Photocatalytic oxidation of aqueous trichloroethylene using dye sensitized buoyant photocatalyst monitored via micro-headspace solid-phase microextration gas chromatography/electron capture detection and mass spectrometry

Trichloroethylene (TCE), a useful industrial agent which unfortunately exhibits carcinogenic properties, has become an extremely prevalent environmental contaminant. As such, new rapid, sensitive, and cost effective detection methods are needed for the identification of potential point sources of contamination. A new analytic micro-headspace method is described, utilizing solid phase micro-extraction (SPME) fibers and routine gas chromatography/electron capture detection (GC/ECD) for the detection of TCE to the 3.89 ppb level in aqueous samples. The polydimethylsiloxane (PDMS) fiber was shown to have the greatest analytical promise, with excellent sensitivity and minimal carry over. This method was employed in the monitoring of the photo-oxidation of TCE using buoyant TiO₂ coated microspheres, which were sensitized using natural anthocyanin dyes obtained from fruits. Solar mediated photo-oxidation was shown to be a successful method for the removal of aqueous organic contaminants. The dye sensitized system yielded excellent remediation with 93% of the TCE removed from the system within 12 h. As irradiation was executed, overall TCE concentrations were reduced, while the expected mineralization product of hydrochloric acid was produced. The micro-headspace SPME procedure described here, offers considerably improved sensitivity, with orders of magnitude improvement in method detection limits, over previously published micro-headspace methods.     

Cyclodextrins for remediation of soils contaminated with chlorinated organics

The effect of random methylated ??CD (RAMEB) on the efficiency of various remediation technologies was studied in lab-scale model-experiments applying soil and groundwater originating from a site contaminated with trichloroethylene (TCE). The solubility of TCE was enhanced to tenfold in 10% solution of RAMEB compared to that in water. This solubilizing effect was utilized for remediation of the TCE contaminated soil using enhanced groundwater extraction and in situ TCE oxidation by ISCO (= in situ chemical oxidation). The effect of CD on TCE extraction from soil was studied using two technologies: ground-water extraction followed by air stripping or UV irradiation. The RAMEB-enhanced ISCO was applied directly to the water-saturated soil without water extraction or separation. The efficiency of air stripping of TCE (removal by bubbling air through the contaminated ground-water obtained by extraction) was decreased in the presence of RAMEB due to the volatility decreasing effect of complexation. The efficiency of the entire technology (extraction and air stripping together) was, however, enhanced as three times more TCE was dissolved, and more than twice as much could be removed when 5% RAMEB solution was applied instead of water. Similar results were obtained by UV irradiation. Although the complexation has a protective effect against degradation caused by irradiation, the efficiency of the technology (extraction and subsequent UV irradiation) is enhanced to approximately threefold, because more than 10 times higher TCE concentration was found in the extract using 20% RAMEB concentration. ISCO is based on Fe-catalyzed oxidation using hydrogen peroxide. The catalytic effect of RAMEB was observed only when it was applied together with Fe(II) salts. Without Fe(II) the effect of complex formation dominated. When hydrogen peroxide and FeSO₄ were applied with RAMEB, over five times enhancement in TCE removal was obtained compared to the technology based on the addition of hydrogen peroxide and Fe(II) salts without RAMEB. This effect shows that the solubilizing effect on iron catalyst is at least as much or even more important than the solubilizing effect on TCE. The ternary complex formation with ferrous/ferric ion and TCE seems to be responsible for the enhanced efficacy.     

A new adsorbent for trace level organic contaminants

Summary A preliminary study has been carried out to evaluate a new adsorbent, Thermosorb, for trace level organic contaminants. For this purpose, a comparison was made with a well-characterized adsorbent, Tenax GC, using a prepared aqueous solution of trace organic components. In addition, a comparison was made of chromatograms of air contaminants obtained using both of these adsorbents, under equivalent conditions. The results clearly indicated the potential of this thermally stable, inorganic adsorbent for many trace organic substances of environmental interest.     

