地下水PRB原位生物修复中一种释氧材料的改进技术及效果分析

释氧材料经济有效的释氧是地下水原位生物修复的关键因素。实验通过在释氧材料中加入膨润土、磷酸二氢钾和硫酸铵等,改进释氧材料的性能。柱实验结果显示,该释氧材料释氧速率缓慢,释氧时间长,可以使溶液中DO长期保持在5 mg/L以上;另外,释氧材料中添加的缓冲剂及天然含水层介质对pH值有较好的缓冲作用,可以使pH值达到后续生物修复的要求。     

In situ bioremediation of nitrate and perchlorate in vadose zone soil for groundwater protection using gaseous electron donor injection technology.

When present in the vadose zone, potentially toxic nitrate and perchlorate anions can be persistent sources of groundwater contamination. Gaseous electron donor injection technology (GEDIT), an anaerobic variation of petroleum hydrocarbon bioventing, involves injecting electron donor gases, such as hydrogen or ethyl acetate, into the vadose zone, to stimulate biodegradation of nitrate and perchlorate. Laboratory microcosm studies demonstrated that hydrogen and ethanol promoted nitrate and perchlorate reduction in vadose zone soil and that moisture content was an important factor. Column studies demonstrated that transport of particular electron donors varied significantly; ethyl acetate and butyraldehyde were transported more rapidly than butyl acetate and ethanol. Nitrate removal in the column studies, up to 100%, was best promoted by ethyl acetate. Up to 39% perchlorate removal was achieved with ethanol and was limited by insufficient incubation time. The results demonstrate that GEDIT is a promising remediation technology warranting further validation.     

In situ measurements of volatile aromatic hydrocarbon biodegradation rates in groundwater

Benzene and alkylbenzene biodegradation rates and patterns were measured using an in situ microcosm in a crude-oil contaminated aquifer near Bemidji, Minnesota. Benzene-D6, toluene, ethylbenzene, o-, m- and p-xylenes and four pairs of C₃- and C₄-benzenes were added to an in situ microcosm and studied over a 3-year period. The microcosm allowed for a mass-balance approach and quantification of hydrocarbon biodegradation rates within a well-defined iron-reducing zone of the anoxic plume. Among the BTEX compounds, the apparent order of persistence is ethylbenzene > benzene > m,p-xylenes > o-xylene ≥ toluene. Threshold concentrations were observed for several compounds in the in situ microcosm, below which degradation was not observed, even after hundreds of days. In addition, long lag times were observed before the onset of degradation of benzene or ethylbenzene. The isomer-specific degradation patterns were compared to observations from a multi-year study conducted using data collected from monitoring wells along a flowpath in the contaminant plume. The data were fit with both first-order and Michaelis-Menten models. First-order kinetics provided a good fit for hydrocarbons with starting concentrations below 1 mg/L and Michaelis-Menten kinetics were a better fit when starting concentrations were above 1 mg/L, as was the case for benzene. The biodegradation rate data from this study were also compared to rates from other investigations reported in the literature.     

地下水中BTEX的原位生物修复研究进展

BTEX是苯、甲苯、乙苯和二甲苯的统称,存在于原油和石油产品中,其作为化工原料,广泛应用于农药、塑料及合成纤维等制造业.BTEX已成为地下水中普遍存在的污染物,自然衰减或生物修复工程已成功应用于地下水中BTEX的去除.自然衰减受BTEX污染的地下水具有良好的效果,但相比之下,生物修复工程更快、更有效.综述了在好氧和厌氧条件下,地下水中BTEX原位生物修复过程的微生物降解机制.     

