Microbial properties of the granular sludge in a psychrophilic UASB reactor fed with electronics industry wastewater containing organic chemicals.

In this study, a lab-scale upflow anaerobic sludge blanket (UASB) reactor was applied to the treatment of artificial electronics industry wastewater containing tetramethylammonium-hydroxide (TMAH), monoethanolamine (MEA), and isopropyl-alcohol (IPA) in order to evaluate process performance and degradation properties. During 800 days of operation, 96% efficiency of chemical oxygen demand (COD) removal was stably achieved at an organic loading rate of 8.5 kgCOD/m3/day at 18-19 °C. MEA degradation, carried out by acid-forming eubacteria, was confirmed within a week. The physical properties of the retained granular sludge were degraded by feeding with TMAH wastewater, but maintained by feeding with MEA wastewater due to an accumulation of species from the genus Methanosaeta and family Geobacteraceae. Analysis of the microbial community structure via SEM and 16S rRNA genes showed a proliferation of Methanomethylovorans-like cells and Methanosaeta-like cells at the surface and in the core of the granular sludge with TMAH, MEA and IPA acclimation. Furthermore, a batch degradation experiment confirmed that process inhibition due to increasing chemical concentration was relatively stronger for TMAH than for MEA or IPA. Thus, controlling the TMAH concentration of the influent to below 1 gCOD/L will be important for the stable treatment of electronics industry wastewater by UASB technology.

Simultaneous Enantioselective Determination of Two New Isopropanol-Triazole Fungicides in Plant-Origin Foods Using Multiwalled Carbon Nanotubes in Reversed-Dispersive Solid-Phase Extraction and Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry.

A simple and sensitive enantiomeric analytical method was established for the determination of two new isopropanol-triazole fungicides mefentrifluconazole and ipfentrifluconazole in plant-origin foods using ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The best enantioseparation of the four target stereoisomers was achieved on a Chiral MX(2)-RH column within 7 min by reversed-phase liquid chromatography, which is a significant improvement in the resolution of different chiral compounds under one set of conditions. A simple and effective pretreatment procedure was developed for the extraction and purification of the two target chiral fungicides using reversed-dispersive solid-phase extraction (r-DSPE) with multiwalled carbon nanotubes (MWCNTs). The influence of the type and amount of MWCNTs on the purification efficiencies and recoveries was evaluated. The mean recoveries for all four stereoisomers were in the range of 76.9-91.2%, with relative standard deviation (RSD) values below 7.2%. The limit of quantification (LOQ) of all stereoisomers of mefentrifluconazole and ipfentrifluconazole was 5 µg/kg for all tested matrixes. The results of the method validation and real samples analysis confirm that the established method is efficient and reliable for the enantiomeric determination of mefentrifluconazole and ipfentrifluconazole in plant-origin food samples.

Metal-organic frameworks for the sorption of acetone and isopropanol in exhaled breath of diabetics prior to quantitation by gas chromatography.

A method is described for non-invasive glucose monitoring of diabetics by means of breath analysis. The metal-organic frameworks (MOFs) ZIF-7, UiO-66 and MOF-5 were chosen as sorbents in packed tubes for sampling and preconcentration of acetone and isopropanol which are established diabetes biomarkers. The MOF UiO-66 was found to be the most appropriate sorbent. Following thermal desorption, acetone and isopropanol where quantified by GC. The method has low limits of detection (0.79-0.84 µg·L-1) and wide linear ranges (5-2000 µg·L-1). It is assumed that the good performance of UiO-66 as a sorbent results from its large surface area and unique porous structure, and from van der Waals interactions. The relative standard deviation for six replicate cycles of sampling and preconcentration using one 50 mg UiO-66 packed tube ranged between 2.3 and 6.7% for intra-day assays, and from 2.7 to 4.3% for inter-day assays. A tube packed with 50 mg of UiO-66 packed tube can be used in over 120 cycles of adsorption/desorption without significant loss of collection efficiency. The GC method has been applied for the analysis of diabetic breath samples, and the recoveries from spiked samples ranged from 89.1 to 107.6%. Graphical abstract Schematic presentation of metal-organic frameworks as sorbents combined with thermal desorption-gas chromatography for the determination of acetone and isopropanol in exhaled breath of diabetics.

