Reversibly enhanced aqueous solubilization of volatile organic compounds using a redox-reversible surfactant

Surfactant-enhanced remediation (SER) is an effective method for the removal of volatile organic compounds (VOCs) from contaminated soils and groundwater. To reuse the surfactant the VOCs must be separated from the surfactant solutions. The water solubility of VOCs can be enhanced using reversible surfactants with a redox-acive group, (ferrocenylmethyl)dodecyldimethylammonium bromide (Fcl2) and (ferrocenylmethyl)tetradecanedimethylammonium bromide (Fcl4), above and below their critical micelle concentrations (CMC) under reducing (I⁺) and oxidative (I²⁺) conditions. The CMC values of Fcl2 and Fcl4 in I⁺ are 0.94 and 0.56 mmol/L and the solubilization of toluene by Fcl2 and Fcl4 in I⁺ for toluene is higher than the solubilization achieved with sodium dodecyl sulfate, cetyltrimethylammonium bromide and Trition X-114. The solubilization capacity of the ferrocenyl surfactants for each tested VOCs ranked as follows: ethylbenzene > toluene > benzene. The solubilities of VOCs by reversible surfactant in I⁺ were 30% higher than those in I²⁺ at comparable surfactant concentrations. The effects of Fcl4 concentrations on VOCs removal efficiency were as follows: benzene > toluene > ethylbenzene. However, an improved removal efficiency was achieved at low ferrocenyl surfactant concentrations. Furthermore, the reversible surfactant could be recycled through chemical approaches to remove organic pollutants, which could significantly reduce the operating costs of SER technology.     

高温状态下受热时间对膨润土物性指标的影响∗

高温状态下膨润土的物性指标变化是高放核废物深地质处置库设计的重要参数之一。通过高温状态下不同受热时间MX80钠基膨润土的比重、液塑限、自由膨胀率试验,研究了受热时间对膨润土基本物性指标的影响规律;并通过热重分析(TGA)、X衍射(XDR)、电镜扫描(SEM)试验,从微观角度对上述变化规律进行了合理解释。研究结果表明:随着受热时间的增加,膨润土的比重、液塑限、自由膨胀率在受热15～30天内急剧下降,降幅分别为2.5%、3.1%和28.3%,之后各值变化量很小;高温状态下,膨润土的矿物成分转化、结合水脱附、微观形貌改变是膨润土物性指标发生变化的根本原因,三者之间相互作用和彼此影响。     

Fouling distribution in forward osmosis membrane process

Fouling behavior along the length of membrane module was systematically investigated by performing simple modeling and lab-scale experiments of forward osmosis （FO） membrane process. The flux distribution model developed in this study showed a good agreement with experimental results, validating the robustness of the model. This model demonstrated, as expected, that the permeate flux decreased along the membrane channel due to decreasing osmotic pressure differential across the FO membrane. A series of fouling experiments were conducted under the draw and feed solutions at various recoveries simulated by the model. The simulated fouling experiments revealed that higher organic （alginate） fouling and thus more flux decline were observed at the last section of a membrane channel, as foulants in feed solution became more concentrated. Furthermore, the water flux in FO process declined more severely as the recovery increased due to more foulants transported to membrane surface with elevated solute concentrations at higher recovery, which created favorable solution environments for organic adsorption. The fouling reversibility also decreased at the last section of the membrane channel, suggesting that fouling distribution on FO membrane along the module should be carefully examined to improve overall cleaning efficiency. Lastly, it was found that such fouling distribution observed with co-current flow operation became less pronounced in counter- current flow operation of FO membrane process.     

Nitrogen mass balance in a constructed wetland treating piggery wastewater effluent

The nitrogen changes and the nitrogen mass balance in a free water surface flow constructed wetland （CW） using the four-year monitoring data from 2008 to 2012 were estimated. The CW was composed of six cells in series that include the first settling basin （Cell 1）, aeration pond （Cell 2）, deep marsh （Cell 3）, shallow marsh （Cell 4）, deep marsh （Cell 5） and final settling basin （Cell 6）. Analysis revealed that the NH4＋-N concentration decreased because of ammonification which was then followed by nitrification. The NO4＋-N and NO4＋-N were also further reduced by means of microbial activities and plant uptake during photosynthesis. The average nitrogen concentration at the influent was 37,819 kg/year and approximately 45% of that amount exited the CW in the effluent. The denitrification amounted to 34% of the net nitrogen input, whereas the accretion of sediment was only 7%. The biomass uptake of plants was able to retain only 1% of total nitrogen load. In order to improve the nutrient removal by plant uptake, plant coverage in four cells （i.e., Cells 1, 3, 4 and 5） could be increased.     