Photooxidation of dibenzothiophene on TiO(2)/hectorite thin films layered catalyst

A new titanium(IV) oxide-hectorite nanofilm photocatalyst was prepared on quartz slides. It was evaluated in the photooxidation of dibenzothiophene (DBT) in nonpolar organic solution (tetradecane), as a model for diesel fuel. A removal regimen was developed consisting of catalytic photooxidation followed by adsorption of products on silica gel. Photooxidation of DBT was performed with and without catalyst, at 254 and 300 nm. Comparison was made with a commercially available TiO(2) catalyst, Degussa P25. The catalyst was analyzed by nitrogen adsorption, XRD, SEM, and TGA-DTA. DBT concentrations were measured by HPLC and UV spectrophotometry. Preliminary qualititative analysis of products was performed by UV and HPLC. Results indicated that the outlined process was effective in reducing sulfur levels to below 10 ppm sulfur.     

菲在TiO2催化下的光降解研究

以汞灯为光源,TiO₂为催化剂,对菲的光催化降解途径进行了研究.将水溶性极小的菲预先吸附到TiO₂上之后,菲可以在紫外线的照射下发生快速、完全的矿化.通过GC-MS手段检测到一些中间产物,给出了菲光催化降解的详细途径.另外,研究了菲在表面活性剂十六烷基三甲基溴化铵(HTAB)的助溶下TiO₂催化的光降解过程,探讨了表面活性剂的浓度和溶液pH值对反应速率的影响.     

Trichloroethylene Combustion in a Submerged Thermal Plasma: Results and Chemical Kinetics Model

This work deals with incineration of organic liquid wastes using an oxygen thermal plasma jet, submerged in water. The results presented here concern incineration of trichloroethylene (TCE). During a trial run, the CO₂ and CO content in the exhaust gas is continuously measured; samples taken periodically from the solution are analyzed by appropriate methods: total organic carbon and chlorine content are measured. Process efficiency during tests with a few L/h of TCE is given by the mineralization rate. The trapping rate of chlorine as HCl is near 100 %. The TCE destruction and removal efficiency, measured by MS/GC, is better than 99.9999 %. A simplified kinetic model of gas quenching was constructed from a single-phase plug-flow reactor model taking into account 14 species and 34 reactions. It satisfies the requirements of heat balance and major components analysis, and reveals the major role of the OH radical on the concentrations of CO as well as HCl and/or Cl₂ in the off-gas stream.     

In vitro Photo‐Oxidation of Pyruvate to Acetyl: A Main Source for the Formation of Acetyl Coenzyme A in the Citric Acid Cycle to Perform Biochemical Reactions

The kinetics of photooxidation of pyruvate was investigated in presence of zinc oxide catalyst under illumination of visible light. The influence of different parameters such as concentrations of reactants, amount of catalyst and irradiation time was studied on the redox reaction under pseudo‐first order conditions. The results indicated that amount of catalyst, presence of electron accepter in solution and irradiation time was the key factors influencing the efficiency of photo‐oxidation of pyruvate to acetyl.     

TiO2气相光催化氧化降解三氯乙烯的产物分布及失活机理研究

用ＧＣ／ＭＳ、ＴＰＤ和ＸＰＳ方法,研究了三氯乙烯的气相光催化降解反应,检测到新的中间体乙二酰氯（ＣＩＣＯＣＯＣＩ）。对产物分布的分析表明,水蒸汽的存在能显著抑制含氯副产物的生成,改变反应产物的分布。使用过的催化剂的ＸＰＳ谱图显示,催化剂表面存在含氯副产物,反应副产物在催化剂表面的积累是导致催化剂失活的主要原因。     

新型仿生光催化剂的合成及在孔雀绿光催化降解中的作用

 通过付-克反应用磺酸铁酞菁(FePcS)修饰中孔分子筛HMS,首次得到了一种新型光反应催化剂(简称为HMS-FePcS),并用XRD,TG,FT-IR, SEM/TEM,元素分析及固体紫外漫反射光谱等手段对催化剂进行了表征. 实验结果表明,催化剂能高效地催化H2O2氧化降解孔雀绿染料,光照下,在500 ml浓度为0.1 mmol/L的孔雀绿溶液中加入0.3 ml 30%的H2O2和20 mg HMS-FePcS催化剂,于50 ℃下反应 1200 min,脱色率接近100%,总有机碳的去除率达到73%. 对孔雀绿光催化降解的机理进行了初步探讨.     

