Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag)

The reactions of group 14 tetrachlorides MCl4 (M=Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures lead to the unique complex ions [M(S2O7)3]2−, which show the central M atoms in coordination with three chelating S2O72− groups. The mean distances M[BOND]O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M[BOND]O bonds. For the silicon compound (NH4)2[Si(S2O7)3], 29Si solid-state NMR measurements have been performed, with the results showing a signal at −215.5 ppm for (NH4)2[Si(S2O7)3], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO6] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S2O7)3]2− ions is achieved by monovalent A+ counter ions (A=NH4, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A+ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S2O7)3]2− ions remain essentially unaffected with the different A+ ions. Furthermore, the nature of the A+ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements.

Optimization of laccase production from Trametes versicolor by solid fermentation

The regulation of culture conditions, especially the optimization of substrate constituents, is crucial for laccase production by solid fermentation. To develop an inexpensive optimized substrate formulation to produce high-activity laccase, a uniform design formulation experiment was devised. The solid fermentation of Trametes versicolor was performed with natural aeration, natural substrate pH (about 6.5), environmental humidity of 60% and two different temperature stages (at 37 °C for 3 days, and then at 30 °C for the next 17 days). From the experiment, a regression equation for laccase activity, in the form of a second-degree polynomial model, was constructed using multivariate regression analysis and solved with unconstrained optimization programming. The optimized substrate formulation for laccase production was then calculated. Tween 80 was found to have a negative effect on laccase production in solid fermentation; the optimized solid substrate formulation was 10.8% glucose, 27.7% wheat bran, 9.0% (NH4)2SO4, and 52.5% water. In a scaled-up verification of solid fermentation at a 10 kg scale, laccase activity from T. versicolor in the optimized substrate formulation reached 110.9 IU/g of dry mass.

Modelling based design of a pilot-scale membrane bioreactor for combined nutrient removal from domestic wastewater

A three stage-treatment of domestic wastewater including anaerobic, anoxic and aerobic phases is employed in this study while a clarifier unit is replaced with a submerged membrane in the aerobic unit. The effects of operational parameters on the performance of a pilot scale submerged membrane bioreactor (SMBR) namely hydraulic retention time (HRT), ratio of return activated sludge (QRS), ratio of internal recycle (QIR), solid retention time (SRT) and dissolved oxygen (DO) are evaluated by simulations, using a hybrid model composed of TUDP model, oxygen transfer model, biofouling model due to extra-cellular polymeric substances (EPS) and turbulent shear model. The results showed that anaerobic HRT of 3 hours, anoxic HRT of 6 hours, QRS of 20% and QIR of 300 % are satisfactory in obtaining a high removal efficiency (>90%) of COD, NH4-N, P04-P as well as a less sludge production. An increase of sludge production causes an increase in EPS, which fouls the membrane surface and increase the cleaning cycle of membrane. Operation of 5MBR system at 2 mg/I of DO and 30 days of SRT can extend the membrane cleaning cycle dramatically. The membrane cleaning cycle however is strongly dependent on the initial and terminal specific fluxes and displays inverse power relationships to those fluxes.

Evaluating the performance of different media in a horizontal subsurface flow constructed wetland

The treatment efficiency of a wetland system requires a balance between pollutant loading rate and hydraulic retention time (HRT), hydraulic loading rate (HLR) and the suitable substrate to be used. The aim of this study was to investigate the treatment efficiency of horizontal subsurface flow constructed wetland planted with phragmites australis and scirpus maritimus containing three different substrates to treat agricultural wastewater under short term operation. Alum sludge and zeolite were used as substrates and gravel was used as a control for a laboratory-scale horizontal flow constructed wetland (CW) units that were made of high-density Polyethylene. The units were operated under 2, 3 and 4 days of HRTs and at different HLR for each substrate. Each beds received 0.012 m3/d to 0.08 m3/d of synthetic wastewater corresponding to a HLR of 0.035 to 0.243 m/d and a COD loading rate of 0.0148 kg COD (m2.d)-1 to 0.026 kg COD (m2.d)-1. The relationships between the substrate, retention time and removal efficiency, especially of organic matter and nutrient removal were investigated. All units showed relatively stable removal for COD during the entire operational period. The COD removal for all units and HRT were in ranged from 67% to 93%. The zeolite unit achieved significantly higher removal of TN, NH4-N and TSS compared to alum sludge and gravel unit at all HRT. The unit with zeolite was highly effective in removing TN (54 to 96%), NH4-N (50 to 99%) and TSS (91 to 96%) respectively, at 2, 3 and 4 days of HRT. Meanwhile, alum sludge was highly effective in removing phosphate. The removal of phosphate from alum sludge unit was ranged from 94 to 97% for all HRT. Compared to gravel CW unit, zeolite and alum sludge CW were proved to be tolerant to high organic loadings and nutrients, suggesting these substrates as viable options for biological treatment of agricultural wastewater.

