堆肥 + 零价铁可渗透反应墙修复黄土高原地下水中铬铅复合污染简

为了研究堆肥+零价铁混合可渗透反应墙（PRB）修复黄土高原地下水中铬铅复合污染的可行性,分别用堆肥、零价铁、堆肥+ 零价铁、堆肥+ 零价铁+活性炭为反应介质,通过模拟柱实验考察PRB修复铬铅复合污染黄土高原地下水的效果。结果表明,在实验进行30 d后当反应柱1和2对六价铬的去除率接近于零,而且对二价铅的去除率迅速下降时,反应柱3对2种污染物仍保持较高的去除率;反应介质质量比为10：2：1的反应柱4和质量比为10：1：2的反应柱5对污染物的去除效果均优于质量比为10：1：1的反应柱3;反应50 d后,添加活性炭的反应柱6对2种污染物的去除率仍在90%。这说明使用堆肥+零价铁混合可渗透反应墙修复黄土高原地下水中铬铅复合污染是可行的;且以堆肥+零价铁作为介质的反应柱去除效果优于单独以堆肥或铁粉为介质的反应柱;增加铁粉或堆肥的用量有利于铬铅复合污染的去除;且同时添加活性炭更有助于污染物的去除。     

Persulfate oxidation of trichloroethylene with and without iron activation in porous media

In situ chemical oxidation with persulfate anion (S2O82*) is a viable technique for remediation of groundwater contaminants such as trichloroethylene (TCE). An accelerated reaction using S2O82* to destroy TCE can be achieved via chemical activation with ferrous ion to generate sulfate radicals (SO4*)(E degrees =2.6 V). The column study presented here simulates persulfate oxidation of TCE in porous media (glass beads and a sandy soil). Initial experiments were conducted to investigate persulfate transport in the absence of TCE in the column. The persulfate flushing exhibited a longer residence time and revealed a moderate persulfate interaction with soils. In TCE treatment experiments, the results indicate that the water or persulfate solution would push dissolved TCE from the column. Therefore, the effluent TCE concentration gradually increased to a maximum when about one pore volume was replaced with the flushing solution in the column. The presence of Fe2+ concentration within the column caused a quick drop in effluent TCE concentration and more TCE degradation was observed. When a TCE solution was flushing through the soil column, breakthrough of TCE concentration in the effluent was relatively slow. In contrast, when the soil column was flushed with a mixed solution of persulfate and TCE, persulfate appeared to preferentially oxidize soil oxidizable matter rather than TCE during transport. Hence, persulfate oxidation of soil organics may possibly reduce the interaction between TCE and soil (e.g., adsorption) and facilitate the transport of TCE through soil columns resulting in faster breakthrough.     

Column studies on transport of deicing additive benzotriazole in a sandy aquifer and a zerovalent iron barrier

Benzotriazole (BTA), a chemical with wide industrial applications, is a typical additive in deicer/anti-icer used at airport. To achieve a better understanding of the transport behaviour and environmental fate of BTA, laboratory column studies have been performed on subsoil samples from Oslo Airport, Gardermoen. To explore possibilities for aquifer remediation, BTA behaviour was also studied in a column of granular zerovalent iron (Fe(0)). The subsoil column study demonstrates a very limited retardation of BTA. Consecutive loadings of BTA of the subsoil column showed no change of the break-through curve (BTC) and complete desorption was observed. The sorption behaviour of BTA to metallic iron (Fe(0)) was rather complex. Considerable retardation was observed in the Fe(0) column and repeated BTA loading resulted in an earlier break-through. Between 20% and 50% of the input concentration was retained permanently in the iron (Fe(0)) column. The BTA sorption to metallic iron was found to be enhanced by chloride which lowered the break-through concentration (i.e the C/C(0) plateau). The fraction of BTA remaining in the iron column was found to vary with the flow rate, indicating a time dependant multilayer sorption mechanism. The steady increase in the amount of adsorbed BTA to the iron column during loading corresponds to a rather strong bonding of 4-15 BTA layers to the iron surface. A very slow desorption of BTA was observed; even after flushing with 753 pore volumes of BTA free water, 7.5% of the BTA remained in the column. A geochemical model was developed based on PHREEQC-2 to simulate the sorption and transport of BTA in the tested materials. The BTA sorption was modelled with Freundlich sorption isotherms, as earlier determined in batch experiments. A slight adjustment of the Freundlich parameters was required to fit the observed column break-through. However, our model was not able to simulate the long-term retainment of BTA in the granular iron columns. The simulations confirm the high mobility of BTA in groundwater aquifers and suggest that zerovalent iron could be used to retain a BTA plume, although oxidation of the sorbent might reduce the long-term performance of such a remediation scheme and slow desorption has been observed.     

