Extraction of cloransulam-methyl from soil with subcritical water and supercritical CO2

Cloransulam-methyl was extracted from soil samples with supercritical CO2, subcritical water and conventional organic solvents. Supercritical CO2 was less efficient than conventional organic solvents; polarity modifiers had no impact on extraction efficiency. Extraction with supercritical CO2 exhibited a strong temperature dependence. Water was as effective as strong organic solvents for the extraction of cloransulam-methyl; however cloransulam-methyl hydrolyzed when extracted at 150 degrees C. Extraction temperature was the most important variable in increasing the efficiency and rate of extraction, while extraction pressure was not a significant variable.     

Photosensitized degradation of organic pollutants in water: processes and analytical applications

Photosensitized degradation has been used to remove a broad range of organic pollutants, generally with mineralization to CO₂ and other inorganic products such as Cl⁻ and . TiO₂ and Fe³⁺ are the photosensitizers mainly used to accelerate the degradation of persistent organic chemicals. Various analytical techniques were used to identify the degradation products and to monitor the degradation kinetics. Chromatographic techniques such as high-performance liquid chromatography (HPLC), gas chromatography (GC) and ion-exchange were used. Other analytical techniques, such as total organic carbon analysis, UV–visible spectrophotometry, spectrofluorimetry, and potentiometry, were also used. When the photodegradation is carried out in water, extraction methods such liquid–liquid extraction or solid-phase extraction need to be used, followed by GC or HPLC analysis. We review the analytical methods used for the identification of the products formed in photodegradation studies. Kinetic studies of the degradation are also reported.     

Comparison of extraction procedures for the determination of arsenic and other elements in lobster tissue by inductively coupled plasma mass spectrometry

A variety of extraction procedures were evaluated for the extraction of arsenic and other analytes from lobster tissue samples using inductively coupled plasma mass spectrometry (ICP-MS) detection. Soxhlet, room temperature mixing, sonication, microwave assisted, supercritical carbon dioxide and subcritical water extractions were evaluated for a variety of solvent systems and optimum conditions determined using a partially defatted Lobster Hepatopancreas marine certified reference material, TORT-2 (National Research Council of Canada). The solubility trends and solvents into which the analytes extracted gave an indication as to the polar/non-polar nature of the compounds present. Analytes that prefer water are probably more polar or inorganic, while those preferring methanol solutions are less polar or organic in nature. Arsenic, cadmium, cobalt, molybdenum and selenium were probably all present in TORT-2 in both polar inorganic and non-polar organic forms. While TORT-2 may have contained similar amounts of selenium in both forms, the results suggested that more of the arsenic was present as less polar or more organic compounds, and cobalt existed mainly as more polar or inorganic species. Most of the extraction techniques suggested that, although there may be some less polar organic forms present, more of the cadmium was probably present as polar inorganic compounds. Additionally, most techniques indicated that molybdenum was possibly all less polar or more organic in nature. In general, microwave assisted extraction (MAE) yielded comparable or improved recoveries for all of the analytes monitored and usually required less solvent. Additionally, MAE proved to be the mildest, fastest, least complicated and most reproducible extraction technique evaluated. MAE at 75 degrees C for 2 min exposure time yielded quantitative recovery of arsenic from TORT-2. These conditions were evaluated for lobster tissue samples purchased from a local restaurant. Separate evaluation of the lobster meat and organs resulted in quantitative recoveries of arsenic from both tissue samples. The results indicated that the extraction efficiencies might have some dependence upon the extraction technique, extraction conditions, analyte, solvent, and sample matrix.     

微波辅助萃取应用研究进展

近年来关于微波辅助萃取(MAE)与其他各种样品前处理技术的结合使用,以及与多种检测技术在线联用的研究越来越多,此外离子液体等新型绿色溶剂作为萃取剂在MAE中的应用也开始得到广泛关注.本文综述了近几年微波辅助萃取在环境、天然产物提取、食品和药物分析领域的应用情况,并对其将来的发展进行了展望.     

Microwave-assisted extraction of C60 and C70 from fullerene soot

Microwave-assisted extraction (MAE) was examined as an alternative to the traditional Soxhlet method of extracting C₆₀ and C₇₀ from fullerene soot. MAE of 0.20 g of fullerene soot with 95:5 toluene–acetonitrile yielded greater than 7.8 mg of C₆₀ and greater than 0.54 mg of C₇₀ in 4 min with no further increase in yield after 30 min of irradiation. By comparison, exhaustive Soxhlet extraction of the same size sample with the same solvent yielded 7.1 mg of C₆₀ and 0.58 mg of C₇₀ in 340 min. Reextraction by MAE of soot initially extracted by Soxhlet increased the yield of Soxhlet alone. Although MAE was limited to less than 0.5-g sample per extraction vessel, multiple samples were extracted with minimal increased extraction time and no reduction in the amount of material recovered.     