Isolation of 1-(3',4'-Dihydroxyphenyl)-3-(2″,4″,6″-trihydroxyphenyl)-propan-2-ol from Grape Seed Extract and Evaluation of its Antioxidant and Antispasmodic Potential.

HPLC profiling of phenolics in grape seed extracts revealed a prominent peak of an unknown substance with concentrations up to 5.3%. Spectroscopic data allowed the identification of the compound 1 as 1-(3',4'-dihydroxyphenyl)-3-(2″,4″,6″-trihydroxyphenyl)-propan-2-ol. 1 is known to be produced from catechin and epicatechin through anaerobic bacteria from human, as well as the rat, intestines. It was hypothesized that the marc remaining after expression of juice from grapes became infested during storage, resulting in the production of 1. Because compound 1 is infrequently found in nature and has never been found in grape seeds, its presence may be considered a marker of an unwanted anaerobic bacterial process occurring during production. The antioxidant potential of 1 was determined by DPPH, ABTS, and FRAP (ferric reducing antioxidant power) assays and compared to the potential of the following compounds: phloroglucine, pyrogallol, gallic acid, catechin, and epicatechin. Furthermore, it was established that 1 significantly reduced guinea pig ileum contraction induced by histamine.

Photocatalytic oxidation of toluene and isopropanol by LaFeO3/black-TiO2.

Large amount of volatile organic compounds (VOCs) are emitted from industrial, mobile, and domestic sources, causing adverse effects on human health and environment. Among VOCs, toluene and isopropanol (IPA) are commonly used as solvent, soldering flux, and spray paint and their emissions need to be reduced. Several VOCs abatement technologies are available to reduce VOC emission and photocatalytic oxidation of VOC is regarded as a viable technique due to its advantage of utilizing solar energy. TiO2 has been investigated for its oxidation capability toward VOCs because of its good photocatalytic activity. However the utilization is limited to UV due to its wider bandgap; furthermore, its fast recombination rate of electron-hole pair reduces the oxidation rate of VOCs. Black-TiO2 and perovskite-type photocatalyst such as LaFeO3 can be applied to enhance photocatalytic activity due to narrower bandgap and longer electron-hole pair lifetime. In this study, black-TiO2 and LaFeO3 are prepared and investigated for their photocatalytic oxidation rates toward toluene and IPA. Results show that toluene removals achieved with black-TiO2 and LaFeO3 are 89% and 98% while IPA removals are 90% and 94%, respectively. Both photocatalysts show better photocatalytic activity than TiO2 and good absorption capability toward visible light. Graphical abstract.

Performance of trickling bed microbial fuel cell treating isopropyl alcohol vapor: Effects of shock-load and shut-down episodes.

This work investigates the enhancement in the removal efficiency of isopropyl alcohol (IPA) vapor by a hollow trickling-bed microbial fuel cell (TB-MFC) that can be achieved by certain modifications. The effects of shock load and shutdown on the performance of TB-MFC were evaluated. When organic loading (OL) of IPA was approximately 22.1-88.5 g m-3 h-1, the removal efficiency of 85.1-93.8% of the TB-MFC was achieved. With an empty bed residence time (EBRT) of 60 s and an inlet IPA concentration of 4.42 g m-3, the TB-MFC achieved its maximum EC of 150 g m-3 h-1, which was 1.7-4 times higher than reported for conventional biofiltration technology. A maximum closed-circuit voltage (CCV) of 173 mV and maximum power density (PDmax) of 53.2 mW m-3 were obtained under optimal conditions (IPA concentration = 0.73 g m-3; EBRT = 60 s). Short-term shutdown (seven days) did not cause significant changes in EC, CCV, and PDmax of the TB-MFC. This investigation establishes the feasibility of using a trickling-bed MFC to substantially increase the removal of IPA and handle shock-load and shut-down events. To increase EC and power output, this laboratory-scale TB-MFC could easily be scaled up by stacking anodes, and has great potential for future application in the field in various industries.