Preparation and electrospinning of acidified-oxidized potato starch

This paper investigates the preparation and electrospinning of acidified-oxidized potato starch. In this article, acidified-oxidized potato starch was prepared by adding ammonium persulfate as an oxidizing agent and hydrochloric acid as a catalyst. The effect of reaction time, temperature, the concentration of hydrochloric acid and the content of ammonium persulfate on the viscosity and content of carboxyl were discussed. The optimum reaction conditions were as follows: 1.5 hours ,50℃, 0.5mol/l HCl, 2.5% (NH4)2S2O8. And then, the acidified-oxidized potato starch prepared at the optimum condition was dissolved in dimethyl sulfoxide (DMSO) to be electrospinned by contrast to native starch. Electrospinning of 5wt%-21wt% of modified starch in DMSO produced beads, beaded fibers, and smooth fibers, depending on the concentration range. Smooth fibers were observed until the concentration reached 19wt%, while native starch was 5wt%.

Denitrification measurements of sediments using cores and chambers

Denitrification is commonly measured using in situ benthic chambers or laboratory incubations of sediment cores. These techniques are similar in principle but differ considerably in cost and practicality. Despite widespread use of both techniques, it is uncertain whether they give comparable results. We compared cores and chambers for measuring fluxes (dissolved oxygen [DO], N 2, NH4+, NO3- and NO 2-) and denitrification efficiency at 2 sites in Port Phillip Bay, Victoria, Australia. Overall, denitrification efficiency was not significantly different between cores and chambers, but fluxes of DO, NO 3- and NO2- differed. Chambers demonstrated higher levels of oxygen consumption and net fluxes of NO 3- and NO2- out of the sediment, suggesting that denitrification and nitrification were closely coupled. In contrast, there was a greater relative importance for uncoupled denitrification in cores as indicated by reduced oxygen consumption and net fluxes of NO 3- into the sediment. We conclude that cores and chambers give different flux results and therefore are not comparable techniques for measuring denitrification. To ascertain the cause of this, we tested the hypothesis that cores failed to adequately incorporate the impacts of macrofauna on fluxes, due to the small size of cores relative to chambers. However, densities of macrofauna were not significantly different in cores and chambers. We then hypothesised that disturbance during core collection, transportation, and handling may account for differences, but cores deployed in situ and in the laboratory gave similar results. We suggest that compression of sediment during insertion of core cylinders into the sediment may account for differences between core and chamber fluxes.

Characterization of the extracellular polymeric substances and microbial community of aerobic granulation sludge exposed to cefalexin

This study characterizes the extracellular polymeric substances and bacterial community composition of aerobic granules exposed to cefalexin (CLX). The presence of CLX potentially decreases granular stabilities, resulting in a lowered granule diameter. Chemical oxygen demand and NH4+-N removal efficiencies were slightly decreased and the denitrification process was inhibited with CLX addition. Extracellular polymeric substance contents were significantly increased in aerobic granules exposed to CLX. The shifts of fluorescence intensities and peak locations in 3D-EEM fluorescence spectra indicated changes of EPS components. High-throughput sequencing analysis showed aerobic granules with CLX addition in synthetic wastewater had superior diversity of microbial species, and this was the reason that the level and components of EPS changed. The species richness for bacteria was increased from 341 to 352, which was revealed by Chao1. The Shannon index of diversity rose slightly from 3.59 to 3.73 with CLX addition. The abundance of Proteobacteria significantly decreased, while the abundance of Bacteroidetes and Chloroflexi underwent a highly significant increase in aerobic granules exposed to CLX.