Extraction of Ni(II) by n-dodecanoic acid dissolved in toluene

The extraction of Ni(II) from nitrate medium of ionic strength 2.0 mol · dm⁻³ by n-dodecanoic acid (HA) dissolved in toluene has been studied at 293 K. Distribution measurements of the metal ion in a wide range of pH and carboxylic acid concentration have been performed. Experimental data, treated by different graphical methods as well as numerically by the LETAGROP-DISTR program, have been explained assuming the presence in the organic phase of the species NiA₂, NiA₂(HA)₂, [NiA₂(HA)₂]₂ and [NiA₂(HA)₂]₃. Equilibrium constants for the different extraction reactions are given.     

Comparison of microwave-assisted extraction of triazines from soils using water and organic solvents as the extractants

Microwave-assisted extraction (MAE) for the separation of atrazine, simazine and prometryne from synthetic soil samples, using water and some organic solvents as the extractants, was studied in detail. The effects of the soil matrix, the soil moisture and the pH of the aqueous extraction system on the MAE efficiency were also studied. It was found that the three triazines could be efficiently extracted under the conditions of 100% magnetron power output (600 W), the first grade of pressure (from 0.1 MPa to 0.5 MPa), 30 ml solvent and 4 min microwave heating with water or organic solvents, except for prometryne with dichloromethane solvent for 1-4 g sandy loam sample. This interesting result was explained by triazines' solubility in water, their sorption properties in soils and the ability of the solvent to absorb microwave energy. Finally, evaluation of the extraction efficiency, as well as the treatment and determination of MAE extracts, suggested that water, as a cheap, safe and environmentally friendly solvent, can be a good alternative to organic solvents, used as the extractants for MAE of triazines from soils.     

From polyoxometalates to polyoxoperoxometalates and back again; potential applications

This short review is concerned with sustainable chemistry and recent research progress in catalysis systems for the use of aqueous hydrogen peroxide or dioxygen. Some achievements in the development of catalysts for epoxidations and for carbon–carbon bond cleavage are presented. Special emphasis is placed on fully inorganic systems, some with the dimeric moiety [M₂O₂(μ-O₂)₂(O₂)₂], (M = V, Mo, W) which have more scope than those containing organic ligands or supports, however robust. Oxoperoxometalate species with or without assembling ligands can be used for homogeneous, two-phase and phase-transfer catalyses and to prepare mesoporous materials (M-MCM-41, M-SBA-15, etc.) and supported catalysts for effective immobilization of activated metal peroxo complexes. Moreover, the decomposition of molybdenum and vanadium oxoperoxo species in water and phosphoric acid leads to an elegant method for preparing H_3+n[PMo_12−nV_nO₄₀]·aq (n = 2–9) at room temperature, avoiding the tedious synthesis with diethyl ether extraction. Spectrometric, structural and reactivity data on the precursor complexes lead to a more rational approach to catalysis systems and to the discovery of novel classes of precursors and/or catalysts for the selective transfer of oxygen to organic substrates.     

黄芩中黄芩苷的亚临界水提取及高效液相色谱分析

建立了黄芩药材中黄芩苷的亚临界水提取 高效液相色谱测定方法。分别考察了温度、压力、提取时间、提取物颗粒度、溶剂比等因素对提取量的影响,并与有机溶剂提取法比较。结果表明,当两者具有相同的提取效果时,亚临界水提取法的提取时间及提取溶剂的消耗量大大减少,避免了使用有机溶剂造成的污染。黄芩苷提取最佳条件为:样品颗粒度80～100目,溶剂比0.2 mL/mg ,5 MPa,130 ℃保持10 min。并通过提取 高效液相色谱联机分析实现了对提取物的实时监测。该技术有望成为从中药材中提取脂溶性成分的有效方法。     

UV-Vis/H2O2/草酸铁络合物法在水处理中的应用

介绍了各光Fenton法的运行机理及存在的优缺点,综述了UV-Vis/H₂O₂/草酸铁络合物法在水处理中的应用状况,并对其今后的发展趋势进行了阐述.UV-Vis/H₂O₂/草酸铁络合物法是一种新的高级氧化技术,是对光Fenton法的发展,在处理高浓度难降解有机废水方面效果优于UV/Fe²⁺/H₂O₂法、UV/H₂O₂法、TiO₂法和WO₃法等,因其具有一定的利用太阳能的潜力,所以具有较好的应用前景.     