A Novel Method to Capture and Analyze Flow in a Gross Pollutant Trap Using Image-Based Vector Visualization

A novel method is developed to capture and analyze several experimental flow regimes through a gross pollutant trap (GPT) with fully and partially blocked screens. Typical flow conditions and screen blockages are based on findings from field investigations that show a high content of organic matter in urban areas. Fluid motion of neutral buoyant particles is tracked using a high-speed camera and particle image velocimetry (PIV) software. The recorded fluid motion is visualized through an image-based, line integral convolution (LIC) algorithm, generally suitable for large computational fluid dynamics (CFD) datasets. The LIC method, a dense representation of streamlines, is found to be superior to the point-based flow visualization (e.g., hedgehog or arrow plots) in highlighting main flow features that are important for understanding litter capture and retention in the GPT. Detailed comparisons are made between the flow regimes, and the results are compared with CFD data previously obtained for fully blocked screens. The LIC technique is a useful tool for identifying flow structures in the GPT and areas that are subjected to abnormalities difficult to detect by conventional methods. The novel method is found to be useful both in the laboratory and in the field, with little preparation and cost. The enhancements and pitfalls of the LIC technique along with the experimentally captured flow field are presented and discussed.     

The use of nanoparticles in polymeric and ceramic membrane structures: Review of manufacturing procedures and performance improvement for water treatment

Membrane separations are powerful tools for various applications, including wastewater treatment and the removal of contaminants from drinking water. The performance of membranes is mainly limited by material properties. Recently, successful attempts have been made to add nanoparticles or nanotubes to polymers in membrane synthesis, with particle sizes ranging from 4 nm up to 100 nm. Ceramic membranes have been fabricated with catalytic nanoparticles for synergistic effects on the membrane performance. Breakthrough effects that have been reported in the field of water and wastewater treatment include fouling mitigation, improvement of permeate quality and flux enhancement. Nanomaterials that have been used include titania, alumina, silica, silver and many others. This paper reviews the role of engineered nanomaterials in (pressure driven) membrane technology for water treatment, to be applied in drinking water production and wastewater recycling. Benefits and drawbacks are described, which should be taken into account in further studies on potential risks related to release of nanoparticles into the environment.     

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.     

Biological monitoring of heavy metal contaminations using owls

Iron, manganese, copper, lead and cadmium were measured in the livers, muscles, kidneys and bones of Eurasian Eagle Owls (Bubo bubo), Brown Hawk Owls (Nixos scutulata) and Collared Scops Owls (Otus lempiji) from Korea. Iron concentrations by tissue within species did not differ, but there were significant differences among tissues across all species. Manganese and copper concentrations in muscles, kidneys and bones, but not livers, differed among species and also differed among tissues in the three owl species. We suggest that manganese and copper concentrations from this study were far below the level associated with their toxicity. Lead concentrations significantly differed among all species for livers and bones, and among tissues for each species. Cadmium concentrations were significantly different among species for all tissues and among tissues in Eurasian Eagle Owls and Collared Scops Owls. For most samples, lead concentrations in livers and bones, and cadmium in livers and kidneys, were within the background levels for wild birds. For some Eurasian Eagle Owls and Collared Scops Owls, lead concentrations were at an acute exposure level, whilst lead concentrations were at a chronic exposure level in Brown Hawk Owls. Cadmium concentrations were at a chronic exposure level in all three owl species. Acute and chronic poisoning was significantly correlated between indicator tissues. We suggest that lead and cadmium contamination in Eurasian Eagle Owls may reflect a Korean source, Brown Hawk Owls may reflect Korean and wintering sites, and Collared Scops Owls may reflect breeding and/or wintering sites.     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

Fraction characteristics of rare earth elements in the surface sediment of Bohai Bay, North China

Surface sediment samples were collected at 27 stations of Bohai Bay, North China. Sequential extractions were carried out in this study. REE were leached out from four labile fractions: Exchangeable (L1), bound to carbonates (L2), bound to Fe–Mn oxides (L3), bound to organic matter (L4), and the remainder was residual (R5). The total contents of REE fluctuate slightly in Bohai Bay, and are mainly concentrated in the middle region, showing relatively higher levels in the north than that in the south of Bohai Bay. Percentages of L1, L2, L3, L4, and R5 for REE suggest that the residual fraction accounts for the major component of REE, whereas Fe–Mn oxides also play important roles in combining labile REE. As the REE complex is not stabilized, the competition of complex could induce dissociation of the complex and redistribution of the REE in various environments. According to REE patterns and Y/Ho ratios of samples, REE are not anthropogenic or oceanic sources but riverine input, whereas suitable environment varieties can slightly affect the patterns and fractionations of REE. As powerful tracers for the variable of environment, higher anomaly of Eu and Ce in southern regions indicates a greater reduction in the condition of surface sediment in the south than that in the north of Bohai Bay.