Photo-induced surface frustrated Lewis pairs for promoted photocatalytic decomposition of perfluorooctanoic acid

● Terminal carboxylate group activation is PFOA degradation’s rate-limiting step. ● Bi₃O(OH)(PO₄)₂ with surface frustrated Lewis pairs (SFLPs) efficiently degrade PFOA. ● Photo-induced Lewis acidic sites and proximal surface hydroxyls constitute SFLPs. ● SFLPs act as collection centers to effectively adsorb PFOA. ● SFLPs endow accessible pathways for photogenerated holes rapid transfer to PFOA. Heterogeneous photocatalysis has gained substantial research interest in treating per- and polyfluoroalkyl substances (PFAS)-contaminated water. However, sluggish degradation kinetics and low defluorination efficiency compromise their practical applications. Here, we report a superior photocatalyst, defected Bi₃O(OH)(PO₄)₂, which could effectively degrade typical PFAS, perfluorooctanoic acid (PFOA), with high defluorination efficiency. The UV light irradiation could in situ generate oxygen vacancies on Bi₃O(OH)(PO₄)₂ through oxidation of the lattice hydroxyls, which further promotes the formation of Lewis acidic coordinately unsaturated bismuth sites. Then, the Lewis acidic sites couple with the proximal surface hydroxyls to constitute the surface frustrated Lewis pairs (SFLPs). With the in-depth spectroscopic analysis, we revealed that the photo-induced SFLPs act as collection centers to effectively adsorb PFOA and endow accessible pathways to transfer photogenerated holes to PFOA rapidly. Consequently, activation of the terminal carboxyl, a rate-limiting step for PFOA decomposition, could be easily achieved over the defected Bi₃O(OH)(PO₄)₂ photocatalyst. These results suggest that SFLPs exhibit great potential in developing highly efficient photocatalysts to degrade persistent organic pollutants.     

石墨烯对RDX机械感度及爆轰性能的影响

炸药添加剂对改善单质炸药安全与能量特性有重要作用。为研究纳米微颗粒石墨烯(Gr)对黑索今(RDX)热性能、机械感度及爆轰性能的影响,设计不同比例含量的Gr/RDX混合药剂配方,并对其进行差热、撞击感度、摩擦感度、爆速及钢凹深度的测试分析。结果表明:与纯RDX相比,Gr/RDX混合药剂DSC（差示扫描量热）曲线分解峰宽变窄、峰形更尖锐,Gr加速RDX的放热过程;Gr/RDX混合药剂撞击感度与摩擦感度随Gr比例含量的增加呈先降低后升高的趋势,少量Gr可使RDX变得钝感,含量增加时,敏化作用逐渐表现出来;Gr/RDX混合药剂爆速与钢凹深度随Gr比例含量的增加而降低;Gr含量为1%时可显著降低RDX的机械感度,而能量基本不衰减。Gr可作为RDX功能添加剂,在确保能量输出的同时,可降低机械感度、提高安全性。     

Pulsed pumping process optimization using a potential flow model

A computational model is applied to the optimization of pulsed pumping systems for efficient in situ remediation of groundwater contaminants. In the pulsed pumping mode of operation, periodic rather than continuous pumping is used. During the pump-off or trapping phase, natural gradient flow transports contaminated groundwater into a treatment zone surrounding a line of injection and extraction wells that transect the contaminant plume. Prior to breakthrough of the contaminated water from the treatment zone, the wells are activated and the pump-on or treatment phase ensues, wherein extracted water is augmented to stimulate pollutant degradation and recirculated for a sufficient period of time to achieve mandated levels of contaminant removal. An important design consideration in pulsed pumping groundwater remediation systems is the pumping schedule adopted to best minimize operational costs for the well grid while still satisfying treatment requirements. Using an analytic two-dimensional potential flow model, optimal pumping frequencies and pumping event durations have been investigated for a set of model aquifer-well systems with different well spacings and well-line lengths, and varying aquifer physical properties. The results for homogeneous systems with greater than five wells and moderate to high pumping rates are reduced to a single, dimensionless correlation. Results for heterogeneous systems are presented graphically in terms of dimensionless parameters to serve as an efficient tool for initial design and selection of the pumping regimen best suited for pulsed pumping operation for a particular well configuration and extraction rate. In the absence of significant retardation or degradation during the pump-off phase, average pumping rates for pulsed operation were found to be greater than the continuous pumping rate required to prevent contaminant breakthrough.     

