的核心指标。在查阅文献的基础上,系统分析了热处置及电阻加热技术相关原理与适用范围,并对ERH处置过程中土壤性质可能发生的变化进行了深入讨论,以期为我国有机污染土壤原位热修复技术的推广和应用提供参考。     

燃气热脱附技术修复有机污染场地研究与应用进展

原位燃气热脱附是目前修复有机污染土壤最具潜力的技术之一。在查阅文献的基础上,结合国内外实际案例,系统梳理了有机污染土壤原位燃气热脱附修复技术的原理、适用范围、优缺点以及工艺施工流程,对国内外燃气热脱附技术的研究现状和工程应用情况进行了对比分析,并对该技术的发展趋势和应用前景进行了展望,以期为我国有机污染土壤原位热修复技术的推广和应用提供参考。     

氯苯污染土壤低温原位热脱附修复

为了考察低温原位热脱附技术对土壤中氯苯的修复效果,以土壤中氯苯为目标污染物,控制热脱附设备设定温度、土壤粒径、土壤含水率,对不同条件下土壤中的氯苯进行测定分析,研究其对热脱附效果的影响。结果表明:原位热脱附过程中土壤温度变化以加热棒为中心,随着距离增加而呈现时间和空间上的滞后效应;原位热脱附设定温度越高,土壤修复效果越好,当土壤设定温度为100℃时,90%土壤样品氯苯去除率达99%以上,与设定温度130℃修复效果相当;土壤粒径越小,其比表面积大,对污染物吸附效率越高,所需热脱附时间越长;含水率影响氯苯在土壤中的挥发速率、有效孔隙率和透气率,含水率过高或过低都不利于氯苯污染土壤原位热脱附修复。热脱附设备设定温度、土壤粒径、土壤含水率对低温原位热脱附技术去除土壤中氯苯的效果具有较大的影响。     

污染场地修复中原位热脱附技术与其他相关技术耦合联用的意义、效果及展望

在有机污染场地修复过程中,原位热脱附技术因具有土方不开挖、不转运、对周围环境干扰小以及污染物去除彻底等诸多优势,故其应用范围逐渐增多。但该技术也存在修复施工成本相对较高的弊端,且此弊端主要是由于采用单一热脱附技术能耗很高的原因造成的。原位热脱附技术与化学氧化、微生物降解以及蒸汽注射等手段的耦合可以很好地弥补这一不足,尤其是针对大型的复杂有机污染场地。针对目前原位热脱附技术在应用过程中存在的主要问题,在分析了国内外大量相关研究与案例的基础上,梳理了原位热脱附与化学氧化、微生物降解及其他原位热处理等技术耦合的应用情况,提出了原位热脱附耦合技术的工程应用建议。     

天津某复杂有机污染地块原位热脱附修复技术中试研究

针对受到挥发性有机物、农药污染形成的复杂有机污染地块,采用原位热脱附修复技术开展中试试验,研究该技术在低渗透区(以粉质黏土/黏土为主)、污染程度复杂、污染严重条件下的技术有效性,同时研究该技术使用过程中的升温规律及影响半径。结果表明,原位热脱附前期,位于加热井所构成正三角形的中心点的测温井以5℃/d的速率升温,当土壤温度到达95～100℃,进入潜热阶段,此时土壤中水分大量汽化,当升温达到100℃左右时,土壤中毛细水未完全去除,升温进入瓶颈期;综合考虑该地块原位热脱附的影响半径为1.5 m。     

有机污染黏壤土热脱附后热导率的变化特性

为探究有机污染土壤热脱附后热导率的变化特性,采集了苏州市某原位热脱附修复场地编号为G01、G06和G09的示范区域深度为0～3 m的土壤(系黏壤土),并利用实验室的小型热脱附装置在350℃的条件下对污染土壤试样进行了1h热脱附;对其热脱附前后的粒径分布以及热脱附后的化学组成(矿物质和有机质的质量分数)进行了表征,并用探针式导热仪测试了其热导率.结果表明,在高温热脱附处理过程中,土壤颗粒的团聚作用比破碎作用更强,导致热脱附后土壤粒径增大;当密度、含水率和温度等条件保持一致时,热脱附后土壤的热导率较场地原位测试时无显著变化,平均值在1.4～1.5W·(m·℃)-1;随温度升高或干密度增大,土壤热导率均增大,且干密度对热导率的影响比温度更加显著.此外,3个采样区域的土壤热导率呈现一定的差异,其中,G06区域的热导率最大而G01区域最小,最多相差0.055W·(m·℃)-1,这主要是由不同区域土壤中矿物质(其热导率是有机质的3倍以上)质量分数的变化所致.本研究结果可为实际热修复场地的地层温升预测提供参考.     