Assessment of the Arsenic Removal From Water Using Lanthanum Ferrite

The catalytic performance of a perovskite-type lanthanum ferrite LaFeO₃ to remove arsenic from water has been investigates for the first time. LaFeO₃ was prepared by citrate auto-combustion of dry gel obtained from a solution of the corresponding nitrates poured into citric acid solution. Kinetic studies were performed in the dark with As(V) and in the dark and under UV-C irradiation at pH 6–7 with As(III) (both 1 mg L⁻¹), and As : Fe molar ratios (MR) of 1 : 10 and 1 : 100 using the LaFeO₃ catalyst. As(V) was removed from solution after 60 min in the dark in 7 % and in 47 % for MR=1 : 10 and MR=1 : 100, respectively, indicating the importance of the amount of the iron material on the removal. Oxidation of As(III) in the dark was negligible after 60 min in contact with the solid sample, but complete removal of As(III) was observed within 60 min of irradiation at 254 nm, due to As(III) photooxidation to As(V) and to As(III) sorption to a minor extent. Morphological and microstructural studies of the catalyst complement the catalytic testing. This work demonstrates that LaFeO₃ can be used for the removal of As(III) from highly arsenic contaminated water.     

A Cross‐linked Conjugated Polymer Photosensitizer Enables Efficient Sunlight‐Induced Photooxidation

Photooxidation under sunlight has potential in organic synthesis, bacterial killing, and organic waste treatment. Photosensitizers (PSs) can play an important role in this process. High ¹O₂ generation efficiency and excellent photostability under sunlight, as well as easy recyclability are ideal properties for PSs, but are not easy to achieve simultaneously. Herein, a pure organic porous conjugated polymer PS, CPTF, shows great photostability, large specific surface area, and high ¹O₂ generation efficiency under sunlight for photooxidation. For the oxidation of aromatic aldehyde to aromatic acid, the PS catalyst shows excellent recyclability, and enables solvent‐free reactions in high yields both under direct sunlight and simulated AM 1.5G irradiation. In addition, the successful application of CPTF as an antibacterial agent and organic waste decomposition under simulated AM 1.5G irradiation indicates the potential of CPTF in sunlight‐induced waste water treatment.     

Gas chromatography–triple quadrupole tandem mass spectrometry: a powerful tool for the (ultra)trace analysis of multiclass environmental contaminants in fish and fish feed

A new method for rapid determination of 73 target organic environmental contaminants including 18 polychlorinated biphenyls, 16 organochlorinated pesticides, 14 brominated flame retardants and 25 polycyclic aromatic hydrocarbons in fish and fish feed using gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC–MS/MS) was developed and validated. GC–MS/MS in electron ionization mode was shown to be a powerful tool for the (ultra)trace analysis of multiclass environmental contaminants in complex matrices, providing measurements with high selectivity and sensitivity. Another positive aspect characterizing the newly developed method is a substantial simplification of the sample preparation, which was achieved by an ethyl acetate QuEChERS (quick, easy, cheap, effective, rugged and safe) based extraction followed by silica minicolumn clean-up. With use of this sample preparation approach the sample laboratory throughput was increased not only because six samples may be prepared in approximately 1 h, but also because all the above-mentioned groups of contaminants can be determined in a single GC–MS/MS run. Under the optimized conditions, the recoveries of all target analytes in both matrices were within the range from 70 to 120 % and the repeatabilities were 20 % or less. The method quantification limits were in the range from 0.005 to 1 μg kg^–1 and from 0.05 to 10 μg kg^–1 for fish muscle tissue and fish feed, respectively. The developed method was successfully applied to the determination of halogenated persistent organic pollutants and polycyclic aromatic hydrocarbons in fish and fish feed samples.     

