Kaimin Shih

Adsorption of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on alumina: Influence of solution pH and cations

The persistent nature of perfluorochemicals (PFCs) has attracted global concern in recent years. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are the most commonly found PFC compounds, and thus their fate and transport play key roles in PFC distribution in the natural environment. As most solid phases in natural water contain alumina, an investigation of PFOS and PFOA adsorption behavior on alumina should prove useful in evaluating the environmental impact of this type of persistent pollutant. Systematic experiments were carried out in this study to investigate the adsorption behavior of PFOS and PFOA onto alumina. The results of adsorption kinetics on alumina show that it takes 48 h to reach equilibrium. The adsorption isotherms reveal maximum adsorption capacities of 0.252 μg/m(2) for PFOS and 0.157 μg/m(2) for PFOA at pH = 4.3, with the difference primarily due to their different functional groups. An increase in pH leads to a decrease in PFOS and PFOA adsorption on alumina, which may be attributed to the reduction in electrostatic interaction. The adsorption of both PFOS and PFOA decreases with an increase in ionic strength for all four types of cations (Na(+), K(+), Mg(2+), and Ca(2+)), due to the compression of the electrical double layer. Furthermore, the results also indicate that both Ca(2+) and Mg(2+) can form bridges with PFOA anions in solution, whereas only PFOS can be bridged by Ca(2+) due to the higher covalent nature of magnesium.

Oxidative degradation of propachlor by ferrous and copper ion activated persulfate

The process of in situ chemical oxidation (ISCO) by persulfate (S(2)O(8)(2-)) can be accelerated by metal ion activation, which more effectively degrades subsurface pollutants by enhancing sulfate radical (SO(4)(-)) generation. This study compared the results of propachlor degradation by Cu(2+) and Fe(2+) activated persulfate and revealed differing degradation kinetics and mechanisms between the two types of activation system. The activation of persulfate by Fe(2+) ions generally resulted in rapid degradation in the early stage, but was accompanied by a dramatic decrease in efficiency due to the rapid depletion of Fe(2+) by the sulfate radicals generated. In contrast, the Cu(2+) activated persulfate had a longer lasting degradation effect and a proportionally greater degradation enhancement at elevated Cu(2+) concentrations. An optimal Fe(2+) concentration should be sought to activate the persulfate, as a high Fe(2+) concentration of 2.5mM or above, as was used in this study, may inhibit propachlor degradation due to the competitive consumption of sulfate radicals by the excess Fe(2+) ions. Higher temperatures (55°C compared with 30°C) resulted in enhanced metal activation, particularly with the Cu(2+) activated system. Furthermore, acidic conditions were found to be more favorable for propachlor degradation by metal activated persulfate. The ecotoxicity of degraded propachlor samples, which was indicated by average well color development (AWCD) for its microbial community activity, was confirmed to be decreased during the degradation processes with these two ions activated persulfate.

Sulfate Radical-Mediated Degradation of Sulfadiazine by CuFeO2 Rhombohedral Crystal-Catalyzed Peroxymonosulfate: Synergistic Effects and Mechanisms

Copper-iron bimetallic oxides have shown great potential for powerful radical production by activating peroxides. In this work, CuFeO2 rhombohedral crystals (RCs) were synthesized and used as heterogeneous catalysts for peroxymonosulfate (PMS) activation under various conditions. Sulfadiazine, a widely used veterinary sulfonamide, was used as a target pollutant to evaluate the efficiency of this combination. The results showed that of all the catalysts tested, the CuFeO2 RCs had the greatest reactivity. Under conditions of 0.1 g L(-1) CuFeO2 RCs and 33.0 μM PMS, the nearly complete degradation of sulfadiazine occurred within 24 min. A synergistic catalytic effect was found between solid Cu(I) and Fe(III), probably due to the accelerated reduction of Fe(III). The two activation stages that produced different radicals (hydroxyl radicals followed by sulfate radicals) existed when solid Cu(I) was used as the catalyst. The CuFeO2 RCs had a higher PMS utilization efficiency than CuFe2O4, probably because the Cu(I)-promoted reduction of solid Fe(III). A total of 10 products were identified, and their evolution was explored. On the basis of the evidence of oxidative product formation, we proposed four possible pathways of sulfadiazine degradation.

Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong.

The study reported in this paper examined the concentrations of nineteen perfluorochemicals (PFCs), including perfluoroalkyl sulfonates, carboxylates, and sulfonamides in samples collected from Hong Kong wastewater treatment plants (WWTPs) and sediments. The study was the first to use an external isolator column to assist in the quantification of PFCs in environmental samples without having to make internal modifications to a liquid chromatography system. Perfluorooctanesulfonate was found to be the dominant PFC pollutant in Hong Kong, and the WWTP sludge was the major sink of PFCs discharged from the urban areas. Compared to discharge influenced by industrial activities, much less perfluorooctanoate was found in waste streams. The significantly lower level of perfluorodecanesulfonate in WWTP sludge reflects the important influence of consumer products on PFC distribution. The dominance of even-chain length perfluoroalkyl carboxylates in all of the WWTP sludge samples investigated further suggests the strong aerobic degradation of fluorotelomer alcohols in WWTPs.

Hexavalent chromium removal from near natural water by copper-iron bimetallic particles

The reduction of hexavalent chromium (Cr(VI)) by zero-valent iron (ZVI) is self-inhibiting in near natural groundwater because insulating Fe(III)-Cr(III) (oxy)hydroxide film forms on the ZVI surface during the reaction. This study tries to overcome this deficiency by coating the surface of ZVI with copper to form copper-iron bimetallic particles. The Cr(VI) removal rate by ZVI rose significantly after the copper coating was applied. The copper loading needed for enhancing Cr(VI) removal was much higher than that needed for enhancing removal of chlorinated organic compounds or other oxidative contaminants, because of the higher oxidation potential of Cr(VI). The results of X-ray photoelectron spectroscopy (XPS) indicate that coating copper onto the surface of ZVI can not only increase the deepness of the oxidation film but also increase the oxidation state of iron in the film. This phenomenon means higher Cr(VI) removal capacity per unit weight of ZVI.

SCR Atmosphere Induced Reduction of Oxidized Mercury over CuO–CeO2/TiO2 Catalyst

CuO-CeO2/TiO2 (CuCeTi) catalyst synthesized by a sol-gel method was employed to investigate mercury conversion under a selective catalytic reduction (SCR) atmosphere (NO, NH3 plus O2). Neither NO nor NH3 individually exhibited an inhibitive effect on elemental mercury (Hg(0)) conversion in the presence of O2. However, Hg(0) conversion over the CuCeTi catalyst was greatly inhibited under SCR atmosphere. Systematic experiments were designed to investigate the inconsistency and explore the in-depth mechanisms. The results show that the copresence of NO and NH3 induced reduction of oxidized mercury (Hg(2+), HgO in this study), which offset the effect of catalytic Hg(0) oxidation, and hence resulted in deactivation of Hg(0) conversion. High NO and NH3 concentrations with a NO/NH3 ratio of 1.0 facilitated Hg(2+) reduction and therefore lowered Hg(0) conversion. Hg(2+) reduction over the CuCeTi catalyst was proposed to follow two possible mechanisms: (1) direct reaction, in which NO and NH3 react directly with HgO to form N2 and Hg(0); (2) indirect reaction, in which the SCR reaction consumed active surface oxygen on the CuCeTi catalyst, and reduced species on the CuCeTi catalyst surface such as Cu2O and Ce2O3 robbed oxygen from adjacent HgO. Different from the conventionally considered mechanisms, that is, competitive adsorption responsible for deactivation of Hg(0) conversion, this study reveals that oxidized mercury can transform into Hg(0) under SCR atmosphere. Such knowledge is of fundamental importance in developing efficient and economical mercury control technologies for coal-fired power plants.

Adsorption behavior of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) on boehmite

Understanding the interaction of perfluorochemicals, persistent pollutants with known human health effects, with mineral compounds in surface water and groundwater environments is essential to determining their fate and transport. Kinetic experiments showed that adsorption equilibrium can be achieved within 48 h and the boehmite (AlOOH) surface is receptive to perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorption. The adsorption isotherms estimated the maximum adsorption capacities of PFOS and PFOA on boehmite as 0.877 μg m(-2) and 0.633 μg m(-2), respectively. Compared to the adsorption capacity on γ-alumina, the abundant hydroxyl groups on boehmite surfaces resulted in the 2-3 times higher adsorption of PFOS and PFOA. Increasing solution pH led to a moderate decrease in PFOS and PFOA adsorption, owing to an increase in ligand exchange reactions and the decrease of electrostatic interactions. The presence of NaCl and CaCl(2) in solution demonstrated negative effects for PFOS and PFOA adsorption on boehmite surfaces, with potential mechanisms being electrical double layer compression, competitive adsorption of chloride, and the Ca(2+) bridging effect between perfluorochemicals.

