Three-dimensional density-dependent flow and multicomponent reactive transport modeling of chlorinated solvent oxidation by potassium permanganate

A popular method for the treatment of aquifers contaminated with chlorinated solvents is chemical oxidation based on the injection of potassium permanganate (KMnO₄). Both the high density (1025 gL^− 1) and reactivity of the treatment solution influence the fate of permanganate (MnO₄) in the subsurface and affect the degree of contaminant treatment. The MIN3P multicomponent reactive transport code was enhanced to simulate permanganate-based remediation, to evaluate the pathways of MnO₄ utilization, and to assess the role of density contrasts for the delivery of the treatment solution. The modified code (MIN3P-D) provides a direct coupling between density-dependent fluid flow, solute transport, contaminant treatment, and geochemical reactions. The model is used to simulate a field trial of TCE oxidation in a sandy aquifer that is underlain by an aquitard. Three-dimensional simulations are conducted for a coupled reactive system comprised of ten aqueous components, two mineral phases, TCE (dissolved, adsorbed, and NAPL), reactive organic matter, and including ion exchange reactions. Model parameters are constrained by literature data and a detailed data set from the field site under investigation. The general spatial and transient evolution in observed concentrations of the oxidant, dissolved TCE, and reaction products are adequately reproduced by the simulations. The model elucidates the important role of density-induced flow and transport on the distribution of the treatment solution into NAPL containing regions located at the aquifer–aquitard interface. Model results further suggest that reactions that do not directly affect the stability of MnO₄ have a negligible effect on solution density and MnO₄ delivery.     

废水中KMnO4对生物处理效果的影响

为减轻和消除含高浓度KMnO4的牛仔服加工废水对生物处理系统的毒害作用,采用模拟序批式活性污泥法,研究KMnO4对活性污泥微生物生长的影响及COD和NH4+-N的降解规律。结果表明,当处理进水COD浓度500 mg/L,NH4+-N浓度23.5 mg/L,污泥浓度为2 000 mg/L时,曝气时间为4 h,KMnO4质量浓度增加对COD和NH4+-N的降解影响很大;同样条件下曝气时间改为8 h,对NH4+-N的降解影响显著减小,但对COD的降解影响减少不多;并且,高浓度KMnO4对NH4+-N去除效果的抑制作用比对COD的大。因此,处理含高浓度KMnO4的废水需要延长一倍曝气时间,可以获得良好的COD和NH4+-N的降解效果。同时,KMnO4对活性污泥的抑制影响较好地吻合非竞争性抑制机理修正莫若特方程的规律。     

Chemical oxidation of cable insulating oil contaminated soil

Leaking cable insulating oil is a common source of soil contamination of high-voltage underground electricity cables in many European countries. In situ remediation of these contaminations is very difficult, due to the nature of the contamination and the high concentrations present. Chemical oxidation leads to partial removal of highly contaminated soil, therefore chemical oxidation was investigated and optimized aiming at a subsequent bioremediation treatment. Chemical oxidation of cable oil was studied with liquid H₂O₂ and solid CaO₂ as well as permanganate at pH 1.8, 3.0 and 7.5. Liquid H₂O₂ most effectively removed cable oil at pH 7.5 (24%). At pH 7.5 poor oil removal of below 5% was observed with solid CaO₂ and permanganate within 2 d contact time, whereas 18% and 29% was removed at pH 1.8, respectively. A prolonged contact time of 7 d showed an increased oil removal for permanganate to 19%, such improvement was not observed for CaO₂.Liquid H₂O₂ treatment at pH 7.5 was most effective with a low acid use and was best fit to a subsequent bioremediation treatment. To further optimize in situ chemical oxidation with subsequent bioremediation the effect of the addition of the iron catalyst and a stepwise liquid H₂O₂ addition was performed. Optimization led to a maximum of 46% cable oil removal with 1469 mM of H₂O₂, and 6.98 mM Fe(II) chelated with citric acid (H₂O₂:FeSO₄ = 210:1 (mol mol⁻¹). The optimum delivery method was a one step addition of the iron catalyst followed by step wise addition of H₂O₂.     

Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils

In situ chemical oxidation is a commonly applied soil and groundwater remediation technology, but can have significant effects on soil properties, which in turn might affect fate and transport of organic contaminants. In this study, it was found that oxidation treatment resulted mainly in breakdown of soil organic matter (SOM) components. Sorption of naphthalene and phenanthrene to the original soils and the KMnO₄-treated soils was linear, indicating that hydrophobic partitioning to SOM was the predominant mechanism for sorption. Desorption from the original and treated soils was highly resistant, and was well modeled with a biphasic desorption model. Desorption of residual naphthalene after treating naphthalene-contaminated soils with different doses of KMnO₄ also followed the biphasic desorption model very well. It appears that neither changes of soil properties caused by chemical oxidation nor direct chemical oxidation of contaminated soils had a noticeable effect on the nature of PAH-SOM interactions.     

