Photocatalytic Degradation of 4,4′-Isopropylidenebis(2,6-dibromophenol) on Magnetite Catalysts vs. Ozonolysis Method: Process Efficiency and Toxicity Assessment of Disinfection By-Products

Flame retardants have attracted growing environmental concern. Recently, an increasing number of studies have been conducted worldwide to investigate flame-retardant sources, environmental distribution, living organisms’ exposure, and toxicity. The presented studies include the degradation of 4,4′-isopropylidenebis(2,6-dibromophenol) (TBBPA) by ozonolysis and photocatalysis. In the photocatalytic process, nano- and micro-magnetite (n-Fe₃O₄ and μ-Fe₃O₄) are used as a catalyst. Monitoring of TBBPA decay in the photocatalysis and ozonolysis showed photocatalysis to be more effective. Significant removal of TBBPA was achieved within 10 min in photocatalysis (ca. 90%), while for ozonation, a comparable effect was observed within 70 min. To determine the best method of TBBPA degradation concentration on COD and TOC, the removals were examined. The highest oxidation state was obtained for photocatalysis on μ-Fe₃O₄, whereas for n-Fe₃O₄ and ozonolysis, the COD/TOC ratio was lower. Acute toxicity results show noticeable differences in the toxicity of TBBPA and its degradation products to Artemia franciscana and Thamnocephalus platyurus. The EC₅₀ values indicate that TBBPA degradation products were toxic to harmful, whereas the TBPPA and post-reaction mixtures were toxic to the invertebrate species tested. The best efficiency in the removal and degradation of TBBPA was in the photocatalysis process on μ-Fe₃O₄ (reaction system 1). The examined crustaceans can be used as a sensitive test for acute toxicity evaluation.     

Lithium conducting ionic liquids based on lithium borate salts

The simple reaction of trialkoxyborates with butyllithium resulted in the obtaining of new lithium borate salts: Li{[CH₃(OCH₂CH₂)_nO]₃BC₄H₉}, containing oxyethylene substituents (EO) of n = 1, 2, 3 and 7. Salts of n ≥ 2 show properties of room temperature ionic liquid (RTIL) of low glass transition temperature, T_g of the order from −70 to −80 °C. The ionic conductivity of the salts depends on the number of EO units, the highest conductivity is shown by the salt with n = 3; in bulk its ambient temperature conductivity is 2 × 10⁻⁵ S cm⁻¹ and in solution in cyclic propylene sulfite or EC/PC mixture, conductivity increases by an order of magnitude. Solid polymer electrolytes with borate salts over a wide concentration range, from 10 to 90 mol.% were obtained and characterized. Three types of polymeric matrices: poly(ethylene oxide) (PEO), poly(trimethylene carbonate) (PTMC) and two copolymers of acrylonitrile and butyl acrylate p(AN-BuA) were used in them as polymer matrices. It has been found that for systems of low salt concentration (10 mol.%) the best conducting properties were shown by solid polymer electrolytes with PEO, whereas for systems of high salt concentration, of the polymer-in-salt type, good results were achieved for PTMC as polymer matrix.     

Phase segregation phenomena in poly(ethylene oxide):LiN(CF3SO2)2 electrolyte studied by local Raman spectroscopy

Polymer electrolyte composed of poly(ethylene oxide) PEO with dissolved lithium bis (trifluoromethanesulfonyl)imide salt LiTFSI of molar ratio EO:Li 16:1 was prepared by casting from solution. The electrolyte has been investigated by microscope observation simultaneous with impedance spectroscopy, differential scanning calorimetry and local Raman spectroscopy. The presented results provide direct support for model of phase segregation which takes place in PEO:LiTFSI electrolytes. According to the model proposed in our earlier publications, crystallization of PEO or PEO:salt complexes causes rejection or drainage of salt from specific regions of electrolyte. Thus, a resulting semicrystalline electrolyte is divided into large domains of different composition. In the case of investigated PEO:LiTFSI 16:1 electrolyte, the results obtained by local Raman spectroscopy indicated, that in areas situated within large circular spherulites the concentration of salt is lower than in molten (amorphous) electrolyte. In areas situated outside of these spherulites, the concentration of salt was considerably higher than for amorphous electrolyte. This is in good agreement with the assumption that the circular spherulites have the crystalline skeleton of pure PEO, whereas the PEO₆:LiTFSI crystalline phase dominates in the areas between their borders.     

