18O/16O and 13C/12C Fractionation During the Reaction of Carbonates with Phosphoric Acid: Effects of Cationic Substitution and Reaction Temperature

Abstract

The factors for ¹⁸O/¹⁶O fractionation between carbonates and CO₂ gas produced by the dissolution of the carbonates in phosphoric acid (sealed vessel method) have been investigated as a function of reaction temperature (20–90°C) and cationic substitution in the solid. Synthetic CaCO₃, Ca_0.75 Mn_0.25 CO₃, MnCO₃, BaCO₃ and SrCO₃ powders, and a natural kutnahorite sample were used as solids. The δ¹⁸O values of the gaseous CO₂ liberated by the reaction with phosphoric acid decrease with increasing temperature and seem to be a linear function of T(°K)^?2. The slopes are specific for different carbonates. No temperature-depended ¹³C/¹²C fractionation seems to exist.     

我国几种地带性土壤中磷素形态的研究

探明土壤磷素的存在形态,有助于揭示其在环境中的累积、迁移和转化过程及生物有效性。目前,在大尺度样带上开展土壤磷素形态空间变异规律的研究较少。本研究中,沿纬度方向采集了我国东部不同气候带分布的7种地带性林地土壤（包括寒温带的棕色针叶林土、中温带的暗棕壤、暖温带的棕壤、北亚热带的黄棕壤、中亚热带的黄壤、南亚热带的赤红壤和热带的砖红壤）,将化学浸提法与溶液磷-31核磁共振（31P NMR）波谱法相结合,分析了土壤中磷素形态以及与其他土壤性质之间的关系,以期为阐明土壤磷素形态的空间变异性及其驱动因素提供基础资料。结果表明：供试土壤中,全磷、有效磷、无机磷和有机磷的含量范围分别为179.8～825.2,2.41～15.3,92.6～351.2和14.7～474.4 mg·kg-1,其中活性、中等活性、中等稳定性和高稳定性有机磷组分的含量范围分别为1.38～30.9,8.63～213.7,3.01～32.2和1.73～199.2 mg·kg-1。根据溶液31P NMR波谱,鉴定出供试土壤中含有无机形态的磷素即正磷酸盐和焦磷酸盐,同时也鉴定出了磷酸单酯、磷酸二酯和膦酸盐等有机形态磷素的存在,其中磷酸单酯中又鉴定出了新-肌醇六磷酸、D-手性-肌醇六磷酸、RNA单核苷酸、α-磷酸甘油、肌-肌醇六磷酸、β-磷酸甘油和鲨-肌醇六磷酸,磷酸二酯中又鉴定出了DNA的存在;所有土壤中均未检测出多聚磷酸盐的存在,除棕色针叶林土和暗棕壤外的其他土壤中未检测出膦酸盐的存在,而赤红壤中未检测出DNA的存在;无机形态的磷素以正磷酸盐为主,而有机形态的磷素则以磷酸单酯为主。总体来看,无论化学浸提法还是溶液31P NMR波谱法,从寒温带的棕色针叶林土到热带的砖红壤,全磷、有效磷、无机磷、有机磷及其组分的含量均呈现下降趋势。溶液31P NMR波谱与化学浸提法鉴定的磷素形态之间存在相关关系,其中正磷酸盐与活性有机磷的关系最为密切,磷酸单酯和膦酸盐与中等活性有机磷的关系最为密切,而焦磷酸盐和磷酸二酯与中等稳定性有机磷的关系最为密切。与化学浸提法相比,溶液31P NMR波谱法能从详细的分子水平上揭示土壤磷素形态的空间变异规律。     

Methodology for Bioassay-Directed Fractionation Studies of Air Particulate Material and Other Complex Environmental Matrices

Abstract

A normal phase HPLC methodology using a semi-preparative polyaminocyano column in conjunction with a selection of short-term genotoxicity assays has been developed for bioassay-directed fractionation studies of complex environmental mixtures. To illustrate the effectiveness of this methodology, an organic extract prepared from respirable air particulate samples collected in Hamilton, Canada was separated into a non-polar aromatic fraction and a polar aromatic fraction using a combination of alumina and Sephadex LH20 chromatography. These fractions were evaluated for their genotoxic potential using the Salmonella/microsome (Ames) assay with six different strains of Salmonella.

The non-polar aromatic fraction was analyzed by normal phase HPLC and the eluent was collected in one-minute subfractions; these subtractions were bioassayed in three different Salmonella strains (YG1021 -S9, YG1024 -S9 and YG1029 +S9) to afford three different mutation profiles of this sample. Some subfractions which exhibited high mutagenic responses were subjected to further chemical analyses using GC/MS in order to identify those compounds responsible for the genotoxic responses. The nitroarene compounds 2-nitrofluoranthene, 1-nitropyrene and 2-nitropyrene and higher molecular weight polycyclic aromatic hydrocarbons such as benzo[a]pyrene and indeno[l,2,3-cd]pyrene were identified and quantified in some of the biologically active subfractions. The normal phase gradient conditions afforded very reproducible retention times for a series of polycyclic aromatic standards with a broad range of compound polarities. In addition, polycyclic aromatic hydrocarbons (PAH) were observed to elute from the normal phase HPLC column in a series of peaks; successive peaks contained PAH of increasing molecular weight while any individual peak was shown to contain PAH of the same molecular weight.     