In situ sequential treatment of a mixed contaminant plume

Groundwater plumes often contain a mixture of contaminants that cannot easily be remediated in situ using a single technology. The purpose of this research was to evaluate an in situ treatment sequence for the control of a mixed organic plume (chlorinated ethenes and petroleum hydrocarbons) within a Funnel-and-Gate. A shallow plume located in the unconfined aquifer at Alameda Point, CA, was found to contain up to 218,000 μg/l of cis-1,2 dichloroethene (cDCE), 16,000 μg/l of vinyl chloride (VC) and <1000 μg/l of 1,1 dichloroethene (1,1 DCE), trans-1,2 dichloroethene (trans-1,2 DCE) and trichloroethene (TCE). Total benzene, toluene, ethylbenzene and xylenes (BTEX) concentrations were <10,000 μg/l. Contaminated groundwater was funneled into a gate, 3.0 m wide, 4.5 m long and 6.0 m deep (keyed into the underlying aquitard) where treatment occurred. The initial gate segment consisted of granular iron, for the reductive dechlorination of the higher chlorinated ethenes. The second segment, the biosparge zone, promoted aerobic biodegradation of petroleum hydrocarbons and any remaining lesser-chlorinated compounds, stimulated by dissolved oxygen (DO) and carbon dioxide (CO₂) additions via an in situ sparge system (CO₂ was used to neutralize the high pH produced from reactions in the iron wall). Groundwater was drawn through the gate by pumping two wells located at the sealed, downgradient, end. Over a 4-month period an estimated 1350 g of cDCE flowed into the treatment gate and the iron wall removed 1230 g, or 91% of the mass. The influent mass of VC was 572 g and the iron wall removed 535 g, corresponding to 94% mass removal. The other chlorinated ethenes had significantly lower influent masses (3 to 108 g) and the iron wall removed the majority of the mass resulting in >96% mass removal for any of the compounds. In spite of these high removal percentages, laboratory column tests indicated that at these levels of chlorinated contaminants, surface saturation of the iron grains likely contributed to lower than expected reaction rates. In the biosparge zone, mass removal of cDCE appeared to occur predominantly by biodegradation (65%) with volatilization (35%) being an important secondary process. The dominant removal process for VC was volatilization (70%) although significant biodegradation was also indicated (30%). Laboratory microcosm results confirmed the potential for aerobic biodegradation of cDCE and VC. When average influent field concentrations for cDCE and VC were 220,000 and 46,000 μg/l, respectively, the sequential treatment unit removed 99.6% of the total mass and when the influent concentrations decreased to 26,000 and 19,000 μg/l for cDCE and VC, respectively, >99.9% removal within the treatment gate was attained. BTEX compounds were found to be significantly retarded in the iron treatment zone. Although they did eventually break through the granular iron, and into the gravel transition zone, none of these compounds was detected in the biosparge zone. No noticeable interferences between the anaerobic (reductive) and aerobic parts of the system occurred during testing. The results of this experiment show that in situ treatment sequences are viable, although further work is needed to optimize performance.     

可渗透反应墙原位修复垃圾渗滤液污染地下水

实验模拟地下环境,以垃圾渗滤液污染地下水为研究对象,分别采用沸石、无烟煤、陶粒、活性炭、炉渣、粉煤灰和零价铁作为填充材料,设计了7种地下可渗透反应器(PRB)。分2个阶段对PRB技术治理污染地下水可行性和有效性进行实验模拟研究,还研究了填充材料配比对PRB修复效率影响,分阶段调整复合填充材料配比,观察反应器产生的不同处理效果。考察了7种反应器内pH、EC和DO的变化情况及对污染物去除效果影响,分析了污染物去除机理;找出了反应器存在的某些不足之处。实验结果显示,2个阶段反应器对COD去除率都较高,分别为82.36%～88.11%和89.45%～93.65%。     

电动力学技术强化原位生物修复研究进展

介绍了利用电动力学技术强化土壤及地下水原位生物修复的原理和最新进展。电动力学强化的基本原理是利用电渗析、电迁移和电泳等电动力学效应加速污染环境中有机污染物和微生物运动,注入营养物、电子受体或活性微生物,或者利用电极反应和电流热效应为地下生物降解创造有利条件。研究表明．电动力学技术能有效地强化原位生物修复,而且该技术不破环生态环境．安装和操作简单,成本低廉．有广泛的应用前景。     

