Mass Spectrometry Study of OH-initiated Photooxidation of Toluene

The composition of products formed from photooxidation of the aromatic hydrocarbon toluene was investigated. The OH-initiated photooxidation experiments were conducted by irradiating toluene/CH3ONO/NO/air mixtures in a smog chamber, the gaseous products were detected under the supersonic beam conditions by utilizing vacuum ultraviolet photoionization mass spectrometer using synchrotron radiation in real-time. And an aerosol time-of-flight mass spectrometer was used to provide on-line measurements of the individual secondary organic aerosol particle resulting from irradiating toluene. The experimental results demonstrated that there were some differences between the gaseous products and that of particle-phase, the products of glyoxal, 2-hydroxyl-3-oxo-butanal, nitrotoluene, and methyl-nitrophenol only existed in the particle-phase. However, furane, methylglyoxal, 2-methylfurane, benzaldehyde, cresol, and benzoic acid were the predominant photooxidation products in both the gas phase and particle phase.

Preparation and improved photocatalytic activity of ordered mesoporous TiO_2 by evaporation induced self-assembly technique using liquid crystal as template

Ordered mesoporous TiO2 （OMPT） was prepared by an evaporation induced self-assembly technique using liquid crystal as template. The key factors affecting the methylene blue （MB） oxidation efficiency were investigated, including the initial concentration of MB, pH value and catalyst concentration. The results show that the obtained OMPT has high thermal stability and shows a 2D hexagonal mesostructure with the small particle size and high surface area, which lead to higher degradation efficiency than commercial P25 or nanoparticle TiO2 （NPT） fabricated by sol-gel process. The optimal conditions are 5 mg/L MB, pH 6 and 1.5 g/L OMPT for the fastest rate of MB degradation. Total organic carbon （TOC） analysis indicates complete mineralization of MB in 240 min by OMPT, with rate constant higher than NPT or P25.

Influence of the post-treatment of HZSM-5 zeolite on catalytic performance for alkylation of benzene with methanol

The porous material HZSM-5 zeolite with micro-mesopore hierarchical porosity was prepared by post-treatment （combined alkali treatment and acid leaching） of parent zeolite and its catalytic performance for benzene alkylation with methanol was investigated. The effect of post-treatment on the textural properties was characterized by various techniques （including ICP-AES, XRD, nitrogen sorption isotherms, SEM, NH3-TPD, Py-IR and TG）. The results indicated that the post-treatment could modify the structural and acidic properties of HZSM-5 zeolite. In this procedure, not only additional mesopores were created by selective extraction of silicon but also the acidity was tuned. Consequently, the modified HZSM-5 zeolite showed larger external surface area with less acid sites as compared to the parent zeolite. It was found out that the modified zeolite exhibited a higher benzene conversion and xylene selectivity for alkylation of benzene with methanol as well as excellent life span of the catalyst than conventional ones. This can be explained by the facts that the presence of additional mesopores improved the diffusion property in the reactions. Furthermore, the modified zeolite showed an appropriate Bronsted acidity for effective suppression of the side reaction of methanol to olefins, thus reduced the accumulation of coke on the HZSM-5 zeolite, which was favorable for the catalyst stability. In comparison with the parent HZSM-5 zeolite, the modified zeolite by alkali treatment and acid leaching showed better performance for the benzene alkylation with methanol.

A modeling study of effective radiative forcing and climate response due to increased methane concentration

An atmospheric general circulation model BCC_AGCM2.0 and observation data from ARIS were used to calculate the effective radiative forcing（ERF） due to increased methane concentration since pre-industrial times and its impacts on climate. The ERF of methane from 1750 to2011 was 0.46 W m^-2 by taking it as a well-mixed greenhouse gas, and the inhomogeneity of methane increased its ERF by about 0.02 W m^-2.The change of methane concentration since pre-industrial led to an increase of 0.31 ℃ in global mean surface air temperature and 0.02 mm d 1in global mean precipitation. The warming was prominent over the middle and high latitudes of the Northern Hemisphere（with a maximum increase exceeding 1.4℃）. The precipitation notably increased（maximum increase of 1.8 mm d^-1） over the ocean between 10°N and 20° N and significantly decreased（maximum decrease 〉-0.6 mm d^-1） between 10° S and 10° N. These changes caused a northward movement of precipitation cell in the Intertropical Convergence Zone（ITCZ）. Cloud cover significantly increased（by approximately 4%） in the high latitudes in both hemispheres, and sharply decreased（by approximately 3%） in tropical areas.