Microwave-assisted extraction: Application to the determination of emerging pollutants in solid samples

Flame retardants, surfactants, pharmaceutical and personal care products, among other compounds, have been the object of numerous environmental studies. In this chapter, the application of microwave-assisted extraction (MAE) in the development of analytical methods for several groups of organic compounds with growing concern as emerging pollutants has been considered. Compared to other extraction techniques, optimization of MAE experimental conditions is rather easy owing to the low number of influential parameters (i.e. matrix moisture, nature of the solvent, time, power, and temperature in closed vessels). The great reduction in the extraction time and solvent consumption, as well as the possibility of performing multiple extractions, increasing the sample throughput, can also be highlighted among MAE advantages. In summary, the study of several applications of MAE to environmental problems demonstrates that this technique constitutes a good alternative for the determination of organic compounds in environmental samples. It can be used as a rapid screening tool, and also to obtain detailed information on the sources, behaviour and fate of emerging pollutants in environmental matrices.     

小晶粒ZSM-5沸石的绿色、经济性合成

通过添加少量silicalite-1做为活性晶种在较宽的SiO₂/Al₂O₃比范围内制备得到了小晶粒ZSM-5沸石,对所得样品进行X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),N₂吸附-脱附,氨程序升温脱附(NH₃-TPD)以及吡啶吸附红外(Py-IR)表征。研究结果表明活性晶种能有效导向生成ZSM-5沸石,避免杂晶形成并可减小所得沸石的晶粒尺寸;所得ZSM-5在低硅铝比(SiO₂/Al₂O₃ ratio = 30)时呈纳米颗粒聚集体形貌,具有多级孔道结构性质;在较高硅铝比时(SiO₂/Al₂O₃ ratio = 60–120)呈小晶粒形貌,颗粒尺寸大约200 nm。值得注意的是由胶态晶种引入的少量TPAOH不完全堵塞沸石的微孔孔道,因此所得所有沸石均无需提前焙烧除去模板剂即可进行离子交换得到具有酸性的H型ZSM-5沸石,所得酸性H型ZSM-5沸石具有和常规方法得到的相同SiO₂/Al₂O₃比的ZSM-5相似的酸类型、强度和酸量,在催化甲醇转化制备烯烃时呈现出相似的甲醇转化率和烯烃选择性。与常规ZSM-5制备方法比较,该方法能够大大减少模板剂的使用量,避免了样品离子交换前的焙烧,方法绿色清洁、成本低廉,具有很好的潜在的工业应用前景。     

三丁基氧化膦-离子液体体系萃取UO2(NO3)2的机理和选择性

研究了三辛基氧化膦(TOPO)和三丁基氧化膦(TBPO)在离子液体(ILs) 1-烷基-3-甲基咪唑双三氟甲基磺酰亚胺盐(C_nmimNTf₂, n=2, 4, 6, 8)中萃取分离UO₂(NO₃)₂. TOPO-C₂mimNTf₂和TOPO-C₄mimNTf₂体系萃取UO₂(NO₃)₂时会出现三相, 而TBPO萃取UO₂(NO₃)₂的萃合物可以很好地溶解在所有离子液体中. 论文也考察了萃取过程中的萃取剂浓度效应、酸效应、盐效应. 水相加入HNO₃会降低萃取效率. 盐效应证明了萃取是一种阳离子交换机理. 水相中加入NO₃^-能够提高U的萃取, 这说明NO₃^-参与萃取. 选择性研究表明: 除了在高酸度下对Zr 的显著萃取, TBPO-C₄mimNTf₂萃取体系在低酸度下对U呈现较好的选择性; 去除U后, 在低酸度下该体系对三价Nd 仍保持较好的选择性. 通过定量比较离子液体中NO₃^-进入量, 电喷雾质谱(ESI-MS)和紫外光谱表征确定了TBPO-C_nmimNTf₂中萃取机理的差异性. 萃取中存在两种萃合物, 即UO₂(TBPO)₃(NO₃)⁺和UO₂(TBPO)₃²⁺, 其中UO₂(TBPO)₃(NO₃)⁺的比例从C₂mimNTf₂体系到C₈mimNTf₂体系逐渐增加.     