Versatile photosensitization system for 1O2-mediated oxidation of alkenes based on nafion-supported platinum(II) terpyridyl acetylide complex

[structure: see text] Platinum(II) terpyridyl acetylide complex (1) was incorporated into Nafion membranes as a photosensitizer, and the Nafion was immersed in an aqueous or organic solution of 7-dehydrocholesterol, alpha-pinene, or cyclopentadiene. This photosensitizer system can generate singlet oxygen ((1)O(2)) in high quantum yield to oxidize the alkenes in the solution outside the Nafion and can be easily removed from the reaction vessel at the end of the photooxidation.     

纳米二氧化钛气相光催化降解三氯乙烯

采用气相色谱－质谱联用方法,Ｘ射线光电子能谱和程序升温脱附方法研究了纳米二氧化钛表面三氯乙烯的气相光催化降解反应。检测到四种新的含三个碳原子的中间体,说明三氯乙烯在反应过程中发生了Ｃ＝Ｃ双键的裂解及加成反应。研究表明,水蒸气对降解反应的影响不公与水蒸气的浓度有关,还与催化剂对水的吸收能力有关。反应副产物在催化剂表面的积累是导致催化剂活性降低的主要原因。催化剂的Ｘ射线光电子能谱显示,反应后催化剂表面     

Aerosol-assisted submicronγ-Fe2O3/C spheres as a promising heterogeneous Fenton-like catalyst for soil and groundwater remediation:Transport,adsorption and catalytic ability

This research reports a novel heterogeneous Fenton-like catalyst which could freely move through the model sediments and easily seize the pollutants in addition to efficiently catalyze H2O2,well suitable for soil and groundwater remediation.Herein,submicron y-Fe2O3/C spheres were synthesized through a facile one-step aerosol-based process.In a series of column tests,these spheres exhibit better transport ability due to their optimal size,conforming to the prediction by the Tufenkji-Elimelech filtration theo ry.Meanwhile,y-Fe2O3/C spheres could act as a strong adsorbent for organic pollutants owing to the presence of carbon,thereby providing a driving force to gather contaminants into their vicinity and facilitating the reaction.In addition,immobilization of y-Fe2O3 nanoparticles into carbon spheres protects iron oxides from aggregation,and thus retains the number of active sites for catalytic decomposition of H2O2.Hence,the system containing the as-prepared y-Fe2O3/C spheres and H2O2 shows the high removal efficiency and degradation efficiency in the remediation of recalcitrant organic contaminants such as methylene blue and sulfamethoxazole.     

Membrane-moderated stripping process for removing VOCs from water in a composite hollow fiber module

The “stripmeation” process for removing volatile organic compounds (VOCs) from water has been introduced and studied. An aqueous solution of the VOC is passed through the bores of hydrophobic microporous polypropylene hollow fibers having a plasma polymerized silicone coating on the fiber outside diameter; a vacuum is maintained on the shell side of the fiber. The VOC is stripped into the gas-filled pores of the hydrophobic substrate, permeates through the nonporous silicone skin and is recovered by condensation of the shell-side permeate stream. Removal of trichloroethylene (TCE) present in a concentration range 200–1040 ppm has been studied at 25°C. Process performance has been obtained over a range of flow rates. The observed TCE permeation and removal behavior has been modeled using a resistances-in-series approach; the two important resistances are the tube-side aqueous boundary layer resistance and the vapor permeation resistance of TCE through the silicone coating. Employing the known Graetz solution for the tube-side flow and the measured vapor permeation resistance of TCE, values of the overall TCE mass-transfer coefficient have been obtained. These values compare well with the experimental values. The conventional pervaporation process where the liquid feed solution is in contact with the nonporous silicone membrane has also been studied by passing the feed on the shell side. The tube-side feed-based operation performs much better than the shell-side based operation.     