Accurate construction of a hierarchical nickel–cobalt oxide multishell yolk–shell structure with large and ultrafast lithium storage capability

Novel hierarchical nickel–cobalt oxide microspheres with a multishell yolk–shell structure have been accurately synthesized via a facile and scalable method. The multishell yolk–shell powder shows a significantly improved electrochemical performance in terms of high reversible capacity, good rate capability and excellent cycling performance.

CO(2)-driven ocean acidification alters and weakens integrity of the calcareous tubes produced by the serpulid tubeworm, Hydroides elegans.

As a consequence of anthropogenic CO2-driven ocean acidification (OA), coastal waters are becoming increasingly challenging for calcifiers due to reductions in saturation states of calcium carbonate (CaCO3) minerals. The response of calcification rate is one of the most frequently investigated symptoms of OA. However, OA may also result in poor quality calcareous products through impaired calcification processes despite there being no observed change in calcification rate. The mineralogy and ultrastructure of the calcareous products under OA conditions may be altered, resulting in changes to the mechanical properties of calcified structures. Here, the warm water biofouling tubeworm, Hydroides elegans, was reared from larva to early juvenile stage at the aragonite saturation state (ΩA) for the current pCO2 level (ambient) and those predicted for the years 2050, 2100 and 2300. Composition, ultrastructure and mechanical strength of the calcareous tubes produced by those early juvenile tubeworms were examined using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and nanoindentation. Juvenile tubes were composed primarily of the highly soluble CaCO3 mineral form, aragonite. Tubes produced in seawater with aragonite saturation states near or below one had significantly higher proportions of the crystalline precursor, amorphous calcium carbonate (ACC) and the calcite/aragonite ratio dramatically increased. These alterations in tube mineralogy resulted in a holistic deterioration of the tube hardness and elasticity. Thus, in conditions where ΩA is near or below one, the aragonite-producing juvenile tubeworms may no longer be able to maintain the integrity of their calcification products, and may result in reduced survivorship due to the weakened tube protection.

Copper Stabilization via Spinel Formation during the Sintering of Simulated Copper-Laden Sludge with Aluminum-Rich Ceramic Precursors

The feasibility of incorporating copper-laden sludge into low-cost ceramic products, such as construction ceramics, was investigated by sintering simulated copper-laden sludge with four aluminum-rich ceramic precursors. The results indicated that all of these precursors (γ-Al(2)O(3), corundum, kaolinite, mullite) could crystallochemically stabilize the hazardous copper in the more durable copper aluminate spinel (CuAl(2)O(4)) structure. To simulate the process of copper transformation into a spinel structure, CuO was mixed with the four aluminum-rich precursors, and fired at 650-1150 °C for 3 h. The products were examined using powder X-ray diffraction (XRD) and scanning electron microscopic techniques. The efficiency of copper transformation among crystalline phases was quantitatively determined through Rietveld refinement analysis of the XRD data. The sintering experiment revealed that the optimal sintering temperature for CuAl(2)O(4) formation was around 1000 °C and that the efficiency of copper incorporation into the crystalline CuAl(2)O(4) structure after 3 h of sintering ranged from 40 to 95%, depending on the type of aluminum precursor used. Prolonged leaching tests were carried out by using acetic acid with an initial pH value of 2.9 to leach CuO and CuAl(2)O(4) samples for 22 d. The sample leachability analysis revealed that the CuAl(2)O(4) spinel structure was more superior to stabilize copper, and suggested a promising and reliable technique for incorporating copper-laden sludge or its incineration ash into usable ceramic products. Such results also demonstrated the potential of a waste-to-resource strategy by using waste materials as part of the raw materials with the attainable temperature range used in the production of ceramics.