高气泡表面积通量浮选柱气浮除藻的研究

湖泊、水库等水源的富营养化，使藻类去除成为饮用水生产的重要任务。本研究采用高气泡表面积通量浮选柱气浮除藻，考察了混凝剂、气泡表面积通量和浮选柱高度等因素的影响。试验表明，高气泡表面积通量浮选柱气浮可高效地去除绿藻、硅藻和蓝藻，叶绿素a和藻类去除率达95％以上，比传统浮选柱气浮和沉降作业有较大幅度提高。与普通气浮柱比较，高气泡表面积通量浮选柱增加了气泡与藻的碰撞几率，防止因大表观充气速率造成的紊流和扰动，使气泡／藻结合体有相对静态的浮升环境，避免了气泡／藻结合体在浮升过程中的脱落，实现对藻类的迅速捕集和转移。     

Enhanced reductive dechlorination in columns treated with edible oil emulsion

The effect of edible oil emulsion treatment on enhanced reductive dechlorination was evaluated in a 14 month laboratory column study. Experimental treatments included: (1) emulsified soybean oil and dilute HCl to inhibit biological activity; (2) emulsified oil only; (3) emulsified oil and anaerobic digester sludge; and (4) continuously feeding soluble substrate. A single application of emulsified oil was effective in generating strongly reducing, anaerobic conditions for over 14 months. PCE was rapidly reduced to cis-DCE in all three live columns. Bioaugmentation with a halorespiring enrichment culture resulted in complete dechlorination of PCE to ethene in the soluble substrate column (yeast extract and lactate). However, an additional treatment with a pulse of yeast extract and bioaugmentation culture was required to stimulate complete dechlorination in the emulsion treated columns. Once the dechlorinating population was established, the emulsion only column degraded PCE from 90-120 microM to below detection with concurrent ethene production in a 33 day contact time. The lower biodegradation rates in the emulsion treated columns compared to the soluble substrate column suggest that emulsified oil barriers may require a somewhat longer contact time for effective treatment. In the HCl inhibited column, partitioning of PCE to the retained oil substantially delayed PCE breakthrough. However, reduction of PCE to more soluble degradation products (cis-DCE, VC and ethene) greatly reduced the impact of oil-water partitioning in live columns. There was only a small decline in the hydraulic conductivity (K) of column #1 (low pH+emulsion, K(final)/K(initial)=0.57) and column #2 (live+emulsion, K(final)/K(initial)=0.73) indicating emulsion injection did not result in appreciable clogging of the clayey sand. However, K loss was greater in column #3 (sludge+emulsion, K(final)/K(initial)=0.12) and column #4 (soluble substrate, K(final)/K(initial)=0.03) indicating clogging due to biomass and/or gas production can be significant.     

A long-term performance test on an autotrophic denitrification column for application as a permeable reactive barrier

The long-term performance of a sulfur-based reactive barrier system was evaluated using autotrophic denitrification in a large-scale column. A bacterial consortium, containing autotrophic denitrifiers attached on sulfur particles, serving as an electron donor, was able to transform 60mgNL(-1) of nitrate into dinitrogen. In the absence of phosphate, the consortium was unable to remove nitrate, but after the addition of phosphate, nitrate removal was readily evident. Once the column operation had stabilized, seepage velocities of 1.0x10(-3) and 0.5x10(-3)cms(-1), corresponding to hydraulic residence times of 24 and 48h, respectively, did not affect the nitrate removal efficiency, as determined by the nitrate concentration in the effluent. However, data on the nitrate, nitrite and sulfate distribution along the column indicated differential transformation patterns with column depths. Based on the dinitrogen concentration in the total gas collected, the denitrification efficiency of the tested column was estimated to be more than 95%. After 500d operation, the hydrodynamic characteristics of the column slightly changed, but these changes did not inhibit the nitrate removal efficiency. Data from a bacterial community analysis obtained from four parts of the column demonstrated the selective a spatial distribution of predominant species depending on available electron acceptors or donors.     

