Reduction and adsorption of Pb in aqueous solution by nano-zero-valent iron—A SEM, TEM and XPS study

This study reports the synthesis, characterisation and application of nano-zero-valent iron (nZVI). The nZVI was produced by a reduction method and compared with commercial available ZVI powder for Pb²⁺ removal from aqueous phase. Comparing with commercial ZVI, the laboratory made nZVI powder has a much higher specific surface area. XRD patterns have revealed zero-valent iron phases in two ZVI materials. Different morphologies have been observed using SEM and TEM techniques. EDX spectrums revealed even distribution of Pb on surface after reaction. The XPS analysis has confirmed that immobilized lead was present in its zero-valent and bivalent forms. ‘Core-shell’ structure of prepared ZVI was revealed based on combination of XRD and XPS characterisations. In addition, comparing with Fluka ZVI, this lab made nZVI has much higher reactivity towards Pb²⁺ and within just 15 min 99.9% removal can be reached. This synthesized nano-ZVI material has shown great potential for heavy metal immobilization from wastewater.     

Remediation of groundwater contaminated with DNAPLs by biodegradable oil emulsion

Emulsion-based remediation with biodegradable vegetable oils was investigated as an alternative technology for the treatment of subsurface DNAPLs (dense non-aqueous phase liquids) such as TCE (trichloroethylene) and PCE (perchloroethylene). Corn and olive oil emulsions obtained by homogenization at 8000rpm for 15min were used. The emulsion droplets prepared with corn and olive oil gave a similar size distribution (1-10microm) and almost all of initially injected oil, >90%, remained in a dispersed state. In batch experiments, 2% (v/v) oil emulsion could adsorb up to 11,000ppm of TCE or 18,000ppm of PCE without creating a free phase. Results of one-dimensional column flushing studies indicated that contaminants with high aqueous solubility could be efficiently removed by flushing with vegetable oil emulsions. Removal efficiencies exceeded 98% for TCE and PCE with both corn and olive oil emulsions. The results of this study show that flushing with biodegradable oil emulsion can be used for the remediation of groundwater contaminated by DNAPLs.     

Waste green sands as reactive media for groundwater contaminated with trichloroethylene (TCE)

Waste green sands are byproducts of the gray iron foundry industry that consist of sand, binding agents, organic carbon, and residual iron particles. Because of their potential sorptive and reactive properties, tests were conducted to determine the feasibility of using waste green sands as a low cost reactive medium for groundwater treatment. Batch and column tests were conducted to determine the reactivity, sorptive characteristics, and transport parameters for trichloroethylene (TCE) solutions in contact with green sands. Normalized rate constants for TCE degradation in the presence of iron particles extracted from green sands were found to be comparable to those for Peerless iron, a common medium used to treat groundwater. Rate constants and partition coefficients obtained from the batch tests were found to be comparable to those from the column tests. Analytical modeling shows that reactive barriers containing green sand potentially can be used to treat contaminated groundwater containing TCE at typical concentrations observed in the field.     

New procedure for preparation of highly stable and well separated carbon nanotubes in an aqueous modified polyacrylonitrile

Carbon nanotubes (CNTs) due to their nonreactive surface can not effectively disperse in polymeric matrix. Efficient exploitation of CNTs properties to improve material performance is generally related to the degree of dispersion, saturation by the matrix and interfacial adhesion. In order to obtain a suitable dispersion, the CNTs usually need treatment before they can be utilized. In this work, an easy procedure for preparation a stable dispersion of well separated and individual CNTs in an aqueous polymeric solution by using of Gum Arabic (GA) and modified polymer has been described. The applied polymer was a modified water soluble acrylonitrile polymer. The modification was carried out through functionalizing polyacrylonitrile by 2‐aminoethanol. Individual dispersion of the CNTs in the aqueous GA solution after two month can be observed. By incorporating the modified polyacrylonitrile to the solution, the stability of the individual CNTs dispersion several times was increased in such a way that after six month, the CNTs were still kept at their individual positions. According to the suggested mechanism of dispersion, hydrogen bonds between GA/CNTs and the modified polyacrylonitrile chains can be formed that increasing the dispersion ability. The effects of salts and temperature on dispersion ability of GA were also studied.     