Measurement and Correlation for Solubility of Dimethyl-2,6-naphthalene Dicarboxylate in Organic Solvents

Solubility of dimethyl-2,6-naphthalene dicarboxylate in acetic acid, N,N-dimethylfonnamide, N,N-dimethyl acetamide, dimethyl sulphoxide, and N-methyl-2-ketopyrrolidine were determined using a dynamic method. The measured systems were correlated by UNIFAC group contribution method. A new main group （aromatic ester, ACCOO） was defined to express the activity coefficients of the aromatic ester. New interaction parameters of the ACCOO group were expressed as the first-order function of temperature and were determined from the experimental data. The calculated results for the new interaction parameters were satisfactory. The measured systems were also correlated with the Wilson and 2-h models, and the results were compared with those of the UNIFAC model.

Application of rRNA probes and fluorescence in situ hybridization for rapid detection of the toxic dinoflagellate Alexandrium minutum

The dinoflagellate Alexandrium minutum is often associated with harmful algal blooms (HABs). This species consists of many strains that differ in their ability to produce toxins but have similar morphology, making identification difficult. In this study, species-specific rRNA probes were designed for whole-cell fluorescence in situ hybridization (FISH) to distinguish A. minutum from two phylogenetic clades. We acquired the complete SSU to LSU rDNA sequences (GenBank accession numbers JF906989-JF906999) of 11 Alexandrium strains and used these to design rRNA targeted oligonucleotide probes. Three ribotype-specific probes, M-GC-1, M-PC-2, and M-PC-3, were designed. The former is specific for the GC clade ("Global clade") of A. minutum, the majority of which have been found non-toxic, and the latter two are specific for the PSP (paralytic shellfish poisoning)-producing PC clade ("Pacific clade"). The specificity of these three probes was confirmed by FISH. All cells in observed fields of view were fluorescently labeled when probes and target species were incubated under optimized FISH conditions. However, the accessibility of rRNA molecules in ribosomes varied among the probe binding positions. Thus, there was variation in the distribution of positive signals in labeled cells within nucleolus and cytosol (M-GC-1, M-PC-3), or just nucleolus (M-PC-2). Our results provide a methodological basis for studying the biogeography and population dynamics of A. minutum, and providing an early warning of toxic HABs.

Excited state proton transfer effect of 7-hydroxyquinoline in dimethyl sulfoxide solvent

7-hydroxyquinoline (7-HQ) is a kind of organic molecule with excited state proton transfer (ESPT) effect,and can be used as the material for all optical switching.This optical switching takes place via the ESPT effect depending on its intermolecular hydrogen bond formed with the solvent,and can have the effect of all optical switching.7-HQ can not form intermolecular hydrogen bond with dimethyl sulfoxide (DMSO),so 7-HQ in DMSO solution cannot display the ESPT effect.However,after the solution was radiated by an UV laser, we found that 7-HQ could have ESPT effect.This phenomenon is reported and the mechanism is investigated for the first time in this paper.

Lipase-catalyzed Kinetic Resolution of Racemic 1-Trimethylsilylethanol in Organic Solvent

The enantioselective esterification of racemic 1-trimethylsilylethanol with acids catalyzed by lipase in organic solvent was successfully performed. The influence of some factors on the reaction was investigated. Among the four lipases explored, Candida rugosa lipase (CRL) showed the highest activity and enantioselectivity. Octanoic acid was the best acyl donor among the eleven acids studied and n-hexane was the most suitable medium for the reaction. The optimum shaking rate and temperature were found to be 150r·min-1 and 20℃ to 30℃, respectively. The enantiomeric excess of the remaining (5)-(-)-1-trimethylsilylethanol was 93% when substrate conversion was 53% upon incubation of the reaction mixture at 30℃, 150r·min-1 for 12 h.