Photocatalytic oxidation of xenobiotics in water with immobilized TIO2 on agitator

Abstract

A novel photocatalytic oxidation reactor, using Degussa P‐25 T_iO₂ as a stationary phase with a thickness of 1.5–2.0 um on the blades of agitator, was developed to study the photocatalytic oxidation of xenobiotics. Particularly in this device, separation of photocatalyst from the purified water after oxidation reaction was not necessary, and no other aeration equipment was required to supply oxygen. To examine the efficiency of this device, photocatalytic degradation of xenobiotic organics such as carbofuran was studied as an example. Results indicated that carbofuran could be degraded completely with mineralization efficiency of 20 % after 6 hours of oxidation under the imposed conditions. The mineralization rate of carbofuran was found to follow the pseudo‐first order reaction kinetics. Moreover, the rate constant of mineralization was found to be proportional to T_iO₂ film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing T_iO₂ film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

Reaction-enhanced mass transfer and transport from non-aqueous phase liquid source zones

The objective of the following research is to theoretically quantify the enhancement of interphase mass transfer of dissolved non-aqueous phase liquid (NAPL) compounds from the non-aqueous phase to the aqueous phase and the enhancement of dispersive mass transport from a NAPL zone due to destruction of dissolved NAPL compounds. For relatively slow reaction rates, such as for permanganate and perchloroethene (PCE), local-scale mass transfer enhancement is expected to be small. Dispersive mass transport with reaction from a horizontal NAPL zone can be quantified using equations derived for a mathematically equivalent falling film reactor system. In contrast to local-scale interphase mass transfer, dispersive mass transport from NAPL zones may be significantly increased by reaction. Enhancement factors due to destruction of the NAPL compound(s) are mainly dependent on NAPL solubility and oxidant concentration and to a lesser extent on reaction rate, stoichiometry, and transverse dispersion coefficients. Higher NAPL solubility and/or lower oxidant concentration reduces the maximum expected enhancement factor. Reaction enhancement factors for mass transport from NAPL zones are expected to be in the range of 5-50 for permanganate and chlorinated solvents. Theoretical results suggest that assuming instantaneous reaction rates may be appropriate for dispersive mass transport from NAPL zones.     

氧化锰矿渣改性制备SCR脱硝催化剂

以锰酸钾生产过程中产生的氧化锰矿渣为原料,制备了一系列Mn基SCR脱硝催化剂。研究了活性炭、二氧化钛、以及含锰量的变化对催化剂的脱硝活性的影响。结果表明,直接由矿渣制备的催化剂和添加活性炭、二氧化钛制备的催化剂,其最大脱硝率分别为40%和78%。XPS表征发现催化剂中的锰元素存在多种氧化价态,活性炭的加入在一定程度上改变了不同价态之间的相对含量;在矿渣中加入硫酸锰后,发现总锰含量达到10%时,催化剂的最大脱硝率从78%降低至57%,XRD测试发现硫酸锰的加入导致S2O27-物种的生成,可能是引起催化剂活性下降的原因之一;而加入醋酸锰至总锰含量达到10%时,增大了催化剂的活性温度窗口,当总锰含量达到20%时,在空速10 000 h-1条件下,催化剂的最大脱硝率达到86.7%。     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Catalytic destruction of pentachlorobenzene in simulated flue gas by a V2O5-WO3/TiO2 catalyst

Pentachlorobenzene (PeCB) in simulated flue gas was destructed by a commercial V₂O₅-WO₃/TiO₂ catalyst in this study. The effects of reaction temperature, oxygen concentration, space velocity and some co-existing pollutants on PeCB conversion were investigated. Furthermore, a possible mechanism for the oxidation of PeCB over the vanadium oxide on the catalysts was proposed. Results show that the increase of gas hourly space velocity (GHSV) and the decrease of operating temperature both resulted in the decrease of PeCB removal over the catalyst, while the effect of the oxygen content in the range of 5-20% (v/v) on PeCB conversion was negligible. PeCB decomposition could be obviously affected by the denitration reactions under the conditions because of the positive effect of NO but negative effect of NH₃. The introduction of SO₂ caused the catalyst poisoning, probably due to the sulfur-containing species formed and deposited on the catalyst surface. The PeCB molecules were first adsorbed on the catalyst surface, and then oxidized into the non-aromatic acyclic intermediates, low chlorinated aromatics and maleic anhydride.     