Formation and mechanism of nanoscale zerovalent iron supported by phosphoric acid modified biochar for highly efficient removal of Cr(VI)

The effect of phosphoric acid modified biochar on activity of nanoscale zero valent iron particles is not clear until now. In this research, Egeria najas powder driven biochar-supported nanoscale zero valent iron was modified by phosphoric acid (P-BC/nZVI) for highly effective removal of Cr(VI) from wastewater. The TEM and XRD of P-BC/nZVI indicated that nZVI particles were successfully immobilized on the P-BC surface. The batch experiment results show that the Cr(VI) removal efficiency by P-BC/nZVI was higher than that of BC/nZVI, nZVI, P-BC and BC. Moreover, the optimal ratio of nZVI to P-BC lies at 3:1 with fixed P-BC/nZVI dosage of 0.75 g/L, initial Cr(VI) concentration of 20 mg/L, solution pH of 2, and reaction temperature of 333 K. Additionally, Cr(VI) removal capacities by nZVI, BC/nZVI and P-BC/nZVI aged for 15 days in water were 12.9 %, 28.55 % and 99.35 %, respectively. Furthermore, corresponding reaction kinetics fitted well with pseudo-second order model, and adsorption isotherm fitted to Sips isothermal model. The SEM-EDS and XPS confirm that Cr(VI) was participated in the reaction, and about 63.43 % of Cr(VI) was reduced to Cr(III), and the rest was adsorbed on the surface of P-BC/nZVI. The removal mechanism of Cr(VI) by P-BC/nZVI was complex, including adsorption, reduction and surface complex formation.     

Thermal conductivity measurement of oil in Water (O/W) nanoemulsion and oil in H2O/LiBr (O/S) binary nanoemulsion for absorption application

Binary nanoemulsions, oil-droplet suspensions in binary solution (H₂O/LiBr), are developed to enhance the heat and mass transfer performance of absorption refrigeration systems. In this study, a novel four-step method is used to prepare the stable oil-in-binary solution (O/S) emulsion. To stabilize the nanoemulsions in a strong electrolyte, four different polymers are used as a steric stabilizer. The droplet size and the thermal conductivity of binary nanoemulsions are measured by the dynamic light scattering method and the transient hot-wire method, respectively. It is found that the measured thermal conductivities of the oil in water (O/W) nanoemulsion and binary nanoemulsion (O/S) with a stabilizer enhance up to 6.4 and 3.6%, respectively compared with the Maxwell’s model. It is also found that GA (Gum Arabic) gives the highest thermal conductivity enhancement. It is finally confirmed that the initial stable condition of the O/S nanoemulsion can be recovered by the re-dispersion in actual absorption systems.     

In situ reductive dechlorination of chlorinated ethenes in high nitrate groundwater

In situ bioremediation using carbohydrate was evaluated as an in situ treatment alternative for trichloroethene (TCE) and cis-1,2-dichloroethene (cDCE) in groundwater containing high nitrate concentrations. Upon addition of carbohydrate to groundwater, sequential reduction of electron acceptors was observed, where nitrate was reduced early in the pilot test, followed by sulfate and TCE. Reduction of cDCE to vinyl chloride and ethene occurred in conjunction with increased iron and manganese, and increased methane concentrations, approximately 7 months into the evaluation period, following depletion of nitrate and sulfate. TCE, cDCE, and vinyl chloride concentrations decreased from approximately 500 to >10 microg/L within 21 months of operation.     