环境技术验证在污染土壤修复领域的应用——以原位热脱附-水平井-化学氧化耦合修复技术为例

环境技术验证评价方法能够科学、客观地评价生态环境创新技术,促进新技术的推广应用。基于焦化污染地块修复技术验证评价方法,对原位热脱附-水平井-化学氧化耦合修复技术在山西某焦化污染地块上应用的可行性、绿色性、资源能源消耗等方面进行了验证评价。结果表明,该技术可以在一个修复周期内(3个月)将焦化污染地块中多环芳烃质量浓度降低到修复目标值,达到修复效果。修复系统运行过程中产生的废气、废水、噪声等污染物经处理后均满足相应排放要求。通过对修复过程中固废产生量、耗水量、耗电量、运行成本等指标的核算,可知该技术具有资源能源消耗较少、处理成本较低、针对不可开挖地块的修复具有较强适用性等特点。原位热脱附-水平井-化学氧化耦合修复技术可应用于焦化污染地块包气带污染土壤的修复治理工作。     

异位热脱附技术与设备在我国污染场地修复工程中的应用

异位热脱附技术具有污染物去除率高、修复周期短、普适性强等显著优势,是目前修复有机污染土壤最有效的技术之一。通过资料、文献查阅及现场调研,梳理了异位热脱附技术及设备在国内外的研究现状及在我国的应用发展历程,结合工程案例,分析了典型直接热脱附设备、间接热脱附设备的工艺技术路线,进而提出开展实际污染场地修复时的设备选择建议,以及热脱附技术的理论研究和设备发展方向,为我国有机污染土壤异位热脱附修复技术的推广和应用提供参考。     

基于过硫酸盐的多环芳烃污染场地原位修复技术研究进展

多环芳烃(PAHs)作为土壤和地下水中常见的有机污染物，严重威胁了人类健康。近年来，基于过硫酸盐(PS)的原位修复技术由于高效快速且成本适中被广泛用于PAHs污染场地修复。介绍了PS的活化方式及机理，分析了4种PS原位注入技术的优缺点及应用条件，综述了土壤环境对PS氧化技术应用的影响，总结了PS在PAHs污染场地修复的实际工程应用，以及基于PS的联合修复技术的发展现状，并对PS氧化技术在实际场地修复的应用和发展进行了展望，以期为PAHs污染场地原位修复提供理论依据和技术支撑。     

污染土壤化学修复技术研究与进展

污染土壤修复环境工程近年来发展迅猛,欧美等发达国家在其技术创新和设备改进2个层面都取得了长足进展。本文概述了化学淋洗修复技术(原位化学修复技术和异位化学修复技术)、化学还原与还原脱氯修复技术、化学氧化修复技术、溶剂浸提技术和土壤性能化学改良修复技术等污染土壤的化学修复技术原理、进展与适用性以及有关关键技术参数,并对其发展前景进行了展望。     

Sorption and desorption of Cu and Cd by macroalgae and microalgae

The sorption and desorption of Cu and Cd by two species of brown macroalgae and five species of microalgae were studied. The two brown macroalgae, Laminaria japonica and Sargassum kjellmanianum, were found to have high capacities at pHs between 4.0 and 5.0 while for microalgae, optimum pH lay at 6.7. The presence of other cations in solution was found to reduce the sorption of the target cation, suggesting a competition for sorption sites on organisms. Sorption isotherms obeyed the Freundlich equation, suggesting involvement of a multiplicity of mechanisms and sorption sites. For the microalgae tested, Spirulina platensis had the highest capacity for Cd, followed by Nannochloropsis oculata, Phaeodactylum tricornutum, Platymonas cordifolia and Chaetoceros minutissimus. The reversibility of metal sorption by macroalgae was examined and the results show that both HCl and EDTA solutions were very effective in desorbing sorbed metal ions from macroalgae, with up to 99.5% of metals being recovered. The regenerated biomass showed undiminished sorption performance for the two metals studied, suggesting the potential of such material for use in water and wastewater treatment.     

Kinetic and structural relationships of transition monomeric and oligomeric carboxyl- and choline-esterases