Effect of organic loading rate on the removal of DMF, MC and IPA by a pilot-scale AnMBR for treating chemical synthesis-based antibiotic solvent wastewater.

This study focuses on the effects of organic loading rate (OLR) on the removal of N,N-Dimethylformamide(DMF), m-Cresol (MC) and isopropyl alcohol (IPA) by a pilot-scale anaerobic membrane bioreactor (AnMBR) for treating chemical synthesis-based antibiotic solvent wastewater at period of improved influent COD concentration with decreased HRT. The whole process was divided into five stages in terms of the variation of OLR ranging from 3.9 to 12.7 kg COD/(m3·d). During 249 days of operating time, the average DMF, MC, IPA removal efficiency were 96.9%,98.2% and 96.4%, respectively. Cake layer was accumulated on the membrane surface acted as a dynamic secondary biofilm which lead to the increase of physical removal rate. In addition, mathematical statistical models was built on the linear regression techniques for exploring the inner relationship between EPS and the performance of the AnMBR.

Two-Ply Composite Membranes with Separation Layers from Chitosan and Sulfoethylcellulose on a Microporous Support Based on Poly(diphenylsulfone-N-phenylphthalimide).

Two-ply composite membranes with separation layers from chitosan and sulfoethylcellulose were developed on a microporous support based on poly(diphenylsulfone-N-phenylphthalimide) and investigated by use of X-ray diffraction and scanning electron microscopy methods. The pervaporation properties of the membranes were studied for the separation of aqueous alcohol (ethanol, propan-2-ol) mixtures of different compositions. When the mixtures to be separated consist of less than 15 wt % water in propan-2-ol, the membranes composed of polyelectrolytes with the same molar fraction of ionogenic groups (-NH3⁺ for chitosan and -SO3- for sulfoethylcellulose) show high permselectivity (the water content in the permeate was 100%). Factors affecting the structure of a non-porous layer of the polyelectrolyte complex formed on the substrate surface and the contribution of that complex to changes in the transport properties of membranes are discussed. The results indicate significant prospects for the use of chitosan and sulfoethylcellulose for the formation of highly selective pervaporation membranes.

Metabolic engineering of isopropyl alcohol-producing Escherichia coli strains with 13 C-metabolic flux analysis.

Metabolic engineering of isopropyl alcohol (IPA)-producing Escherichia coli strains was conducted along with 13 C-metabolic flux analysis (MFA). A metabolically engineered E. coli strain expressing the adc gene derived from Clostridium acetobutylicum and the IPADH gene from C. beijerinckii did not produce IPA during its exponential growth phase in the aerobic batch culture. 13 C-MFA was carried out, and revealed a deficiency in NADPH regeneration for IPA production in growth phase. Based on these findings, we used nitrogen-starved culture conditions to reduce NADPH consumption for biomass synthesis. As a result, IPA yield was increased to 20% mol/mol glucose. 13 C-MFA revealed that the relative flux levels through the oxidative pentose phosphate (PP) pathway and the TCA cycle were elevated in nitrogen-starved condition relative to glucose uptake rate. To prevent CO2 release in the 6-phosphogluconate dehydrogenase (6PGDH) reaction, metabolism of this E. coli strain was further engineered to redirect glycolytic flux to the glucose 6-phosphate dehydrogenase (G6PDH) and Entner-Doudoroff (ED) pathway. IPA yield of 55% mol/mol glucose was achieved by combining the nitrogen-starved culture condition with the metabolic redirection. The 13 C-MFA data and intracellular NADPH levels obtained under these IPA production conditions revealed linear correlations between the specific IPA production rate and NADPH concentration, as well as between IPA yield and the pyruvate dehydrogenase (PDH) flux. Our results showed that 13 C-MFA is a helpful tool for metabolic engineering studies, and that further improvement in IPA production by E. coli may be achieved by fine-tuning the cofactor ratio and concentrations, as well as optimizing the metabolic pathways and culture conditions.

Improving isopropanol tolerance and production of Clostridium beijerinckii DSM 6423 by random mutagenesis and genome shuffling.