HER-2/Neu expression as a progression marker in pancreatic intraepithelial neoplasia

Dietary restriction is the only intervention shown to increase maximal life span, and to retard the rate of aging in rodents. As part of a long-term randomized trial of the effects of a 20-30% dietary restriction (DR) on adult rhesus macaques, female (N = 30) and male (N = 16) monkeys were assessed at baseline and 6, 12 and 18 months, following randomization to control (C) or dietary restricted (R) groups, for body composition by dual-energy x-ray absorptiometry. At baseline, there were no significant differences between C and R groups in any body composition parameters measured. Males had significantly (p < 0.05) greater values at baseline than females for body weight (BW), body mass index (BMI), total body lean tissue mass (LTM), appendicular skeletal muscle mass (ASM), and total body bone mineral content (BMC). When analyzed longitudinally through 18 months of DR, C females had significantly increased BW, total body fat tissue mass (FTM), total body percent fat tissue mass (%FTM), LTM, ASM, BMC and abdominal fat tissue mass (AbFTM) relative to R animals. Male C animals had significantly increased BW, FTM, %FTM, BMC and AbFTM relative to R males. The primary effect of DR on body composition in these animals was on FTM.     

Application of an ozonation–adsorption–ultrafiltration system for surface water treatment

Investigations are presented on the effect of the preliminary ozonation on ultrafiltration (UF) and powdered activated carbon (PAC) /UF process performance, especially on permeate flux decline and the effectiveness of model organics removal. Flat membranes from regenerated cellulose were used. A model solution was prepared as a mixture of humic acids and phenol. PAC dosage was equal to 100 mg/l⁻¹. The ozone dosages were in the range of 1–3 mg O₃ l⁻¹ (0.2–0.6 mg O₃/mg TOC). It was found that the most advantageous configuration was preliminary ozonation with an ozone dosage of 0.4 mgO₃/mg TOC–UF. The permeate flux reached a value equal to the pure water flux value. Moreover, a very high effectiveness of model organics removal was obtained: TOC was reduced by about 96% and UV₂₅₄ absorbance was removed completely. When PAC was added to the feed containing humic acids without ozonation, a drop in a permeate flux was observed compared to UF. Similarly, the addition of PAC to feed treated with ozone resulted in a significant drop in the permeate flux in comparison with pure water flux, regardless of ozone dosage applied.     

Studies on the effect of humic acids and phenol on adsorption-ultrafiltration process performance

Application of pressure-driven membrane processes, such as ultrafiltration (UF) and microfiltration (MF) for surface water treatment have become very popular during last decades. Membrane fouling by humic substances (HS) is one of the major limiting factors in these processes. In order to alleviate the unfavorable effects of the presence of HS in the feed on the process performance UF and MF are often combined with adsorption on powdered activated carbon (PAC). The main goal of the present study was to evaluate the effect of humic acid (HA) on membrane fouling during UF. Moreover, the effect of PAC addition to the feed on UF process, especially on flux decline was determined. The applicability of the adsorption-ultrafiltration (PAC/UF) system to purification of water containing low (phenol) and high molecular (HA) was also investigated. Three different polymer UF membranes, prepared from polysulfone (PSF), cellulose acetate (CA) or polyacrylonitrile (PAN) were applied. It was found that the membranes prepared from PSF and CA are very susceptible to fouling caused by HA. The permeate flux decreased for ca. 50% during UF of HA solution through the PSF membrane and for ca. 45%-through the CA membrane. In the case of the PAN membrane, a negligible effect of HA on the flux was observed. On the basis of the FTIR spectra it was found that the drop in the permeate flux through these membranes may result from interactions between the negatively charged functional groups present on the membrane surface, such as carboxyl groups (CA) and sulfone groups (PSF) with HA, which results in coating of the membrane surface with HA. When PAC was added to the feed containing HA, the permeate flux through the CA and PAN membranes was maintained on a practically unchanged level. However, in case of the PSF membrane, a 50% drop in the permeate flux in comparison with the flux value, when process was conducted without PAC addition was observed. That was supposed to be due to attractive forces among hydrophobic PAC particles, HA molecules and PSF membrane surface. The performed studies showed that the application of PAC/UF system was very effective in the removal of organic substances having both, low and high molecular weights. The role of PAC suspended in a feed in the PAC/UF system is the adsorption of low molecular organic compounds, which cannot be removed by UF alone.     