Influence of NO2 on S(IV) oxidation in aqueous suspensions of aerosol particles from two different origins

The influence of soluble compounds leached from real atmospheric aerosol particles (size range D_ae: 0.17–1.6 μm) and dissolved NO₂ on S(IV) oxidation in aqueous solution is presented. Experiments were conducted with aerosol particles of two different origins (i.e., urban and industrial) and at concentrations of trace gases in the gas mixtures (SO₂/air and SO₂/NO₂/air) typical for a polluted atmosphere. During the introduction of SO₂/air into the aqueous aerosol suspensions under dark conditions at pH 4, the formation of SO₄²⁻ was very slow with a long induction period. However, in the presence of NO₂ the oxidation rate of dissolved SO₂ in suspensions of aerosols from both origins increased substantially (about 10 times). The results suggest that soluble compounds eluted from atmospheric aerosols have not only a catalytic (e.g. Fe, Mn), but also a pronounced inhibiting effect (e.g., oxalate, formate, acetate, glycolate) on S(IV) autoxidation. When NO₂ was also introduced into the aerosol suspensions, the inhibition was not so highly expressed. An explanation for this is that the radical chain mechanism is mainly initiated by the interaction of dissolved NO₂ and HSO₃⁻. Therefore, at conditions typical for a polluted atmosphere dissolved NO₂ can have a significant influence on the secondary formation of SO₄²⁻.     

Using slow-release permanganate candles to remove TCE from a low permeable aquifer at a former landfill

Past disposal of industrial solvents into unregulated landfills is a significant source of groundwater contamination. In 2009, we began investigating a former unregulated landfill with known trichloroethene (TCE) contamination. Our objective was to pinpoint the location of the plume and treat the TCE using in situ chemical oxidation (ISCO). We accomplished this by using electrical resistivity imaging (ERI) to survey the landfill and map the subsurface lithology. We then used the ERI survey maps to guide direct push groundwater sampling. A TCE plume (100-600 μg L⁻¹) was identified in a low permeable silty-clay aquifer (K_h = 0.5 m d⁻¹) that was within 6 m of ground surface. To treat the TCE, we manufactured slow-release potassium permanganate candles (SRPCs) that were 91.4 cm long and either 5.1 cm or 7.6 cm in dia. For comparison, we inserted equal masses of SRPCs (7.6-cm versus 5.1-cm dia) into the low permeable aquifer in staggered rows that intersected the TCE plume. The 5.1-cm dia candles were inserted using direct push rods while the 7.6-cm SRPCs were placed in 10 permanent wells. Pneumatic circulators that emitted small air bubbles were placed below the 7.6-cm SRPCs in the second year. Results 15 months after installation showed significant TCE reductions in the 7.6-cm candle treatment zone (67-85%) and between 10% and 66% decrease in wells impacted by the direct push candles. These results support using slow-release permanganate candles as a means of treating chlorinated solvents in low permeable aquifers.     

改性矿物吸附法和 O3氧化法对维生素 B12废水脱色处理简

采用改性矿物吸附法和O₃氧化法对某制药厂维生素B₁₂废水进行脱色处理。以废水色度去除率大于50%为目的，通过实验确定改性矿物吸附法和O₃氧化法处理维生素B₁₂废水的最佳工艺条件：废水的pH为3.00，有机化膨润土的投加量为5 g/L，PAC的投加量为6 g/L，投加有机化膨润土后搅拌时间为30 min时，废水的色度去除率可达到51.3%，处理成本为12.85元/t。O₃氧化法的最佳条件：废水的pH保持不变，O₃流量为5 g/h，反应时间为2 min，废水的色度去除率可达到68.8%，处理成本为0.96元/t。对比这2种方法，O₃氧化法处理该废水成本更低、效率更高，并且能提高废水的可生化性以便后续处理。     

Fenton氧化降解垃圾渗滤液中COD的动力学研究

对絮凝预处理后的垃圾渗滤液进行Fenton氧化处理。通过微分法对Fenton氧化的反应级数进行求解,确定其反应级数为2,并初步建立了Fenton氧化的动力学模型,即1/c=1/c0+kt,由此建立起来的降解的动力学模型与实验数据相吻合;在4个实验基准条件下———初始COD浓度为960 mg/L、pH值4、H2O2投加量0.4 mol/L、nH2O2/nFe2+3∶1,探讨了其中某一变量对反应速率的影响。实验水样为絮凝反应出水,进水COD浓度为912～960 mg/L,出水COD浓度为80～112 mg/L,COD去除率在87%～92%之间,表明Fenton试剂能够有效地处理垃圾渗滤液。     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

钛基IrO2-SnO2电极在烟气海水脱硫恢复系统中的应用

采用浸渍-热分解法制备了含IrOx-TiO2中间层的IrO2-SnO2电极,得到的电极具有较高的析氯电催化活性和较强的稳定性,并通过电化学氧化法对Na2SO3海水脱硫模拟液进行处理,考察了电流密度、温度、pH值和电解时间等电解工艺参数对Na2SO3去除率和化学需氧量COD的影响.结果表明,在电流密度为200 mA/cm...     