Comparisons of soxhlet extraction, pressurized liquid extraction, supercritical fluid extraction and subcritical water extraction for environmental solids: recovery, selectivity and effects on sample matrix

Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100 degrees C), supercritical fluid extraction (SFE) (1 h at 150 degrees C with pure CO2), and subcritical water (1 h at 250 degrees C, or 30 min at 300 degrees C). Although minor differences in recoveries for some PAHs resulted from the different methods, quantitative agreement between all of the methods was generally good. However, the extract quality differed greatly. The organic solvent extracts (Soxhlet and PLE) were much darker, while the extracts from subcritical water (collected in toluene) were orange, and the extracts from SFE (collected in CH2Cl2) were light yellow. The organic solvent extracts also yielded more artifact peaks in the gas chromatography (GC)-mass spectrometry and GC-flame ionization detection chromatograms, especially compared to supercritical CO2. Based on elemental analysis (carbon and nitrogen) of the soil residues after each extraction, subcritical water, PLE, and Soxhlet extraction had poor selectivity for PAHs versus bulk soil organic matter (approximately 1/4 to 1/3 of the bulk soil organic matter was extracted along with the PAHs), while SFE with pure CO2 removed only 8% of the bulk organic matrix. Selectivities for different compound classes also vary with extraction method. Extraction of urban air particulate matter with organic solvents yields very high concentrations of n- and branched alkanes (approximately C18 to C30) from diesel exhaust as well as lower levels of PAHs, and no selectivity between the bulk alkanes and PAHs is obtained during organic solvent extraction. Some moderate selectivity with supercritical CO2 can be achieved by first extracting the bulk alkanes at mild conditions, followed by stronger conditions to extract the remaining PAHs, i.e., the least polar organics are the easiest organics to extract with pure CO2. In direct contrast, subcritical water prefers the more polar analytes, i.e., PAHs were efficiently extracted from urban air particulates at 250 degrees C, with little or no extraction of the alkanes. Finally, recent work has demonstrated that many pollutant molecules become "sequestered" as they age for decades in the environment (i.e., more tightly bound to soil particles and less available to organisms or transport). Therefore, it may be more important for an extraction method to only recover pollutant molecules that are environmentally-relevant, rather than the conventional attempts to extract all pollutant molecules regardless of how tightly bound they are to the soil or sediment matrix. Initial work comparing SFE extraction behavior using mild to strong conditions with bioremediation behavior of PAHs shows great promise to develop extraction methodology to measure environmentally-relevant concentrations of pollutants in addition to their total concentrations.     

Elution of organic solutes from different polarity sorbents using subcritical water

The intermolecular interactions between organic solutes and sorbent matrices under subcritical water conditions have been investigated at a pressure of 50 bar and temperatures ranging from 50 to 250°C. Both polar and nonpolar organics (chlorophenols, amines, n-alkanes, and polycyclic aromatic hydrocarbons) and five different sorbent matrices (glass beads, alumina, Florisil, silica-bonded C₁₈, and polymeric XAD-4 resins) were used. From the same matrix, the polar solutes always eluted at lower temperatures, while the moderately polar and nonpolar solutes only eluted at higher temperatures. Similar to matrix effects previously observed using supercritical carbon dioxide, the sorbent type greatly influenced the elution efficiency under subcritical water conditions. Lower temperatures are sufficient to elute a particular solute from glass beads, alumina, and Florisil, but higher temperatures (less polar water) are needed to elute the same solute from silica-bonded C₁₈. The highest temperatures were required to elute aromatic organics from XAD-4. These matrix effects demonstrate that, while low temperature water can break inert or dipole interactions between solutes and glass beads, alumina, and Florisil, higher temperature water is required to interrupt the van der Waals attractions between solutes and silica-bonded C₁₈, and even higher temperatures needed to overcome the π-electron interactions between aromatic solutes and XAD-4.     

Microwave- and ultrasound-assisted extraction of vanillin and its quantification by high-performance liquid chromatography in Vanilla planifolia

Microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE) and conventional extraction of vanillin and its quantification by HPLC in pods of Vanilla planifolia is described. A range of nonpolar to polar solvents were used for the extraction of vanillin employing MAE, UAE and conventional methods. Various extraction parameters such as nature of the solvent, solvent volume, time of irradiation, microwave and ultrasound energy inputs were optimized. HPLC was performed on RP ODS column (4.6 mm ID x 250 mm, 5 microm, Waters), a photodiode array detector (Waters 2996) using gradient solvent system of ACN and ortho-phosphoric acid in water (0.001:99.999 v/v) at 25 degrees C. Regression equation revealed a linear relationship (r2 > 0.9998) between the mass of vanillin injected and the peak areas. The detection limit (S/N = 3) and limit of quantification (S/N = 10) were 0.65 and 1.2 microg/g, respectively. Recovery was achieved in the range 98.5-99.6% for vanillin. Maximum yield of vanilla extract (29.81, 29.068 and 14.31% by conventional extraction, MAE and UAE, respectively) was found in a mixture of ethanol/water (40:60 v/v). Dehydrated ethanolic extract showed the highest amount of vanillin (1.8, 1.25 and 0.99% by MAE, conventional extraction and UAE, respectively).     