Nickel-containing nano-sized islands grown on Ge(111)-c(2 × 8) and Ag/Ge(111)-(√3 × √3) surfaces

The formation of nano-islands on both a Ge(111)-c(2 × 8) surface and an Ag/Ge(111)-(√3 × √3) surface evaporated with 0.1 ML Ni was investigated by scanning tunneling microscopy (STM). We have noticed that at temperatures lower than 670 K, the reaction between Ni and the individual substrate surfaces proceeds to form different structures: flat-topped islands with a 2√7 × 2√7 or a 3 × 3 reconstruction on the Ni/Ge(111)-c(2 × 8) surface vs. islands with a 7 × 7 reconstruction on the Ni/Ag/Ge(111)-(√3 × √3) surface. From this we have inferred that within a temperature range between room temperature and 670 K, the intermediate Ag layer retards mixing between Ni and Ge atoms. As a result, the grown islands are composed of pure Ni atoms. Within a temperature range from 670 to 770 K, most islands produced on the Ag/Ge(111)-(√3 × √3) surface are identical with those formed on the Ni/Ge(111)-c(2 × 8) surface, suggesting that above 670 K, Ni atoms are likely to bind with Ge atoms. However, an essential difference between STM images of the surfaces under study exists in the appearance of large elongated islands on the Ni/Ag/Ge(111)-(√3 × √3) surface. The formation of the latter is explained in terms of a difference in energy for Ni diffusion on the Ge(111)-c(2 × 8) and Ag/Ge(111)-(√3 × √3) surfaces.     

Rigid poly(vinyl chloride) (PVC) gelation in the brabender measuring mixer. I. Equilibrium state between sliding,breaking, and gelation of PVC

This article discusses the first part of the Brabender typical torque process curves. Rigid poly(vinyl chloride) (PVC; Polanwil S‐61) was processed at various temperatures between 160 and 200°C with blade speeds in the range of 5–40 min^?1. The morphological changes of the processed compound was characterized by scanning electron microscopy and optical microscopy, and the degree of gelation was estimated on the basis of DSC thermograms. The values of torque minimum strongly depends on temperature. Shear rate affects mainly the time of reaching the minimum torque. The grains are disintegrated into the nonuniform particles and aggregates of the dimensions between 20 and 4 μm. The significant variation of the gelation degree was found for the sample produced in the same conditions and unloaded from Brabender chamber at minimum of torque. It was found that the value of the minimum of torque described momentary equilibrium state between sliding of breaking grains and increasing degree of PVC gelation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 966–971, 2004     

Removal of organic matter by coagulation enhanced with adsorption on PAC

The removal of humic acids and phenol from model solution by coagulation and adsorption on powdered activated carbon (PAC) was investigated. A PAX XL-69 polyaluminum chloride was applied as a coagulant. The adsorption of humic acids and phenol on activated carbon for single- and bi- component solutions was studied. It was found that coagulation without PAC addition was less effective than the adsorption-coagulation integrated system. Coagulation enhanced with adsorption on activated carbon was more effective when coagulation was preceded by adsorption than when the two processes were carried out simultaneously. The best results were obtained at pH 7. Phenol and color were removed pletely, UV₂₅₄ absorbance was reduced by about 99% and COD-Mn was reduced by 81-89%.