Removal and transformation of dissolved organic matter in secondary effluent during granular activated carbon treatment

This paper focused on the removal and transformation of the dissolved organic matter （DOM） in secondary effluent during the granular activated carbon （GAC） treatment. Using XAD-8/XAD-4 resins, DOM was fractionated into five classes： hydrophobic acid （HPO-A）, hydrophobic neutral （HPO-N）, transphilic acid （TPI-A）, transphilic neutral （TPI-N） and hydrophilic fraction （HPI）. Subsequently, the water quality parameters of dissolved organic carbon （DOC）, absorbance of ultraviolet light at 254 nm （UV-254）, specific ultraviolet light absorbance （SUVA） and trihalomethane formation potential （THMFP） were analyzed for the unfractionated and fractionated water samples. The results showed that the order of the DOC removal with respect to DOM fractions was observed to be HPI〉HPO-A〉HPO-N〉TPI-A〉TPI-N. During the GAC treatment, the THMFP of the unfractionated water samples decreased from 397.4 μg/L to 176.5 μg/L, resulting in a removal efficiency of 55.6%. The removal order of the trilaalomethanes （THMs） precursor was as follows： HPO-A〉TPI-A〉TPI-N〉HPO-N〉HPI. By the GAC treatment, the specific THMFP of HPO-A, TPI-A, TPI-N and the original unfractionated water samples had a noticeable decrease, while that of HPO-N and HPI showed a converse trend. The Fourier transform infrared （FTIR） results showed that the hydroxide groups, carboxylic acids, aliphatic C-H were significantly reduced by GAC treatment.

Variability of micropollutants and microorganisms in water distribution system

The variation of water quality in water distribution system was investigated with assimilable organic carbon (AOC)and trihalomethanes(THMs) used as assessment indexes. Bacterium was identified in water distribution. The result showed that there were pathogenic parasites in water distribution system. The variation of AOC is related to chlorine residual and bacterium activity, and AOC concentration decreased first and then increased with the extension of water distribution system. The formation of THMs was related to the consumption of chlorine inside the distribution system, and THMs concentration increased with the extension of water pipe line.

Removal of Organic Matter and Ammonia Nitrogen in Azodicarbonamide Wastewater by a Combination of Power Ultrasound Radiation and Hydrogen Peroxide

A simple and efficient sonochemical method was developed for the degradation of organic matter and ammonia nitrogen in azodicarbonamide wastewater.The effects of initial pH,ultrasound format and peripheral water level on the sonolysis of hydrazine,urea,COD and ammonia nitrogen were investigated.It is found that the initial pH has a significant influence on the degradation of hydrazine and ammonia nitrogen,whereas this impact to urea is relatively small.It also shows that a noticeable enhancement of ammonia nitrogen removal could be achieved in a proper intermittent ultrasound operation mode,i.e.,1/1 min on/off mode.The height difference between the periph-eral water level and the inner water level of the flask affects the efficiency of ultrasonic treatment as well.

Flow, Transport and Biodegradation of Toluene During Bioventing

Bioventing is conducted on one-dimensional soil columns. A numerical model is developed for simulating the mass exchange, advective and dispersive transport and biodegradation of toluene. The model parameters are estimated independently through laboratory batch experiments, or from literature. Simulations are found to provide reasonable agreement with experimental data. Experimental results show that toluene removal due to biodegradation is more important at the later stage. The total cleanup time when NAPL (non-aqueous phase liquid) phase exists was twice more than that without NAPL. Sensitivity analysis of parameters suggests that model predictions are mainly dependent on mass transfer coefficient and microbial parameters, such as the half-saturation coefficient and maximum specific substrate utilization rate.

Organic‐free synthesis of MOR nanoassemblies with excellent DME carbonylation performance

Seed‐assisted low alkalinity gel system was developed to explore the organic‐free synthesis of MORzeolite.MOR nanoassemblies with Si/Al ratio(SAR)up to 9.4 and high solid yield(84–94%)weresuccessfully obtained under controlled low alkalinity conditions.Characterization results demonstratethat the acid strength increases in parallel with the SAR,while the total acid amount and theproton distribution in the main channels and the side pockets are similar for the samples.The protondistribution in the H‐MOR is not straightforwardly related to the Na+distribution in theas‐synthesized MOR,implying the transfer of the protons among the oxygen sites of framework Tatom.Relative to low‐silica samples I‐5.3 and I‐7.4,sample I‐9.4 displays the best mass transferperformance and accessibility of the acid sites by pyridine due to its relatively low Al density andmild dealumination degree.Correspondingly,sample I‐9.4(pyridine‐modified catalyst)shows thebest activity with ca.100%selectivity of methyl acetate(MAc)in the DME carbonylation reaction.The high steady MAc yield(6.8 mmol/g/h)over sample I‐9.4 suggests the promising application ofMOR nanoassemblies synthesized by this economical organic‐free strategy.