高气泡表面积通量浮选柱气浮除藻的研究

湖泊、水库等水源的富营养化,使藻类去除成为饮用水生产的重要任务.本研究采用高气泡表面积通量浮选柱气浮除藻,考察了混凝剂、气泡表面积通量和浮选柱高度等因素的影响.试验表明,高气泡表面积通量浮选柱气浮可高效地去除绿藻、硅藻和蓝藻,叶绿素a和藻类去除率达95%以上,比传统浮选柱气浮和沉降作业有较大幅度提高.与普通气浮柱比较,高气泡表面积通量浮选柱增加了气泡与藻的碰撞几率,防止因大表观充气速率造成的紊流和扰动,使气泡/藻结合体有相对静态的浮升环境,避免了气泡/藻结合体在浮升过程中的脱落,实现对藻类的迅速捕集和转移.     

Sorption of anionic surfactants on a fixed bed of rubber granules

The performance of a fixed-bed adsorber (FBR) column for the removal of anionic surfactants from aquatic environments has been studied. Waste tyre rubber granules were used as the adsorbent material, and sodium dodecyl sulfate, an anionic surfactant, as the adsorbate. The FBR column design parameters were evaluated using the column breakthrough data at different bed depths. The Bohert and Adams model was used with the bed depth service time approach for the design of the column. The bed efficiency obtained was 90.97%.     

Continuous-flow column study of reductive dehalogenation of PCE upon bioaugmentation with the Evanite enrichment culture

A continuous-flow anaerobic column experiment was conducted to evaluate the reductive dechlorination of tetrachloroethene (PCE) in Hanford aquifer material after bioaugmentation with the Evanite (EV) culture. An influent PCE concentration of 0.09 mM was transformed to vinyl chloride (VC) and ethene (ETH) within a hydraulic residence time of 1.3 days. The experimental breakthrough curves were described by the one-dimensional two-site-nonequilibrium transport model. PCE dechlorination was observed after bioaugmentation and after the lactate concentration was increased from 0.35 to 0.67 mM. At the onset of reductive dehalogenation, cis-dichloroethene (c-DCE) concentrations in the column effluent exceeded the influent PCE concentration indicating enhanced PCE desorption and transformation. When the lactate concentration was increased to 1.34 mM, c-DCE reduction to vinyl chloride (VC) and ethene (ETH) occurred. Spatial rates of PCE and VC transformation were determined in batch-incubated microcosms constructed with aquifer samples obtained from the column. PCE transformation rates were highest in the first 5 cm from the column inlet and decreased towards the column effluent. Dehalococcoides cell numbers dropped from approximately 73.5% of the total Bacterial population in the original inocula, to about 0.5% to 4% throughout the column. The results were consistent with estimates of electron donor utilization, with 4% going towards dehalogenation reactions.     

Utilization of fly ash to improve the quality of the acid mine drainage generated by oxidation of a sulphide-rich mining waste: column experiments

The production of Acid Mine Drainage (AMD) as a result of the oxidative dissolution of sulphides is one of the main pollution problems affecting natural watercourses in mining environments with sulphide-rich residues. In this work, the generation of AMD was prevented by means of the addition of fly ash to sulphide-rich residues in non-saturated column experiments. A column experiment filled with a pyrite-rich sludge with artificial irrigation leached acid drainages (pH approx. 2) containing high concentrations of sulphate, iron and other metals. However, non-saturated column experiments filled with pyritic-rich sludge and fly ash drained leachates characterized by alkaline pH (pH up to 10), low sulphate concentration, and lack of iron and other metals in solution. The pyrite oxidative dissolution at high pH, as a consequence of the leaching of fly ash, favours the metal precipitation inside the column (mainly iron), the coating of pyrite grains, and the attenuation of the oxidation process, resulting in a great improvement in the quality of the leachates.     

锆负载型树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂 ,并在评价了该树脂对氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明 ,锆的最佳负载的最佳浓度为0 .5mol/L ,该负载树脂的最佳吸附pH为 3.0— 4 .0 ,用填充柱进行的动态实验结果表明 ,pH =3时的吸附容量显著高于 pH=4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理 ,当柱流量为 35mL/min(SV10 )、第二柱穿透时 ,第一柱的吸附容量为 10 2 2 8mg/L湿树脂 ;用 0 .1mol/L的NaOH溶液进行再生 ,柱流量选择为 35mL/min(SV10 )时 ,脱附率在 95 %以上。     

Assessment of municipal waste compost as a daily cover material for odour control at landfill sites