Silicone emulsion-enhanced recovery of chlorinated solvents: batch and column studies

Batch and column experiments were conducted to investigate the feasibility of flushing with silicone oil emulsion for the removal of chlorinated solvents, including trichloroethylene (TCE), perchloroethylene (PCE) and 1,2-dichlorobenzene (DCB). In the batch experiments, solubilization potentials of emulsion and effects of surfactants as additives were examined. The emulsion prepared with 2% (v/v) silicone oil could solubilize 90.7% of 10,000 ppm TCE, 97.3% of 4000 ppm PCE and 99.7% of 7,800 ppm DCB. Results of one-dimensional column studies indicated that aqueous solubility and sorption of contaminants determined the flushing efficiency. The addition of surfactants below their critical micelle concentration (CMC) did not affect the removal of chlorinated solvents in batch and column experiments. The results of this study show that flushing with oil-based emulsion can be applied to treat the chlorinated solvents.     

Synthesis of granular activated carbon/zero valent iron composites for simultaneous adsorption/dechlorination of trichloroethylene

The coupling adsorption and degradation of trichloroethylene (TCE) through dechlorination using synthetic granular activated carbon and zerovalent iron (GAC-ZVI) composites was studied. The GAC-ZVI composites were prepared from aqueous Fe²⁺ solutions by impregnation with and without the use of a PEG dispersant and then heated at 105 °C or 700 °C under a stream of N₂. Pseudo-first-order rate constant data on the removal of TCE demonstrates that the adsorption kinetics of GAC is similar to those of GAC-ZVI composites. However, the usage of GAC-ZVI composites liberated a greater amount of Cl than when ZVI was used alone. The highest degree of reductive dechlorination of TCE was achieved using a GAC-ZVI700P composite (synthesized using PEG under 700 °C). A modified Langmuir-Hinshelwood rate law was employed to depict the behavior of Cl liberation. As a result, a zero-order Cl liberation reaction was observed and the desorption limited TCE degradation rate constant decreased as the composite dosage was increased. The GAC-ZVI composites can be employed as a reactive GAC that is not subject to the limitations of using GAC and ZVI separately.     

阿拉伯树胶对胶原-羟基磷灰石复合材料性能的影响

为改善胶原-羟基磷灰石复合材料的界面结合性能, 将阿拉伯树胶引入该体系中, 以Ca(NO₃)₂·4H₂O、(NH₄)₂HPO₄、酸溶胶原、阿拉伯树胶为原料, 原位合成了胶原-羟基磷灰石/阿拉伯树胶复合材料. 采用FT-IR, XRD, SEM表征材料的晶相结构、化学组成和微观形貌, 研究了阿拉伯树胶对胶原-羟基磷灰石复合材料结构与性能的影响. 结果表明, 阿拉伯树胶改变了胶原-羟基磷灰石复合材料的界面形态与结构; 随阿拉伯树胶含量的增加, 胶原-羟基磷灰石复合材料的晶粒变小, 结晶度降低; 复合材料的吸水性能和体外酶降解能力都显著下降(P<0.01),其机械性能在一定范围内得到提高. 阿拉伯树胶与胶原或胶原-羟基磷灰石之间可能形成了蛋白-多糖复合物, 从而起到了交联作用.     

Synthesis and characterization of supported polysugar-stabilized palladium nanoparticle catalysts for enhanced hydrodechlorination of trichloroethylene

Palladium (Pd) nanoparticle catalysts were successfully synthesized within an aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping ligand which offers a green alternative to conventional nanoparticle synthesis techniques. The CMC-stabilized Pd nanoparticles were subsequently dispersed within support materials using the incipient wetness impregnation technique for utilization in heterogeneous catalyst systems. The unsupported and supported (both calcined and uncalcined) Pd nanoparticle catalysts were characterized using transmission electron microscopy, energy dispersive x-ray spectrometry, x-ray diffraction, and Brunauer-Emmett-Teller surface area measurement and their catalytic activity toward the hydrodechlorination of trichloroethylene (TCE) in aqueous media was examined using homogeneous and heterogeneous catalyst systems, respectively. The unsupported Pd nanoparticles showed considerable activity toward the degradation of TCE, as demonstrated by the reaction kinetics. Although the supported Pd nanoparticle catalysts had a lower catalytic activity than the unsupported particles that were homogeneously dispersed in the aqueous solutions, the supported catalysts retained sufficient activity toward the degradation of TCE. In addition, the use of the hydrophilic Al(2)O(3) support material induced a mass transfer resistance to TCE that affected the initial hydrodechlorination rate. This paper demonstrates that supported Pd catalysts can be applied to the heterogeneous catalytic hydrodechlorination of TCE.     