Effects of glutathione peroxidase and catalase on hemolysis and methemoglobin modifications induced by photooxidized psoralen

Psoralen photooxidation products (POP products) were obtained by UVA irradiation (365 nm, 180-640 W/m2) of an aqueous psoralen solution with fluences of 0-800 kJ/m2. Preincubation of POP products with glutathione peroxidase (GSHPer) or catalase, as well as presence of catalase during UVA irradiation of the aqueous psoralen solution did not influence their hemolytic activity. However, both GSHPer and catalase inhibited POP-induced conversion of methemoglobin. This indicates that hydrogen peroxide and psoralen peroxides destructible by GSHPer, which are being produced during psoralen photooxidation, do not possess hemolytic activity. Furthermore, hydrogen peroxide does not appear to serve as an intermediate in the process of hemolysin formation. Hydrogen peroxide generated during psoralen photooxidation is apparently the main POP product responsible for MetHb conversion.     

Photooxidation of poly(N-vinylpyrrolidone) (PVP) in the solid state and in aqueous solution

The photooxidation of poly(N-vinylpyrrolidone) (PVP) in the solid state and in an aqueous solution has been studied under irradiation at long wavelengths (at λ ≥ 300 nm) and in the presence of oxygen, as these conditions of irradiation are those of natural outdoor aging. Infrared spectroscopy was used to follow the photochemical evolution of the polymer either for solid films of PVP or for PVP irradiated in an aqueous solution. Chemical treatments (NH₃, SF₄) were carried out on the photooxidized samples, and aqueous solutions of PVP were characterized by viscometry and size exclusion chromatography (SEC). Based on photooxidation results obtained in both the solid state and in an aqueous solution, a general mechanism that accounts for the main routes of oxidation is proposed. It was shown that the rates of oxidation and the stoichiometries of the reactions were strongly influenced by the physical state of the polymer (solid state or aqueous solution).     

Aqueous solubility data for pressurized hot water extraction for solid heterocyclic analogs of anthracene, phenanthrene and fluorene

We report the aqueous solubilities of phenanthrene and several solid three-ring aromatic heterocycles (phenanthridine, acridine, phenazine, thianthrene, phenothiazine, phenoxathiin, phenoxazine, carbazole, dibenzofuran, dibenzothiophene, and 4,6-dimethyldibenzothiophene) at temperatures ranging from 313K to the solute melting point and at a pressure of 5MPa. The data were measured by dynamic saturation method using an in-house-assembled apparatus for pressurized hot water extraction (PHWE). The solute from a known mass of the saturated aqueous solution was transferred to an organic solvent (hexane or toluene), and the organic phase was analyzed by GC/MS. In any of the solutes, the GC/MS records did not indicate any noticeable decomposition within the temperature range of the measurements. The resultant solubilities were converted to activity coefficients of the individual solutes in saturated aqueous solutions, and the results are discussed in terms of temperature and type/number of heteroatoms.     

Efficient removal of cadmium and 2-chlorophenol in aqueous systems by natural clay: Adsorption and photo-Fenton degradation processes

Adsorption and photo-Fenton processes were used as handy tools to ascertain the capability of natural clays to remove cadmium (Cd) and 2-chlorophenol (2-CP) from aqueous solution. Natural Fe-rich clay collected from Tejera-Esghira in Medenine area, south Tunisia, was used as a catalyst in the heterogeneous photo-Fenton oxidation of 2-CP in aqueous solution. Clay samples were acid activated to improve their adsorptive capacity for the removal of Cd. Experimental results indicated that the adsorption of Cd ions onto natural red clay of Tejera-Esghira followed the pseudo-second-order kinetic model. Langmuir model was found to describe the equilibrium data with the calculated maximum adsorption capacity of 23.59 mg g^?1 for acid-activated clay. Photo-Fenton experiments proved high activity of the natural clay catalyst, which was able to completely degrade the phenol present in the treated solution after 30 min and in the presence of ultraviolet light C (UV-C). Total organic carbon and gas chromatography analysis confirmed a 2-CP degradation mechanism toward an almost complete mineralization of the organic compound.