The kinetic and structural relationships of eight electrophoretically pure mammalian serum and liver serine carboxylesterases (CE) and cholinesterases (ChE) have been studied. Eight CE's and ChE's, which were fully resolved but only partially purified, provided additional information. Five of the electrophoretically pure esterases were monomeric, and of these, four belonged to a new and widely distributed class. These four monomeric esterases hydrolyzed choline esters, but at widely differing rates. Thus two were termed monomeric butyrylcholinesterases, mBuChE I and II, and two were monomeric CE's (mCE). The rabbit liver mCE was not a subunit of the oligomeric CE (oCE), although the oCE also hydrolyzed choline esters at a very low rate. The complex kinetics of the mCE's, mBuChE's, oCE's, and of the oligomeric BuChE's of horse and human serum could be interpreted according to a single reaction scheme involving an allosteric site and the equation derived from it. Thus activation and inhibition at high substrate concentrations, together with sigmoidal activity versus substrate concentration plots, all of which characterize the reactions of these esterases, could be interpreted by a single scheme and equation. Structural and kinetic comparisons showed a progressive transition of properties from the oCE's through the mCE's to the oBuChE's. One of the purified mCE's was from horse serum, and it exhibited physical and kinetic properties unlike those of the liver mCE's or oCE's.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

Bacterial and archaeal diversity in oil fields and reservoirs and their potential role in hydrocarbon recovery and bioprospecting

Environmental Science and Pollution Research - Hydrocarbon is a primary source of energy in the current urbanized society. Considering the increasing demand, worldwide oil productions are declining...     

畜禽养殖业污染与循环经济

解决畜禽养殖业的污染问题要以充分利用资源为根本出发点，通过对污染全过程控制及废物综合利用，达到畜禽粪便的减量化、无害化、资源化，走循环经济的发展道路。     

Isocyanatocyclohexane and isothiocyanatocyclohexane levels in urban and industrial areas and possible emission-related activities

Isocyanatocyclohexane and isothiocyanatocyclohexane are becoming relevant compounds in urban and industrial air, as they are used in important amounts in automobile industry and building insulation, as well as in the manufacture of foams, rubber, paints and varnishes. Glass multi-sorbent tubes (Carbotrap, Carbopack, Carboxen) were connected to LCMA-UPC pump samplers for the retention of iso- and isothiocyanatocyclohexanes. The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detector (MSD). TD-GC/MS was chosen as analytical method due to its versatility and the possibility of analysis of a wide range of volatility and polarity VOC in air samples. The method was satisfactory sensitive, selective and reproducible for the studied compounds. The concentrations of iso- and isothioisocyanatocyclohexanes were evaluated in different urban, residential and industrial locations from extensive VOC air quality and odour episode studies in several cities in the Northeastern edge of Spain. Around 200–300 VOC were determined qualitatively in each sample. Higher values of iso- and isothiocyanatocyclohexane were found in industrial areas than in urban or residential locations. The concentrations ranged between n.d.−246 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively, for industrial areas. On the other hand, urban and residential locations showed concentrations ranging between n.d.−164 and n.d.−29 μg m⁻³ for isocyanatocyclohexane and isothiocyanatocyclohexane, respectively. The site location (urban or industrial), the kind and nearness of possible iso- and isothiocyanatocyclohexane emission activities (industrial or building construction) and the changes of wind regimes throughout the year have been found the most important factors influencing the concentrations of these compounds in the different places.     

Degradation in soil and water and ecotoxicity of rimsulfuron and its metabolites.

The degradation and ecotoxicity of sulfonylurea herbicide rimsulfuron and its major metabolites were examined in batch samples of an alluvial sandy loam and in freshwater. An HPLC-DAD method was adapted to simultaneously identify and quantify rimsulfuron and its metabolites, which was successfully validated by GC-MS analysis. In aqueous solutions, pure rimsulfuron was rapidly hydrolyzed into metabolite 1 (N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinylurea)), which itself was transformed into the more stable metabolite 2 (N-((3-(ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine)), with half-life (t(1/2)) values of 2 and 2.5 days, respectively. Hydrolysis was instantaneous under alkaline conditions (pH = 10). In aqueous suspensions of the alluvial soil (pH = 8), formulated rimsulfuron had a half-life of 7 days, whereas that of metabolite 1 was similar to that in water (about 3.5 days). The degradation of the two major metabolites was also studied in soil suspensions with the pure compounds at concentrations ranging from 1 to 10 mg l(-1). The half-life of metabolite 1 ranged from 3.9 to 5 days, close to the previous values. Metabolite 2 was more persistent and its degradation is strongly dependent on the initial concentration (C0): half-life values ranged from 8.1 to 55 days at 2-10 mg l(-1), respectively. These values are higher than those determined from the kinetics of metabolite 1 transformation into metabolite 2 (t(1/2) = 8-19 days). The ecotoxicity of the three chemicals was evaluated through their effect on Daphnia magna and Vibrio fischeri (Microtox bioassay). No effect was observed on D. magna with 24 and 48 h acute toxicity tests. Similarly, no toxic effect was observed with the Microtox test for the three chemicals in the range of concentrations tested that included the field application dose. Thus, being of low persistence and lacking acute toxicity, these chemicals present a low environmental risk. However, chronic effects should be studied in order to confirm the safety of rimsulfuron and its major metabolites.