聚乙烯醇/纳米零价铁复合膜的制备及性能

为了克服脱氧剂小袋包装与食品混装带来的工艺不足和安全问题,采用水热法制备了纳米零价铁（nZVI）,并将其与聚乙烯醇（PVA）进行溶液共混,制备了结构及阻氧性能更为优异的聚乙烯醇/纳米零价铁复合膜。利用傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、热重分析（TG）、差示扫描量热法（DSC）等对膜的结构和性能进行表征。结果表明：复合膜中PVA和nZVI实现了良好复合;加入nZVI后,复合膜的玻璃化温度（Tg）升高、热稳定性降低;随着nZVI含量的增加,复合膜的力学性能先增强后减弱,在nZVI质量分数为2%时,复合膜的抗拉强度和断后伸长率达到最大;复合膜的氧气透过系数随着nZVI含量的增加呈现先减小后增大的趋势,在nVZI质量分数为3%时,复合膜的氧气透过系数最小。在复合膜中,nZVI和PVA的羟基之间能形成一种强的相互作用,改善了复合材料的结构和性能,但nZVI及其表面部分氧化的变价铁催化加速了PVA的热降解。     

Persulfate regeneration of trichloroethylene spent activated carbon

The objective of this study was to demonstrate the regeneration of trichloroethylene (TCE) spent activated carbon using persulfate oxidation and iron activated persulfate (IAP) oxidation. Both processes resulted in decreases in the adsorbability of regenerated activated carbons. IAP was shown to rapidly degrade the aqueous TCE and causes a significant mineralization of the TCE. The release of chloride ions provided evidence of this. Persulfate oxidation mainly resulted in desorption of TCE from the activated carbon and only partial mineralization of the TCE through a carbon activated persulfate reaction mechanism. Concerning destruction of the TCE, in the regeneration test using persulfate, 30% of the original TCE was present in the solution and 9% remained on the activated carbon after the first regeneration cycle. In contrast, in the test that used IAP, it was observed that no TCE was present in the solution and only approximately 5% of the original TCE remained on the activated carbon after the first regeneration. Following the regeneration cycles, elemental analysis was carried out on the samples. BET surface area and EDS analysis showed some effects on the physico-chemical properties of the activated carbon such as a slight decrease in the surface area and the presence of iron precipitates on the carbon.     

水性聚氨酯制备工艺对乳液黏度和胶粒尺寸的影响

以异佛尔酮二异氰酸酯(IPDI)、聚四氢呋喃醚二醇(PTMG)、聚己内酯二醇(PCLD)、2,2-二羟甲基丙酸(DMPA)以及1,4-丁二醇等为主要原料,经自乳化法分别制备出IPDI型水性聚氨酯PTMG-PU、PCLD-PU。红外光谱(FT-IR)测试证实了二者结构上的差别。通过研究合成制备工艺过程中多种因素对乳液黏度及胶粒粒径的影响,发现当控制中和度为90%~100%、n(NCO)/n(OH)比为1.13~1.20、DMPA质量分数为2.5%~9.0%以及乳化时叶片转速为1500 r/min~2000 r/min、加水速度为100 mL/min~200 mL/min(体系总体积200 mL)时,可制得乳液黏度和胶粒粒径适中且固含量可达40%以上稳定的IPDI型聚氨酯乳液。     

Chemical oxidation of chlorinated non-aqueous phase liquid by hydrogen peroxide in natural sand systems