植物混种原位修复多环芳烃污染农田土壤

通过比较实验前后土壤微生物主要类群数量、PAHs降解菌数量、土壤PAHs含量和植物不同部位PAHs含量变化,评价植物单种和混种野外原位修复多环芳烃(PAHs)污染农田土壤的效果。结果显示,150 d天生长期内,黑麦草/小麦混种及黑麦草/蚕豆混种修复效果最好,对土壤PAHs总量的降解率分别达到了59.4%和64.8%。同时,这2个混种处理土壤细菌、真菌和PAHs降解菌数量分别显著高于相应的小麦、蚕豆和黑麦草单种处理。植物不同部位PAHs含量高低次序为根部>茎叶≈籽粒。混种模式下,蚕豆和小麦不同部位PAHs含量比单种模式的不同程度降低,特别是籽粒部。植物混种模式不仅显著提高了土壤PAHs的降解率,还降低了农作物体内PAHs含量,实现了边生产边修复,在污染农田土壤修复领域有着广阔的应用前景。     

地下水中污染物运移过程数值模拟算法的比较

数值模拟已成为目前地下水有机污染现场中,预测和评价溶解相有机污染物运移的主要手段.自从MT3D问世以来,它在地下水溶质运移的模拟中得到了广泛的应用.MT3D中包含有4种不同的数值算法--MOC,MMOC,HMOC和UFDM.利用Processing MODFLOW Pro.7.0.5建立了均质一维流动的地下水数学模型,考虑溶解相有机污染物在地下水中运移时的4个主要影响因素--对流、弥散、吸附和降解,设定了14种代表性的情形,模拟了等浓度污染源条件下污染物的运移,并将不同数值算法的计算结果与理论解进行比较,从而研究不同数值算法的优缺点,为实际数值模拟时算法的选择提供依据.     

Prospects in the bioremediation of petroleum hydrocarbon contaminants from hypersaline environments: A review

Hypersaline environments are underappreciated and are frequently exposed to pollution from petroleum hydrocarbons. Unlike other environs, the high salinity conditions present are a deterrent to various remediation techniques. There is also production of hypersaline waters from oil-polluted ecosystems which contain toxic hydrophobic pollutants that are threat to public health, environmental protection, and sustainability. Currently, innovative advances are being proposed for the remediation of oil-contaminated hypersaline regions. Such advancements include the exploration and stimulation of native microbial communities capable of utilizing and degrading petroleum hydrocarbons. However, prevailing salinity in these environments is unfavourable for the growth of non-halophylic microorganisms, thus limiting effective bioremediation options. An in-depth understanding of the potentials of various remediation technologies of hydrocarbon-polluted hypersaline environments is lacking. Thus, we present an overview of petroleum hydrocarbon pollution in hypersaline ecosystems and discuss the challenges and prospects associated with several technologies that may be employed in remediation of hydrocarbon pollution in the presence of delimiting high salinities. The application of biological remediation technologies including the utilization of halophilic and halotolerant microorganisms is also discussed.

     

Sulfur and oxygen isotope tracing in zero valent iron based In situ remediation system for metal contaminants

In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20 ± 1 °C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ³⁴S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ³⁴S and δ¹⁸O in biotic conditions and we also highlight a good relationship between δ³⁴S and sulfate reduction rate in biotic columns.     

In situ modification of an aquifer material by a cationic surfactant to enhance retardation of organic contaminants

Sorption of hexadecyltrimethylammonium chloride (HDTMA), a cationic surfactant, on aquifer material from Columbus AFB, Mississippi, U.S.A., was examined. Transport studies using flow-through columns and a box model aquifer showed that an almost stationary zone of HDTMA-modified aquifer material could be produced in situ without a significant decrease in hydraulic conductivity.Perchloroethylene (PCE) and naphthalene sorption isotherms on the HDTMA-modified aquifer material were linear, and sorption coefficients were increased by over two orders of magnitude relative to the unmodified material. The retardation of PCE by insitu emplaced HDTMA zones within a column was examined. Agreement between batch- and column-derived sorption coefficients and breakthrough curve symmetry indicates that local equilibrium was attained. Significant retardation of a naphthalene plume by an in situ emplaced surfactant zone was demonstrated in the box model aquifer system.The experimental results indicate that it is feasible to create in situ a sorbent zone within an aquifer using cationic surfactants. In most situations, the sorbent zone concept needs to be coupled with contaminant degradation processes for sorbent emplacement to be a practical tool in the remediation of groundwater contamination sites. Sorbent zones may be of benefit in the engineering of suitable environments for microbial or abiotic degradation reactions and by providing time slow reactions to occur.     