Selective aerobic oxidation promoted by highly efficient multi-nitroxy organocatalysts

Selective oxidation with molecular oxygen as the sole oxidant under mild conditions is of crucialimportance for the long‐term sustainable exploitation of available feedstocks and the formation ofrequired intermediates for organic synthesis and industrial processes.Among the developed oxidationprotocols,innovative strategies using hydroxyimide organocatalysts in combination with metallicor metal‐free cocatalysts have attracted much attention because of the good activities andselectivities of such catalysts in the oxo functionalization of hydrocarbons.This method is based onthe reaction using N‐hydroxyphthalimide,which was first reported by Ishii’s group in the1990s.Although the important and wide‐ranging applications of such catalysts have been summarizedrecently,there are no reviews that focus solely on oxidation strategies using multi‐nitroxy organocatalysts,which have interesting properties and high reactivities.This review covers the concisesynthetic methods and mechanistic profiles of known multi‐nitroxy organocatalysts and summarizessignificant advances in their use in efficient aerobic oxidation.Based on a combination of experimentaland theoretical results,guidelines for the future rational design of multi‐nitroxy organocatalystsare proposed,and the properties of various model multi‐nitroxy organocatalysts are predicted.The present overview of the advantages,limitations,and potential applications of multi‐nitroxyorganocatalysts can provide useful tools for researchers in the field of selective oxidation.

Characterization of NOM and THM formation potential in eutrophic reservoir water

Resin adsorption technique with XAD-8 and XAD-4 was used to characterize the raw water from Erlong reservoir in Jilin province of China. The NOM chemical composition sequences of four organic fractions in the raw water, from high to low, are fulvic acid （FA） fraction, hydrophilic non-acid （HPINA） fraction, hydrophilic acid （HPIA） fraction, and humic acid （HA） fraction. Experimental results show that FA is the main precursor of THMFP among the four organic fractions. However, HA or hydrophobie acid exhibits the highest chlorination activity in forming THMs. It is also found that the value of FI/DOC or SUVA and the specific THMFP have better positive correlation. It is implied that certain source water has unique nature of NOM and DBPs.

Three-dimensional fluorescence characteristics of dissolved organic matter produced by Prorocentrum donghaiense Lu

Filtration and cross-flow ultrafiltration techniques were used to separate culture media of Prorocentrurn donghaiense at the exponential growth, stationary and decline stages into 〈0.45 μm filtrate, 100 kDa-0.45 μm, 1%100 kDa and 1-10 kDa retentate and 〈1 kDa ultrafiltrate fractions. The fluorescence properties of different molecular weights of dissolved organic matter （DOM） were measured by excitation-emission matrix spectra. Protein-like and humic-like fluorophores were observed in the DOM produced by P. donghaiense. The central positions of protein-like fluorophores showed a red shift with prolonged growth duration, shifting from tyrosine-like properties at the exponential growth stage to tryptophan-like properties at the stationary and decline stages. The excitation wavelengths of protein-like fluorophores exhibited some change in the exponential growth and stationary stages with increased molecular size, but showed little change in the decline stage. However, the emission wavelengths in the decline stage exhibited a blue shift. Very distinct C type and A type peaks in humic-like fluorophores were observed. With a prolonged culture time, the intensities of both of the peaks became strong and the excitation wavelengths of peak A showed a red shift, while the A：C ratios fell. More than 94% of fluorescent DOM was in the lower than 1 kDa molecular weight fraction.