Random mutagenesis and genome shuffling was applied to improve solvent tolerance and isopropanol/butanol/ethanol (IBE) production in the strictly anaerobic bacteria Clostridium beijerinckii DSM 6423. Following chemical mutagenesis with N-methyl-N-nitro-N-nitrosoguanidine (NTG), screening of putatively improved strains was done by submitting the mutants to toxic levels of inhibitory chemicals or by screening for their tolerance to isopropanol (>35 g/L). Suicide substrates, such as ethyl or methyl bromobutyrate or alcohol dehydrogenase inhibitors like allyl alcohol, were tested and, finally, 36 mutants were isolated. The fermentation profiles of these NTG mutant strains were characterized, and the best performing mutants were used for consecutive rounds of genome shuffling. Screening of strains with further enhancement in isopropanol tolerance at each recursive shuffling step was then used to spot additionally improved strains. Three highly tolerant strains were finally isolated and able to withstand up to 50 g/L isopropanol on plates. Even if increased tolerance to the desired end product was not always accompanied by higher production capabilities, some shuffled strains showed increased solvent titers compared to the parental strains and the original C. beijerinckii DSM 6423. This study confirms the efficiency of genome shuffling to generate improved strains toward a desired phenotype such as alcohol tolerance. This tool also offers the possibility of obtaining improved strains of Clostridium species for which targeted genetic engineering approaches have not been described yet.

[Development of identification method for isopropyl citrate].

In Japan's Specification and Standards for Food Additive, 8th edition, two identification tests involving isopropyl citrate for detecting isopropyl alcohol and citrate are stipulated. However, these identification tests use mercury compound, which is toxic, or require a time-consuming pretreatment process. To solve these problems, an identification test method using GC-FID for detecting isopropyl alcohol was developed. In this test, a good linearity was observed in the range of 0.1-40 mg/mL of isopropyl alcohol. While investigating the pretreatment process, we found that isopropyl alcohol could be detected using GC-FID in the distillation step only, without involving any reflux step. The study also showed that the citrate moiety of isopropyl citrate was identified using the solution remaining after conducting the distillation of isopropyl alcohol. The developed identification tests for isopropyl citrate are simple and use no toxic materials.

Determination of odor release in hydrocolloid model systems containing original or carboxylated cellulose at different pH values using static headspace gas chromatographic (SHS-GC) analysis.

Static headspace gas chromatographic (SHS-GC) analysis was performed to determine the release of 13 odorants in hydrocolloid model systems containing original or regio-selectively carboxylated cellulose at different pH values. The release of most odor compounds was decreased in the hydrocolloid solutions compared to control, with the amounts of 2-propanol, 3-methyl-1-butanol, and 2,3-butanedione released into the headspace being less than those of any other odor compound in the hydrocolloid model systems. However, there was no considerable difference between original cellulose-containing and carboxylated-cellulose containing systems in the release of most compounds, except for relatively long-chain esters such as ethyl caprylate and ethyl nonanoate. The release from the original and carboxylated cellulose solutions controlled to pH 10 was significantly higher than that from solutions adjusted to pH 4 and 7 in the case of some esters (ethyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, butyl propionate, ethyl caproate) and alcohols (2-propanol, 3-methyl-1-butanol), in particular, ethyl butyrate and 3-methyl-1-butanol. In contrast, the release of 2,3-butanedione from both the original and carboxylated cellulose solutions was increased at pH 4 and 7 compared to that at pH 10 by about 70% and 130%, respectively. Our study demonstrated that the release of some odorants could be changed significantly by addition of both original and carboxylated cellulose in hydrocolloid model systems, but only minor effect was observed in pH of the solution.

Biotrickling filtration of isopropanol under intermittent loading conditions.