Metals and emerging contaminants in groundwater and human health risk assessment

Environmental Science and Pollution Research - Groundwaters are normally consumed without previous treatment and therefore the monitoring of contaminants in order to guarantee its safety is...     

Nitrate-enhanced bioremediation of BTEX-contaminated groundwater: parameter estimation from natural-gradient tracer experiments

Two natural-gradient pulse tracer tests were conducted in a petroleum-contaminated aquifer to evaluate the potential for benzene, toluene, ethylbenzene, and xylenes (BTEX) biodegradation under enhanced nitrate-reducing conditions. Addition of nitrate resulted in loss of toluene, ethylbenzene, and m,p-xylenes (TEX) after an initial lag period of approximately 9 days. Losses of benzene were not observed over the 60-day monitoring period. Tracer breakthrough curves (BTCs) were analyzed to derive transport and biodegradation parameters, including advective velocities, retardation factors, dispersion coefficients, biodegradation rate constants, and nitrate utilization ratios. Using the parameters derived from the BTC analysis, numerical simulations of one of the tracer experiments were conducted using BIONAPL/3D [Molson, J., BIONAPL/3D User Guide, A 3D Coupled Flow and Multi-Component Reactive transport model. University of Waterloo, Waterloo, Ontario, Canada]. Simulations using the BTC-derived transport and biodegradation parameters successfully reproduced benzene, TEX, and nitrate concentrations measured during the tracer experiment. Comparisons of observed and simulated nitrate concentrations indicate that the mass ratio of nitrate-N utilized to TEX degraded increased over time during the experiment, reaching values many times that expected based on stoichiometry of TEX oxidation coupled to nitrate reduction. Excess nitrate loss is likely due to oxidation of other organics in addition to TEX.     

Successive identification of biodegradation rates for multiple sequentially reactive contaminants in groundwater.

At the field scale, the biodegradation rate is usually estimated from analytical solutions to single species transport with first-order reactions, using measured data as input. Because many contaminants, e.g., chlorinated solvents, are degraded in a sequential pattern, with degradation products further reacting to produce new species, it is of great interest to quantify the transformation rate of every reaction. The conventional inverse solutions for identifying the transformation rates are limited to single species problems. In the present study, we propose a successive optimization approach to identify the biodegradation rate for each species by using a previously developed analytical solution to multi-species first-order reactive transport using data obtained at the field scale. By specifying a link between analytical solutions to sequentially reactive transport problems and optimization methods and assuming constant transport parameters (velocity, dispersivities, and retardation factors), the first-order transformation rates are optimized successively from parent species to its daughter species.     

复配介质去除地下水中腐殖酸

以模拟地下水为研究对象,进行了复配介质去除地下水中腐殖酸的实验研究。探讨了配比、粒径、固液比、pH和温度对腐殖酸去除效果的影响。腐殖酸的浓度通过紫外分光光度法测定。结果表明:在不加活性炭的条件下,H物质∶X物质∶Q物质=1∶8∶8时,其硬度较好;在初始pH=6.34、反应时间为4 h时,去除率可达到95%以上;当反应时间≤1 h时,去除率随粒径增大而减小,而当反应时间为2～6 h时,小粒径和中等粒径复配介质对腐殖酸去除率略高于大粒径;一定浓度范围内,腐殖酸的去除率与固液比呈正相关,但固液比增大时,并不能无限提高去除率,当固液比为1∶200～1∶50时,去除率呈现平台;pH对复配介质去除效果影响不大,而温度对腐殖酸的去除有显著影响,较低温度(16.8℃)下的去除率比较高温度(35.0℃)下的去除率高5%。该复配介质去除地下水中腐殖酸是有效可行的,可作为PRB(permeable reactive barrier,渗透反应格栅)的潜在反应介质。     

Engineered and subsequent intrinsic in situ bioremediation of a diesel fuel contaminated aquifer