Preparation of MIL-88B(Fe_(x),Co_(1‒x))catalysts and their application in one-step liquid-phase methanol oxidation to methyl formate using H_(2)O_(2)

The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products.The development of highly efficient and stable catalysts is critical for this transformation.In this study,a series of MIL-88B(Fe_(x),Co_(1‒x))bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method.X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,energy dispersive spectroscopy,Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy,N2 adsorption-desorption,and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts.The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H_(2)O_(2)in a liquid-phase batch reactor.The results show that the MIL-88B(Fe_(x),Co_(1‒x))catalysts exhibit uniform needle-like morphologies with an average length and width of 400-600 nm and 100-150 nm,respectively.Co^(2+)is incorporated into the framework by partially replacing Fe^(3+)in MIL-88B.Moreover,the catalyst efficiently promoted the conversion of methanol to methyl formate.When MIL-88B(Fe_(0.7),Co_(0.3))catalyst was used with a molar ratio of H_(2)O_(2)to methanol of 0.5 at 80℃for 60 min,34.8%methanol conversion was achieved,and the selectivity toward methyl formate was 67.6%.The catalysts also showed great stability with a steady conversion and selectivity even after four cycles.The preliminary oxidation mechanism was also studied.It was determined that H_(2)O_(2)is first adsorbed on the Fe^(3+)sites and subsequently activates these sites.Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid.Subsequently,formic acid reacts with the residual methanol at the Fe^(3+)and Co^(2+)Lewis acid sites to form methyl formate.

Toxic Effects of Phthalates on Ocean Algae

This article discusses the interaction of phthalates and ocean algae based on the standard appraisal method of chemical medicine for algae toxicity. Through the experiments on the toxic effects of dimethyl (o-) phthalate (DMP), diethyl (o-) phthalate (DEP), dibutyl (o-) phthalate (DBP) on ocean algae, the 50 % lethal concentration of the three substances in 48 h and 96 h for plaeodectylum tricornutum, platymonas sp, isochrysis galbana, and skeletonema costatum is obtained. Tolerance limits of the above ocean algae of DMP, DEP, and DBP are discussed.

Removal of organic solvent from cathodic electrophoretic emulsion paint by vacuum steam stripping

The production of environmental friendly emulsion paint is of great significance. Vacuum steam stripping of methyl isobutyl ketone （MIBK） and methyl ethyl ketone （MEK） from cathodic electrophoretic emulsion was studied. The effects of mass ratio of vapor to feed （V/F）, vacuum degree and feed temperature on removal rate of MIBK and MEK, emulsion size and solid volume fraction of the emulsion were investigated, and the removal of MIBK and MEK from cathodic electrophoretic emulsion by vacuum desorption was also studied. The results show that removal rates of both MIBK and MEK increase with the increase of V/F, vacuum degree and feed temperature. Removal rates of MIBK and MEK are 98.3% and 93.6%, respectively, at the operating condition V/F of 0.7, feed temperature of 27℃ and vacuum degree of 90 kPa. The emulsion size of cathodic electrophoretic emulsion increases slightly with feed temperature when temperature is below 42 ℃, and increases rapidly with feed temperature when temperature is above 42℃. Solid volume fraction increases by 10% as vacuum degree increases from 0 to 90 kPa at V/F of 0.7 and feed temperature of 27 ℃. Compared with vacuum desorption, vacuum steam stripping can get a higher removal rate of MIBK and MEK under the same feed flow, vacuum degree and feed temperature.

Composite Materials for Adsorption-Catalytic Purification of Toxic Organic Impurities

Design of high effective catalysts with unique properties opens good perspectives for solving environmental problems of cleaning waste gas, particularly from toxic impurities of organic solvents. A new thermostable nanostructured composite materials based on shungyte was obtained and determined their adsorption capacity on the model substance o-xylene. Xylene used as a model substance is a part of the organic solvent presents in waste industrial gases. Best xylene sorbents （449.7 mg/g）--activated shungyte containing 70% carbon and saksaul charcoal （554.3 mg/g）. Then polyoxide catalysts on the base of transition metals （Ni, Mn, Cu） modified by the rare earth elements （La, Ce and Nd）, supported on a granular carrier were studied in the reaction of deep oxidation of o-xylene. 100% activity showed 7.0% Cu-Mn-Ce-catalyst at T： 250-300℃, Cxylene： 0.6 g/ms, the optimum space velocity of gas--1,200 h^1 for catalysts supported on a granular carrier. The results obtained can be used in the purification of waste gas from paint, furniture, cable, printing and other enterprises from the impurities of toxic organic solvents.