The ability of municipal waste compost as a daily cover material to reduce the odorous emissions associated with landfill surfaces was investigated. Trials were carried out using landfill gas, a certified sulphurous gas mix and ambient air as a control. Odorous gas was passed through portable test column filled with compost at different densities (590 kg/m3 and 740 kg/m3). Gas samples were taken from the inlet, outlet and at varying column depths and examined using a combination of sensory analysis (olfactometry) and a novel analytical method (Transportable Selected Ion Flow Tube--TSIFT). Results for the trials using landfill gas showed a 69% odour reduction (OU/m3) through the column for compost with a bulk density of 590 kg/m3, and a reduction of 97% using compost with a bulk density of 740 kg/m3. TSIFT analysis showed an overall decrease in the concentration of terpenes, and sulphurous compounds in the outlet gas from the column for both bulk densities. No significant trend could be identified for the concentrations at different depths within the column. Results show the ability of compost to reduce landfill odours under differing conditions. The inconclusive data provided by TSIFT analysis may be due to the analysis of compounds that are not contributing to odour, and thus highlights the potential for synergetic effects and the importance of sensory measurement when examining odorous emissions.     

Transport of silver nanoparticles (AgNPs) in soil

The effect of soil properties on the transport of silver nanoparticles (AgNPs) was studied in a set of laboratory column experiments, using different combinations of size fractions of a Mediterranean sandy clay soil. The AgNPs with average size of ∼30 nm yielded a stable suspension in water with zeta potential of −39 mV. Early breakthrough of AgNPs in soil was observed in column transport experiments. AgNPs were found to have high mobility in soil with outlet relative concentrations ranging from 30% to 70%, depending on experimental conditions. AgNP mobility through the column decreased when the fraction of smaller soil aggregates was larger. The early breakthrough pattern was not observed for AgNPs in pure quartz columns nor for bromide tracer in soil columns, suggesting that early breakthrough is related to the nature of AgNP transport in natural soils. Micro-CT and image analysis used to investigate structural features of the soil, suggest that soil aggregate size strongly affects AgNP transport in natural soil. The retention of AgNPs in the soil column was reduced when humic acid was added to the leaching solution, while a lower flow rate (Darcy velocity of 0.17 cm/min versus 0.66 cm/min) resulted in higher retention of AgNPs in the soil. When soil residual chloride was exchanged by nitrate prior to column experiments, significantly improved mobility of AgNPs was observed in the soil column. These findings point to the importance of AgNP-soil chemical interactions as a retention mechanism, and demonstrate the need to employ natural soils rather than glass beads or quartz in representative experimental investigations.     

The influence of mass transfer on solute transport in column experiments with an aggregated soil

The spreading of concentration fronts in dynamic column experiments conducted with a porous, aggregated soil is analyzed by means of a previously documented transport model (DFPSDM) that accounts for longitudinal dispersion, external mass transfer in the boundary layer surrounding the aggregate particles, and diffusion in the intra-aggregate pores. The data are drawn from a previous report on the transport of tritiated water, chloride, and calcium ion in a column filled with Ione soil having an average aggregate particle diameter of 0.34 cm, at pore water velocities from 3 to 143 cm/h. The parameters for dispersion, external mass transfer, and internal diffusion were predicted for the experimental conditions by means of generalized correlations, independent of the column data. The predicted degree of solute front-spreading agreed well with the experimental observations. Consistent with the aggregate porosity of 45%, the tortuosity factor for internal pore diffusion was approximately equal to 2. Quantitative criteria for the spreading influence of the three mechanisms are evaluated with respect to the column data. Hydrodynamic dispersion is thought to have governed the front shape in the experiments at low velocity, and internal pore diffusion is believed to have dominated at high velocity; the external mass transfer resistance played a minor role under all conditions. A transport model such as DFPSDM is useful for interpreting column data with regard to the mechanisms controlling concentration front dynamics, but care must be exercised to avoid confounding the effects of the relevant processes.     

生物通风技术修复柴油污染土壤的土柱模拟实验

生物通风技术是将土壤气相抽提和生物降解结合起来的原位强迫氧化降解方法,对于修复因地下储油罐泄漏引起的土壤污染具有广阔的应用前景。通过室内土柱模拟柴油泄漏污染土壤,分析了不同历时残余总石油烃(total pe-troleum hydrocarbon,TPH)的平衡分布规律以及土壤中不同深度柴油量、总柴油量的变化。结果表明:(1)各柱残余TPH剖面分布差异的原因受土柱的初始装填情况的影响较大;(2)残余TPH平衡分布曲线呈双峰型的土柱,柴油的去除主要以挥发作用及生物降解作用为主;(3)挥发作用主要是由通风孔隙体积数及土壤含水率来影响的;重力作用则主要是由初始油浓度、土壤含水率、C∶N∶P影响的;除通风方式外,其余4个因素都对生物降解作用有影响;(4)初始油浓度较大,土壤含水率较小的柱8和柱11,生物降解作用最明显,柴油去除效果最好。该成果可为生物通风过程的强化提供理论依据。     