This paper investigates the removal of isopropanol by gas-phase biotrickling filtration. Two plastic packing materials, one structured and one random, have been evaluated in terms of oxygen mass transfer and isopropanol removal efficiency. Oxygen mass transfer experiments were performed at gas velocities of 104 and 312 m h⁻¹ and liquid velocities between 3 and 33 m h⁻¹. Both materials showed similar mass transfer coefficients up to liquid velocities of 15 m h⁻¹. At greater liquid velocities, the structured packing exhibited greater oxygen mass transfer coefficients. Biotrickling filtration experiments were carried out at inlet loads (IL) from 20 to 65 g C m⁻³ h⁻¹ and empty bed residence times (EBRT) from 14 to 160 s. To simulate typical industrial emissions, intermittent isopropanol loading (16 h/day, 5 day/week) and intermittent spraying frequency (15 min/1.5 h) were applied. Maximum elimination capacity of 51 g C m⁻³ h⁻¹ has been obtained for the random packing (IL of 65 g C m⁻³ h⁻¹, EBRT of 50 s). The decrease in irrigation frequency to 15 min every 3 h caused a decrease in the outlet emissions from 86 to 59 mg C Nm⁻³ (inlet of 500 mg C Nm⁻³). The expansion of spraying to night and weekend periods promoted the degradation of the isopropanol accumulated in the water tank during the day, reaching effluent concentrations as low as 44 mg C Nm⁻³. After a 7-week starvation period, the performance was recovered in less than 10 days, proving the robustness of the process.

Microbial community analysis in biotrickling filters treating isopropanol air emissions.

The evolution of the microbial community was analysed over one year in two biotrickling filters operating under intermittent feeding conditions and treating isopropanol emissions, a pollutant typically found in the flexography sector. Each reactor was packed with one media: plastic cross-flow-structured material or polypropylene rings. The communities were monitored by fluorescence in situ hybridization (FISH) and denaturing gradient gel electrophoresis (DGGE) analysis of the 16S rRNA region. After inoculation with activated sludge, the biotrickling filters were operated using inlet loads (ILs) from 20 to 65 g C m(-3) h(-1) and empty-bed residence times (EBRTs) from 14 to 160 s. Removal efficiencies higher than 80% were obtained with ILs up to 35 g C m(-3) h(-1) working at EBRTs as low as 24 s. There was an increase in the total percentage of the target domains of up to around 80% at the end of the experiment. Specifically, the Gammaproteobacteria domain group, which includes the well-known volatile organic compound (VOC)-degrading species such as Pseudomonas putida, showed a noticeable rise in the two biotrickling filters of 26% and 27%, respectively. DGGE pattern band analysis revealed a stable band of Pseudomonas putida in all the samples monitored, even in the lower diversity communities. In addition, at similar operational conditions, the biotrickling filter with a greater relative abundance of Pseudomonas sp. (19.2% vs. 8%) showed higher removal efficiency (90% vs. 79%). Results indicate the importance of undertaking a further in-depth study of the involved species in the biofiltration process and their specific function.

[Determination of residual organic solvents in flunixin meglumine raw material by headspace gas chromatography].

A method for the determination of five kinds of residual organic solvents in flunixin meglumine raw material was developed by headspace gas chromatography. An HP-FFAP capillary column (30 m x 0.32 mm x 1.0 microm), a flame ionization detector and the external standard method were used for the separation and quantitative analysis. The effects of equilibrium temperature and equilibrium time on the determination of residual organic solvents were investigated. The good results were obtained in the equilibrium temperature of 90 degrees C and equilibrium time of 30 min. The standard curves were linear in the range of 0.40-7.93 mg/L (r = 0.999 8) for ethyl acetate, 7.32-146.48 mg/L (r = 0.999 6) for methanol, 4.53-90.61 mg/L (r = 0.999 9) for isopropanol, 3.62-72.32 mg/L (r = 0.999 8) for ethanol and 2.31-46.24 mg/L (r = 0.999 6) for acetonitrile. The recoveries for the five residual organic solvents were between 95.96% and 100.31% with relative standard deviations (RSDs) (n = 6) of 1.97%-3.28%. The detection limits of ethyl acetate, methanol, isopropanol, ethanol and acetonitrile were 0.08, 0.9, 0.2, 0.4 and 0.3 mg/L, respectively. The proposed method was successfully applied to analyze the residual organic solvents in the real sample of flunixin meglumine raw material. The results showed that only isopropanol and ethanol were found in the sample with the contents of 177.44 microg/g and 69.32 microg/g, respectively. The method is rapid, sensitive and accurate for the content determination of residual solvents in flunixin meglumine raw material.