Determination of Lignans in Schisandra sphenanthera and Schisandra chinensis Using Ionic Liquid-based Ultrasonic-assisted Extraction and High-performance Liquid Chromatography

A green, rapid and precise sample pretreatment technique, IL-based UAE(ionic liquid-based ultrasonic-assisted extraction), was coupled with high-performance liquid chromatographic separation to identify the main effective components in Schisandra sphenanthera(S. sphenanthera) and Schisandra chinensis(S. chinensis) including schisantherin A, schisandrin A, and deoxyschizandrin. Four different types of ionic liquids have been investigated, finally[C₆MIM] [BF₄] was used as the extraction solvent. A powder form of S. sphenanthera and S. chinensis was mixed with the[C₆MIM] [BF₄] to produce a suspension. This suspension was ultrasonically extracted in a water bath at room temperature. Several of the process parameters were optimized, including the type of ionic liquid used and its volume, the sample amount, the size of the sample particle, the extraction time, etc. HPLC calibration curves were established for all the analytes and proved to be linear(r>0.9999). The lowest detection level for schisandrin A was 0.12 μg/mL, for schisantherin A was 0.08 μg/mL, and for deoxyschizandrin was 0.10 μg/mL. The recoveries of the target compounds were from 74.19% to 109.33%. The standard deviations for detection were generally no more than 6.31%. In contrast to conventional extraction methods, the IL-based UAE did not involve volatile organic volatile solvents, and the analysis time, required sample and solvent volumes were also lower than those of the conventional techniques.     

Supported liquid membranes (SLM) for recovery of bismuth from aqueous solutions

In this study, the extraction of Bi(III) from synthetic solutions of 2 M H₂SO₄/0.5 M HCl by supported liquid membranes (SLM) using tri-n-octylphosphine oxide (Cyanex 921) as extractant is reported. First, the nature of the Bi(III)/Cyanex 921 solvates extracted to organic phase (in a solvent extraction system) was determined by the slope method. It was found that Bi(III) reacts with 2 molecules of Cyanex 921 to form the solvate BiCl₃·2Cyanex 921. In the recovery of Bi(III) by the SLM system, parameters that influence extraction efficiency were evaluated, including: support, feed solution and stripping solution nature, and extractant concentration in the organic phase which impregnates the support. Results indicate that Cyanex 921 dissolved in kerosene is not able to extract Bi(III) from H₂SO₄ media. Moreover, transfer of H₂SO₄ was observed. HCl addition to the feed solution up to a maximum concentration of 0.5 M increases Bi(III) extraction. Further increase in HCl concentration causes a decrease in Bi(III) transfer. Likewise, the concentration of Cyanex 921 in the SLM organic phase which produced the maximum Bi(III) extraction was found to be 0.3 M. The performance of H₂O and 0.2 M H₂SO₄ as stripping solutions was evaluated, and it was found that only H₂SO₄ enabled Bi(III) transfer.     

Extraction of Fe(III) by n-dodecanoic acid dissolved in toluene

The extraction of Fe(III) from a nitrate medium of ionic strength 1.0 mol dm⁻³ by n-dodecanoic acid (HA) dissolved in toluene has been studied by distribution measurements. Experimental data, treated by different graphical and numerical methods, have been explained assuming the extraction of the species (FeA₃)₃ into the organic phase as well as the formation of a Fe(III)-HA complex in the aqueous phase.     

X型Gemini表面活性剂改性类水滑石的制备及其吸附对甲酚性能

传统表面活性剂-类水滑石(HTlc)纳米复合物可有效吸附水中主要有机污染物酚类污染物,如酚类污染物,以高性能Gemini双子表面活性剂代替传统表面活性剂有望提高其去除效率。本文采用剥离-重组法制备了X型Gemini表面活性剂(MXC_6)-HTlc纳米复合物,并采用粉末X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、比表面和元素分析等技术手段对样品进行了表征。结果表明,MXC_6成功重组于HTlc层间。分别从吸附动力学和热力学研究了MXC_6-HTlc纳米复合物对对甲酚的吸附行为:吸附动力学曲线符合准一级动力学方程;吸附等温线符合Linear方程;吸附量显著高于HTlc,且随p H值和温度的增加而降低。实验表明,MXC_6-HTlc纳米复合物是一种新型高效水中酚类污染物处理剂。