Estimation of mechanical dispersion and dispersivity in a soil-gas system by column experiments and the dusty gas model

In a previous study, column experiments were carried out with Toyoura sand (permeability 2.05×10(-11)m(2)) and Toyoura sand mixed with bentonite (permeability 9.96×10(-13)m(2)) to obtain the molecular diffusion coefficient, the Knudsen diffusion coefficient, the tortuosity for the molecular diffusion coefficient, and the mechanical dispersion coefficient of soil-gas systems. In this study, we conducted column experiments with field soil (permeability 2.0×10(-13)m(2)) and showed that the above parameters can be obtained for both less-permeable and more-permeable soils by using the proposed method for obtaining the parameters and performing column experiments. We then estimated dispersivity from the mechanical dispersion coefficients obtained by the column experiments. We found that the dispersivity depended on the mole fraction of the tracer gas and could be represented by a quadratic equation.     

An in situ study of the effect of nitrate on the reduction of trichloroethylene by granular iron

The effect of nitrate on the reduction of TCE by commercial granular iron was investigated in column experiments designed to allow for the in situ monitoring of the iron surface film with Raman spectroscopy. Three column experiments were conducted; one with an influent solution of 100 mg/l nitrate+1.5 mg/l TCE, and two control columns, one saturated directly with 100 mg/l nitrate solution, the other pre-treated with Millipore water prior to the introduction of a 100 mg/l nitrate solution. In the presence of nitrate, TCE adsorbed onto the iron, but there was little TCE reduction to end-products ethene and ethane. The iron used (Connelly, GPM, Chicago) is a product typical of those used in permeable granular iron walls. The material is covered by an air-formed high-temperature oxidation film, consisting of an inner layer of Fe(3)O(4), and an outer, passive layer of Fe(2)O(3). In the control column pre-treated with Millipore water, the passive Fe(2)O(3) layer was removed upon contact with the water in a manner consistent with an autoreduction reaction. In the TCE+nitrate column and the direct nitrate saturation column, nitrate interfered with the removal of the passive layer and maintained conditions such that high valency protective corrosion species, including Fe(2)O(3) and FeOOH, were stable at the iron surface. The lack of TCE reduction is explained by the presence of these species, as they inhibit both mechanisms proposed for TCE reduction by iron, including catalytic hydrogenation, and direct electron transfer.     

Optimization of the purification method for dioxin analysis in human serum and temporal changes in background dioxin levels in the general population

To perform high quality and high throughput measurements, complicated purification procedure by two rounds of open column chromatography was simplified by appraising the components and adding a sufficient amount of adsorbents to the column. The procedure consists of two open column techniques using a multi-layer silica gel column and an active carbon dispersed silica gel column. This purification procedure is used in "Standard manual for dioxin analysis in human blood" published in 2000 (Ministry of Health and Welfare, Japan, 2000). Consequently, a purification procedure using only 1 g of 10% AgNO(3)/silica gel can remove the matrix of blood serum as effectively as a multi-layer silica gel column. In addition, 0.1 g of carbon silica gel, equivalent to 1/10 the weight used currently in analyses, separates and recovers the dioxins in purified extract of blood serum. Furthermore, changes in the background level in the general population were clarified by monitoring the dioxin concentrations in human blood. The dioxin concentrations and ratios in blood in the general population remained at a tolerable level for three months. Therefore, the blood serum was available for the detection of a remarkable elevation in dioxins level considered to be indicative of contamination due to high-density exposure.     

Studies into the formation of dioxins in the sintering process used in the iron and steel industry. 1. Characterisation of isomer profiles in particulate and gaseous emissions

Dioxin analyses using a DB5MS chromatography column are presented for samples of dust from an electrostatic precipitator and emissions from the main stack of a UK sinter plant. The analyses have been repeated using the SP2331 column, for which the elution order has been determined for the whole range of tetra to octachlorodibenzo-p-dioxins and dibenzofurans, and which provides a larger degree of separation than the DB5MS column. Polychlorinated dibenzofurans are present in significantly larger amounts in both the dust and stack emissions, and are the main contributors to the I-TEQ. Analysis using the SP2331 column for dioxins show considerable similarity to those of Bacher et al. for soot from a wood-burning fire, but differ markedly from those of Addink et al. for simulation of waste incineration. The similarities to Bacher's results are less for the dibenzofurans. Comparison of absolute concentrations with reported vapour pressures shows the retention of significant dioxin in the dust to involve mechanisms other than pure condensation.