Combining steam injection with hydraulic fracturing for the in situ remediation of the unsaturated zone of a fractured soil polluted by jet fuel

A steam injection pilot-scale experiment was performed on the unsaturated zone of a strongly heterogeneous fractured soil contaminated by jet fuel. Before the treatment, the soil was stimulated by creating sub-horizontal sand-filled hydraulic fractures at three depths. The steam was injected through one hydraulic fracture and gas/water/non-aqueous phase liquid (NAPL) was extracted from the remaining fractures by applying a vacuum to extraction wells. The injection strategy was designed to maximize the heat delivery over the entire cell (10 m × 10 m × 5 m). The soil temperature profile, the recovered NAPL, the extracted water, and the concentrations of volatile organic compounds (VOCs) in the gas phase were monitored during the field test. GC-MS chemical analyses of pre- and post-treatment soil samples allowed for the quantitative assessment of the remediation efficiency. The growth of the heat front followed the configuration of hydraulic fractures. The average concentration of total hydrocarbons (g/kg of soil) was reduced by ～ 43% in the upper target zone (depth = 1.5-3.9 m) and by ～ 72% over the entire zone (depth = 1.5-5.5 m). The total NAPL mass removal based on gas and liquid stream measurements and the free-NAPL product were almost 30% and 2%, respectively, of those estimated from chemical analyses of pre- and post-treatment soil samples. The dominant mechanisms of soil remediation was the vaporization of jet fuel compounds at temperatures lower than their normal boiling points (steam distillation) enhanced by the ventilation of porous matrix due to the forced convective flow of air. In addition, the significant reduction of the NAPL mass in the less-heated deeper zone may be attributed to the counter-current imbibition of condensed water from natural fractures into the porous matrix and the gravity drainage associated with seasonal fluctuations of the water table.     

Estimating an homogeneous series of a population abundance indicator despite changes in data collection procedure: A hierarchical Bayesian modelling approach

Abundance indicators are required both to assess and to manage wild populations. As new techniques are developed and teams in charge of gathering the data change, data collection procedures (DCPs) can evolve in space and time. How to estimate an homogeneous series of abundance indicator despite changes in DCP? To tackle this question a hierarchical Bayesian modelling (HBM) approach is proposed. It integrates multiple DCPs in order to derive a single abundance indicator that can be compared over space and time irrespective of the DCP used. Compared to single DCP models, it takes further advantage for abundance estimation of the joint treatment of a larger set of spatio-temporal units. After presenting the general formulation of our HBM approach, it is applied to the juvenile Atlantic salmon (Salmo salar L.) population of the River Nivelle (France). Posterior model checking, using χ² discrepancy measure, do not reveal any inadequacy between the model and the data. Despite a change in the DCP used (successive removals to catch-per-unit of effort), a unique abundance indicator for the 425 spatio-temporal units (site × year) sampled over twenty-four years (1985-2008) is estimated. The HBM approach allows the assessment of precision of the abundance estimates and shows variation between DCPs: a reduction in precision is observed during the most recent years (2005-2008) when only the catch-per-unit of effort DCP was used. The merits and generality of our HBM approach are discussed. We contend it extends previous single DCP models or inter-calibration of two DCPs, and it could be applied to a wide range of specific situations (taxon and DCPs).     