[Process of adsorption and separating recovery solvents from vapor mixture directly].

Experiment on process feasibility of adsorption and separating recovery of organic compounds directly from waste gas was conducted with the activated carbon column train consists of 4 units in serial. Isopropyl alcohol and toluene vapor mixture was used as target gas, which are the common constituents of the gas emitted from fine ceramic manufacture. The experimental results showed obvious adsorption stratification phenomena alone the activated carbon column length for the vapor mixture. Under the condition of superficial gas velocity of 0.42 m x s(-1), inlet concentration of 477 mg x m(-3) and 746 mg x m(-3) for isopropyl alcohol and toluene respectively, 26 cm total carbon packing length of the four column serial train, when the adsorption time reached 798 min, the adsorption capacities for toluene and isopropyl alcohol are 184.5 mg x g(-1) and 0 mg x g(-1) respectively in 0-10 cm section, and 0.92 mg x g(-1) and 91.2 mg x g(-1) respectively in 21-26 cm section, liquids with over 99% purity of isopropyl alcohol and toluene were recovered separately from the two end columns of the carbon column train. There is a gaseous concentration amplifier zone in the carbon column for the weaker adsorbate, isopropyl alcohol, which make the adsorption capacity of isopropyl alcohol increase over 27% in part of the down flow zone in this experiment. It is possible to directly recover the pure solvent liquid separately from the vapor mixture by the way of a serial adsorption column with separating stage recovering.

Improvement of isopropanol production by metabolically engineered Escherichia coli using gas stripping.

To improve isopropanol production by metabolically engineered Escherichia coli strain TA76, the optimization of fermentation conditions and isopropanol removal by gas stripping were performed. Isopropanol is one of the simplest secondary alcohols, and it can be dehydrated to yield propylene, which is currently derived from petroleum as a monomer for making polypropylene. Initially, using a pH-controlled fed-batch culture with the intermittent addition of glucose, strain TA76 produced 667 mM (40.1g/L) of isopropanol after 60 h, representing 73.2% (mol isopropanol/mol glucose) of the theoretical maximum yield. Because the accumulation of isopropanol drastically reduced production yields, a gas stripping recovery method was incorporated into the fed-batch culture system. Using this approach, strain TA76 produced 2378 mM (143 g/L) of isopropanol after 240 h with a yield of 67.4% (mol/mol). To our knowledge, this titer represents the highest level of isopropanol production by E. coli to date and suggests that strain TA76 has a great potential for commercial fermentative isopropanol production.

Preparation of visible light active S-doped TiO2 photocatalysts and their photocatalytic activities.

Although titanium dioxide photocatalysts having an anatase phase are a promising substrate for photodegradation of pollutants in water and air, their photocatalytic activities show only under UV light. To utilize solar light which has a large amount of visible light, the development of the photocatalysts whose activities show under visible light is one of the most important strategies. We have succeeded in synthesizing chemically modified titanium dioxide photocatalysts in which S (S4+) substitutes for some of the lattice titanium atoms. They show strong absorption for visible light and high activities for degradation of 2-propanol in aqueous solution and partial oxidation of adamantane in acetonitrile under irradiation at wavelengths longer than 440 nm. The oxidation state of the S atoms incorporated into the TiO2 particles is determined to be mainly S4+ from XPS spectra.

Evaluation of sample preparation techniques for mass measurements of PCR products using ESI-FT-ICR mass spectrometry.

Elimination of PCR buffer components and alkali metal cations (i.e., Na+, K+) is of critical importance to allow for accurate mass measurements of PCR products for genotyping and sequencing applications. Ethanol precipitation followed by microdialysis has been repeatedly shown to efficiently desalt PCR products for analysis by mass spectrometry and is considered the gold standard. Alternative cleanup techniques that are compatible with automation are explored here with the intent of expanding the bottleneck that exists between the production of PCR products and analysis by electrospray ionization mass spectrometry (ESI-MS). Numerous combinations of approaches were evaluated that included PCR purification kits and alcohol precipitations. The data shown here support alternative approaches to an ethanol precipitation followed by microdialysis that have comparable desalting efficiency and can be utilized for cleanup of PCR products generated from single reactions.