A diesel fuel contaminated aquifer in Menziken, Switzerland was treated for 4.5 years by injecting aerated groundwater, supplemented with KNO3 and NH4H2PO4 to stimulate indigenous populations of petroleum hydrocarbon (PHC) degrading microorganisms. After dissolved PHC concentrations had stabilized at a low level, engineered in situ bioremediation was terminated. The main objective of this study was to evaluate the efficacy of intrinsic in situ bioremediation as a follow-up measure to remove PHC remaining in the aquifer after terminating engineered in situ bioremediation. In the first 7 months of intrinsic in situ bioremediation, redox conditions in the source area became more reducing as indicated by lower concentrations of SO4(2-) and higher concentrations of Fe(II) and CH4. In the core of the source area, strongly reducing conditions prevailed during the remaining study period (3 years) and dissolved PHC concentrations were higher than during engineered in situ bioremediation. This suggests that biodegradation in the core zone was limited by the availability of oxidants. In lateral zones of the source area, however, gradually more oxidized conditions were reestablished again, suggesting that PHC availability increasingly limited biodegradation. The total DIC production rate in the aquifer decreased within 2 years to about 25% of that during engineered in situ bioremediation and remained at that level. Stable carbon isotope analysis confirmed that the produced DIC mainly originated from PHC mineralization. The total rate of DIC and CH4 production in the source area was more than 300 times larger than the rate of PHC elution. This indicates that biodegradation coupled to consumption of naturally occurring oxidants was an important process for removal of PHC which remained in the aquifer after terminating engineered measures.     

Enhanced in situ bioremediation of phenol in bioestimulated unsaturated and saturated sand-bed columns.

Biodegradation of phenol was observed in unsaturated sandbed columns, in which phenol concentration declined from 298 mg phenol/kg sand to less than 1 mg/kg after 21 days. In saturated sand-bed columns, phenol concentration declined from 230 mg phenol/kg to less than 1 mg/kg after 37 days. Pseudo-first-order phenol biodegradation rates were in the range 0.25 days(-1) (R2 = 0.9) to 0.66 days(-1) (R2 = 0.85) and 0.08 days(-1) (R2 = 0.68) to 0.14 days(-1) (R2 = 0.84) in the unsaturated and saturated sand-bed columns, respectively. Unsaturated columns presented a higher biomass density (21.5 mg/g) in the sand-bed and lower biomass concentration in the aqueous phase (3.5 NTU) compared with the saturated columns (6.4 mg/g and 14.0 NTU). A high concentration of phenol releases in the sand-bed columns resulted in an initial inhibition of microbial activity and destabilization of the attached biomass.     

Transport of reactive colloids and contaminants in groundwater: effect of nonlinear kinetic interactions

Transport of reactive colloids in groundwater may enhance the transport of contaminants in groundwater. Often, the interpretation of results of transport experiments is not a simple task as both reactions of colloids with the solid matrix and reactions of contaminants with the solid matrix and mobile and immobile colloids may be time dependent and nonlinear. Further colloid transport properties may differ from solute transport properties. In this paper, a one-dimensional model for coupled and contaminant in a porous medium (COLTRAP) is presented together with simulation results. Calculated breakthrough curves (BTC's) during contamination and decontamination show systematically the effect of nonlinear and kinetic interactions on contaminant transport in the presence of reactive colloids, and the effect of colloid transport properties that differ from solute transport properties. It is shown that in case of linear kinetic reactions, the rate of exchange of mobile and immobile colloids have a large impact on the shape of BTC's even if the solid matrix is saturated with respect to colloids. BTC's during the contamination and decontamination phase have identical shapes in this case. Moreover, the slow reactions of contaminants and colloids may lead to unretarded breakthrough of contaminants. Independent of reaction rates, nonlinear reactions lead to BTC's that are steeper during contamination than in the linear case. A characteristic aspect of nonlinear sorption is that shapes of BTC's differ during the contamination and decontamination phase. It has been observed that shapes of some of the simulated adsorption and desorption curves are similar as shapes found in experiments reported in literature. This stresses the importance of incorporating both kinetics and nonlinearity in models for coupled colloid and contaminant transport and the capability of COLTRAP to interpret experimental results. Finally, to figure out whether nonlinear processes play a role, it is very important to consider both contamination and decontamination in transport experiments.