Enhanced activation of peroxydisulfate by strontium modified BiFeO3perovskite for ciprofloxacin degradation

A series of Sr-doped BiFeO₃ perovskites (Bi_1-xSr_xFeO₃, BSFO) fabricated via sol-gel method was applied as peroxydisulfate (PDS) activator for ciprofloxacin (CIP) degradation. Various technologies were used to characterize the morphology and physicochemical features of prepared BSFO samples and the results indicated that Sr was successfully inserted into the perovskites lattice. The catalytic performance of BiFeO₃ was significantly boosted by strontium doping. Specifically, Bi_0.9Sr_0.1FeO₃ (0.1BSFO) exhibited the highest catalytic performance for PDS activation to remove CIP, where 95% of CIP (10 mg/L) could be degraded with the addition of 1 g/L 0.1BSFO and 1 mmol/L PDS within 60 min. Moreover, 0.1BSFO displayed high reusability and stability with lower metal leaching. Weak acidic condition was preferred to neutral and alkaline conditions in 0.1BSFO/PDS system. The boosted catalytic performance can be interpreted as the lower oxidation state of Fe and the existence of affluent oxygen vacancies generated by Sr doping, that induced the formation of singlet oxygen (¹O₂) which was confirmed as the dominant reactive species by radical scavenging studies and electron spin resonance (ESR) tests. The catalytic oxidation mechanism related to major ¹O₂ and minor free radicals was proposed. Current study opens a new avenue to develop effective A-site modified perovskite and expands their application for PDS activation in wastewater remediation.     

Review on heterogeneous oxidation and adsorption for arsenic removal from drinking water

The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.     

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

Removing lignin model pollutants with BiFeO3–g-C3N4 compound as an efficient visible-light-heterogeneous Fenton-like catalyst

BiFeO_3–g-C_3N_4 nanoscaled composite was prepared with a hydrothermal method and evaluated as a highly efficient photo-Fenton like catalyst under visible light irradiation. The BiFeO_3–g-C_3N_4 composite exhibited much stronger adsorption ability to lignin model pollutant(guaiacol) than that of BiFeO_3, which may be due to the higher specific surface area(BiFeO_3–g-C_3N_4: 35.59 m~2/g BiFeO_3: 7.42 m~2/g) and the adsorption form of π–π stack between g-C_3N_4 and guaiacol. The composite exhibited excellent visible light-Fenton like catalysis activity, being influenced by the solution pH value and the proportions of BiFeO_3 and g-C_3N_4 nanosheets. Under optimal conditions with visible light irradiation, the BiFeO_3–g-C_3N_4 composite yielded fast degradation of guaiacol with an apparent rate constant of 0.0452 min~(-1), which were 5.21 and 6.80 folds of that achieved by using BiFeO_3 and the mixture of BiFeO_3 and g-C_3N_4 nanosheets, respectively. The significantly enhanced visible light-Fenton like catalytic properties of the BiFeO_3–g-C_3N_4 composite in comparison with that of BiFeO_3 was attributed to a large surface area, much increased adsorption capacity and the semiconductor coupling effect between BiFeO_3 and g-C_3N_4 in the composite.     

Effect of ignition position on the run-up distance to DDT for hydrogen-air explosions

The method described in this paper enabled reliable and accurate positioning of an overdriven detonation by calculation of shock wave velocities (detonation and retonation) for hydrogen explosions in a closed 18 m long horizontal DN150 pipe. This enabled an empirical correlation between the ignition position and the run-up distance to DDT to be determined. It was shown that the initial ability of the flame to expand unobstructed and the piston-like effect of burnt gas expanding against the closed end of the tube contributed to initial flame acceleration and hence were able to affect the run-up distance to overdriven detonation. Flame speeds and rates of initial pressure rise were also used to explain how these two competing effects were able to produce a minimum in the run-up distance to DDT. The shortest run-up distance to DDT, relative to the ignition position, for this pipe and gas configuration was found when the ignition position was placed 5.6 pipe diameters (or 0.9 m) from the closed pipe end. The shortest run-up distance to DDT relative to the end of the pipe was recorded when the ignition source was placed 4.4 pipe diameters or 0.7 m from the pipe end.