This study explored the Fenton-like oxidation of trichloroethylene (TCE) existing as dense non-aqueous phase liquid (DNAPL) in natural silica sand (iron=0.04 g/kg) and the sand from an aquifer (iron=2.01 g/kg). Glass bead containing no iron mineral was used as the control. Batch oxidation experiments were conducted to assess interactions between oxidant and TCE DNAPL. Column experiments were performed to evaluate dynamics of TCE and H(2)O(2) during oxidation. The pH was not altered. In the batch system, a single application of 3% H(2)O(2) to the aquifer sand oxidized 40% of the added TCE DNAPL in 1 h, which was four times of that by dissolution with the gas purge procedure. This demonstrated the ability of mineral-catalyzed Fenton-like reaction to directly oxidize TCE in non-aqueous liquid. In the column experiments, after passing 7 pore volumes (PVs) of 1.5 and 3% H(2)O(2) solution, the residual TCE in aquifer sand column was 12.0 and 2.6% of the initial added, respectively. On the other hand, 28.4% of the added TCE still remained in the silica sand column by 7 PVs of 3% H(2)O(2). The distribution of TCE in column and effluent indicated the occurring of direct oxidation of TCE DNAPL and the increased solubilization, which probably due to size reduction of DNAPL droplets, followed by water-phased TCE oxidation.     

Chemical stability of teniposide in aqueous and parenteral lipid emulsions

The purpose of this study was to investigate the degradation kinetics of teniposide in lipid emulsion and aqueous solution. The chemical stability of teniposide in lipid emulsion and aqueous solution at various pH values and temperatures was monitored by high-performance liquid chromatography. In addition, the viscosities of emulsion at different temperatures were investigated. The degradation of teniposide both in emulsion and in aqueous solution was shown to follow pseudo-first-order degradation kinetics. The t (1/2) values of teniposide lipid emulsion (TLE) and the aqueous solution were 80 and 2.6 days at 10 degrees C, respectively. Under the most stable pH range of 6.0-6.5, stability of teniposide in the emulsion increased more than 30-fold compared with that in aqueous solution. Furthermore, there was a difference between the shelf life of TLE actually measured (29 days) at 10 degrees C and the one deduced (15 days) from the degradation data of high temperatures by Arrhenius equation. It could be hypothesized that the difference was due to a slower diffusion of teniposide from oil phase to aqueous phase at the lower temperatures, which would be a speed-limited process in the degradation of TLE. The results of viscosity test confirmed the presumption.     

Effects of pH on dechlorination of trichloroethylene by zero-valent iron

The surface normalized reaction rate constants (k(sa)) of trichloroethylene (TCE) and zero-valent iron (ZVI) were quantified in batch reactors at pH values between 1.7 and 10. The k(sa) of TCE linearly decreased from 0.044 to 0.009l/hm(2) between pH 3.8 and 8.0, whereas the k(sa) at pH 1.7 was more than an order higher than that at pH 3.8. The degradation of TCE was not observed at pH values of 9 and 10. The k(sa) of iron corrosion linearly decreased from 0.092 to 0.018l/hm(2) between pH 4.9 and 9.8, whereas it is significantly higher at pH 1.7 and 3.8. The k(sa) of TCE was 30-300 times higher than those reported in literature. The difference can be attributed to the pH effects and precipitation of iron hydroxide. The k(sa) of TCE degradation and iron corrosion at a head space of 6 and 10ml were about twice of those at zero head space. The effect was attributed to the formation of hydrogen bubbles on ZVI, which hindered the transport the TCE between the solution and reaction sites on ZVI. The optimal TCE degradation rate was achieved at a pH of 4.9. This suggests that lowering solution pH might not expedite the degradation rate of TCE by ZVI as it also caused faster disappearance of ZVI, and hence decreased the ZVI surface concentration.     