Lactate oxidation in pyrite suspension: a Fenton-like process in situ generating H2O2

Pyrite is a common mineral at many mining sites. In this study, the mineral pyrite was studied as a Fenton-like reagent for environmental concerns. We selected lactate as a model target molecule to evaluate the Fenton-like catalytic efficiency of pyrite upon organic oxidation. A complete set of control experiments in both aerobic and anaerobic atmospheres unequivocally established that the pyrite in aqueous solution could spontaneously in situ generate OH and H₂O₂, serving as a Fenton-like reagent to catalyze the oxidation of lactate to pyruvate with no need for additional H₂O₂. We called it the pyrite-only Fenton-like (PF) reagent. Monitoring concentration changes of lactate and pyruvate with the time indicated that the pyrite mediated the favorable pyruvate formation at pH 4.5, 60 °C, under air atmosphere. The PF reaction could be stimulated by visible light illumination. Under the optimum conditions, up to 50% of lactate was degraded within 10 d. The results suggest that pyrite and its Fenton-like processes may be potentially practical in wastewater treatment.     

Photocatalytic degradation of an azo dye using N-doped NaTaO3 synthesized by one-step hydrothermal process

N-doped NaTaO₃ compounds (NaTaO_3−xN_x) with nano-cubic morphology were successfully synthesized by one-step hydrothermal method and Methyl Orange (MO) was used as a model dye to evaluate their photocatalytic efficiency under visible-light irradiation. The as-prepared NaTaO_3−xN_x samples were characterized by various techniques, such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and UV-vis diffuse reflectance spectra and GC-MS. The results indicate that NaTaO_3−xN_x displays a pure perovskite structure when the synthesis temperature is higher than 180 °C. Moreover, as observed by SEM images, the particles of resultant NaTaO_3−xN_x show cubic morphology with the edge length of 200-500 nm, which can be easily removed by filtration after photocatalytic reaction. Doping of N increases the photocatalytic activity of NaTaO₃, and NaTaO_2.953N_0.047 shows the highest visible-light photocatalytic activity for the degradation of MO. Based on the experiment results, a possible mechanism of the photocatalysis over NaTaO_3−xN_x and the photodegradation pathway of MO were proposed.     

Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Fenton-混凝法处理苯胺废水

农药生产过程中产生的苯胺废水,COD浓度高、生物毒性强、可生化性差,一般生化方法很难处理。研究了Fenton与PAC联用处理苯胺废水。结果表明,Fenton氧化处理苯胺废水在最佳条件为pH=6、m（H2O2）/m（COD）=1.8、n（H2O2）/n（Fe2＋）=8时,COD和色度去除率分别为78.4%和92.3%。Fenton氧化后废水B/C值由0.037提高到0.324。最佳条件下联用PAC,在投加量为320 mg/L时COD与色度去除率分别为83.6%和94.8%,并且处理时间显著缩短,实际应用中可减少水力停留时间和构筑物体积。     

Iron-catalyzed oxidation of s(IV) species by oxygen in aqueous solution: Influence of pH on the redox cycling of iron

Redox cycling of Fe(II)/Fe(III) during the catalyzed aqueous S(IV) oxidation by dissolved oxygen in the presence of Fe(II) and/or Fe(III) at an initial pH_i of 4.4, often observed in atmospheric waters, was studied in detail. It has been found that the reaction rate is not considerably affected by the oxidation state of iron at the start of the reaction. An equilibrium between Fe(II) and Fe(III) was established a few minutes after the start of the reaction, regardless of the oxidation state of iron at the beginning of the experiment. The prevailing oxidation state of iron in a particular phase of the reaction depends on the concentration of S(IV) in the reaction solution. It has been found that the formation of polymerized hydroxo Fe(III) species is also included in the mechanism of the Fe-catalyzed oxidation of S(IV). The formation of these species was confirmed by the on-line measurement of Fe(II) and Fe_reac. The results also clearly demonstrate that the pH_i of the solution is a major factor, controlling the concentration of Fe(III) ions, the form of S(IV) species, and consequently the reaction rate of S(IV) oxidation by oxygen.