Chemical Stability of Teniposide in Aqueous and Parenteral Lipid Emulsions

The purpose of this study was to investigate the degradation kinetics of teniposide in lipid emulsion and aqueous solution. The chemical stability of teniposide in lipid emulsion and aqueous solution at various pH values and temperatures was monitored by high-performance liquid chromatography. In addition, the viscosities of emulsion at different temperatures were investigated. The degradation of teniposide both in emulsion and in aqueous solution was shown to follow pseudo-first-order degradation kinetics. The t_1/2 values of teniposide lipid emulsion (TLE) and the aqueous solution were 80 and 2.6 days at 10°C, respectively. Under the most stable pH range of 6.0–6.5, stability of teniposide in the emulsion increased more than 30-fold compared with that in aqueous solution. Furthermore, there was a difference between the shelf life of TLE actually measured (29 days) at 10°C and the one deduced (15 days) from the degradation data of high temperatures by Arrhenius equation. It could be hypothesized that the difference was due to a slower diffusion of teniposide from oil phase to aqueous phase at the lower temperatures, which would be a speed-limited process in the degradation of TLE. The results of viscosity test confirmed the presumption.     

The mechanism and applicability of in situ oxidation of trichloroethylene with Fenton's reagent

Fenton's reagent is the result of reaction between hydrogen peroxide (H(2)O(2)) and ferrous iron (Fe(2+)), producing the hydroxyl radical (-*OH). The hydroxyl radical is a strong oxidant capable of oxidizing various organic compounds. The mechanism of oxidizing trichloroethylene (TCE) in groundwater and soil slurries with Fenton's reagent and the feasibility of injecting Fenton's reagent into a sandy aquifer were examined with bench-scale soil column and batch experiment studies. Under batch experimental conditions and low pH values ( approximately 3), Fenton's reagent was able to oxidize 93-100% (by weight) of dissolved TCE in groundwater and 98-102% (by weight) of TCE in soil slurries. Hydrogen peroxide decomposed rapidly in the test soil medium in both batch and column experiments. Due to competition between H(2)O(2) and TCE for hydroxyl radicals in the aqueous solutions and soil slurries, the presence of TCE significantly decreased the degradation rate of H(2)O(2) and was preferentially degraded by hydroxyl radicals. In the batch experiments, Fenton's reagent was able to completely dechlorinate the aqueous-phase TCE with and without the presence of soil and no VOC intermediates or by-products were found in the oxidation process. In the soil column experiments, it was found that application of high concentrations of H(2)O(2) with addition of no Fe(2+) generated large quantities of gas in a short period of time, sparging about 70% of the dissolved TCE into the gaseous phase with little or no detectable oxidation taking place. Fenton's reagent completely oxidized the dissolved phase TCE in the soil column experiment when TCE and Fenton's regent were simultaneously fed into the column. The results of this study showed that the feasibility of injecting Fenton's reagent or H(2)O(2) as a Fenton-type oxidant into the subsurface is highly dependent on the soil oxidant demand (SOD), presence of sufficient quantities of ferrous iron in the application area, and the proximity of the injection area to the zone of high aqueous concentration of the target contaminant. Also, it was found that in situ application of H(2)O(2) could have a gas-sparging effect on the dissolved VOC in groundwater, requiring careful attention to the remedial system design.     

Generation of High‐Order All‐Aqueous Emulsion Drops by Osmosis‐Driven Phase Separation

Droplets containing ternary mixtures can spontaneously phase‐separate into high‐order structures upon a change in composition, which provides an alternative strategy to form multiphase droplets. However, existing strategies always involve nonaqueous solvents that limit the potential applications of the resulting multiple droplets, such as encapsulation of biomolecules. Here, a robust approach to achieve high‐order emulsion drops with an all‐aqueous nature from two aqueous phases by osmosis‐induced phase separation on a microfluidic platform is presented. This technique is enabled by the existence of an interface of the two aqueous phases and phase separation caused by an osmolality difference between the two phases. The complexity of emulsion drops induced by phase separation could be controlled by varying the initial concentration of solutes and is systematically illustrated in a state diagram. In particular, this technique is utilized to successfully achieve high‐order all‐aqueous droplets in a different aqueous two‐phase system. The proposed method is simple since it only requires two initial aqueous solutions for generating multilayered, organic‐solvent‐free all‐aqueous emulsion drops, and thus these multiphase emulsion drops can be further tailored to serve as highly biocompatible material templates.