Separation and characterization of gold nanoparticle mixtures by flow-field-flow fractionation

We show that using asymmetric flow-field-flow fractionation and UV-vis detector it is possible to separate, characterize, and quantify the correct number size distribution of gold nanoparticle (AuNP) mixtures of various sizes in the 5-60 nm range for which simple dynamic light scattering measurements give misleading information. The size of the collected nanoparticles fractions can be determined both in solution and in the solid state, and their surface chemistry characterized by NMR. This method will find widespread applications both in the process of "size purification" after the synthesis of AuNP and in the identification and characterization of gold-based nanomaterials in consumer products.     

Probing the early stages of thermal fractionation by successive self‐nucleation and annealing performed with fast scanning chip‐calorimetry

The thermal fractionation kinetics of a linear low‐density polyethylene (LLDPE) during Successive Self‐Nucleation and Annealing (SSA) is investigated by fast scanning chip‐calorimetry (FSC), by systematically varying the holding times (t_s) at each fractionation temperature (T_s). The range of explored fractionation times spans four orders of magnitude, from 0.001 to 10 s. Discernible thermal fractions are already detected in the very early stages of the process, at t_s shorter than one second. As t_s increases, the melting endotherm after SSA indicates a progressive lamellar thickening and narrowing of the thicknesses distribution of the various crystalline fractions. The largest variations are observed for the families of crystals containing the longest crystallizable sequences, which also undergo a change of their relative content as a consequence of self‐nucleated crystallization at T_s. The quality of the thermal fractionation obtained in 10 seconds with FSC is equivalent to that of conventional differential scanning calorimetry SSA (t_s = 300 s). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2200–2209     

Characterisation of the comonomer composition and distribution of copolymers using chemometric techniques

Chemometric techniques have been applied to FTIR and DSC data to correlate polymer composition. Since structural differences in the polymers with only hydrocarbon structure, often cause subtle changes in spectra, the ability of chemometric techniques is required to discern these differences. FTIR spectra and thermal fractionation using DSC were measured for 28 types of polyethylenes (PE) varying in chain branching type, content and distribution. Unsupervised clustering methods such as principal component analysis (PCA) and supervised discriminant analysis were used to classify the PEs according to their structural class. The DSC data was the more successful in both classifying PEs according to their class. This revised version was published online in July 2006 with corrections to the Cover Date.     

Size-based analysis of incinerator fly ash using gravitational SPLITT fractionation, sedimentation field-flow fractionation, and inductively coupled plasma-atomic emission spectroscopy

Fly ash has been regarded as hazardous because of its high adsorption of toxic organic and/or inorganic pollutants. Fly ash is also known to have broad distributions of different chemical and physical properties, such as size and density. In this study, fly ash emitted from a solid waste incinerator was pre-fractionated into six sub-populations by use of gravitational SPLITT fractionation (GSF). The GSF fractions were then analyzed by sedimentation field-flow fractionation (SdFFF) and ICP–AES. SdFFF analysis showed the fly ash has a broad size distribution ranging from a few nanometers up to about 50 µm. SdFFF results were confirmed by electron microscopy. Inductively coupled plasma–atomic emission spectroscopy (ICP–AES) analysis of the GSF fractions showed the fly-ash particles contain a variety of inorganic elements including Ca, Si, Mg, Fe, and Pb. The most abundant in fly ash was Ca, followed by Si then Mg. No correlations were found between trace element concentration and particle size.     

Cytochrome c–dimyristoylphosphatidylglycerol interactions studied by asymmetrical flow field-flow fractionation

Lipid membranes are well recognized ligands that bind peripheral and integral proteins in a specific manner and regulate their function. Cytochrome c (cyt c) is one of the partner peripheral protein that binds to the lipid membranes via electrostatic and hydrophobic interactions. In this study, asymmetrical flow field-flow fractionation (AsFlFFF) was used to compare the interactions of cyt c with the acidic phospholipid 1,2-dimyristoyl-sn-glycero-3-phospho-rac-glycerol (DMPG), oleic acid (OA), and sodium dodecyl sulfate (SDS). The influence of pH and the cyt c–lipid molar mass ratios were evaluated by monitoring the diffusion coefficients and particle diameter distributions obtained for the free and lipid-bound protein. The hydrodynamic particle diameter of cyt c (pI 10) was 4.1 nm at pH 11.4 and around 4.2 nm at pH 7.0 and 8.0. Standard molar mass marker proteins were used for calibration to obtain the molar masses of free cyt c and its complexes with lipids. AsFlFFF revealed the binding of cyt c to DMPG and to OA to be mainly electrostatic. In the absence of electrostatic interactions, minor complex formation occurred, possibly due to the extended lipid anchorage involving the hydrophobic cavity of cyt c and the hydrocarbon chains of DMPG or SDS. The possibility of the formation of the molten globule state of cyt c, induced by the interaction between cyt c and lipids, is discussed.Electronic Supplementary Material Supplementary material is available for this article at     

Optimization of simulated moving bed chromatography with fractionation and feedback: Part II. Fractionation of both outlets

A new improvement based on outlet fractionation and feedback has been developed for simulated moving bed (SMB) chromatography. In this contribution, this fractionation and feedback SMB (FF-SMB) concept is extended to the general scenario which integrates a simultaneous fractionation of both outlet streams. A model-based optimization approach, previously adopted to investigate single fractionation, is extended to consider this flexible fractionation policy. Quantitative optimization studies based on a specific separation problem reveal that the double fractionation is the most efficient operating scheme in terms of maximum feed throughput, while the two existing single fractionation modes discussed in our previous study are also significantly superior to the conventional SMB operation. The advantages of the double fractionation extension are further demonstrated in terms of several more detailed performance criteria. In order to evaluate the applicability of the fractionation and feedback modification, the effect of product purity, adsorption selectivity, column efficiency and column number on the relative potential of FF-SMB over SMB is examined.     

Temporal variability of colloidal material in agricultural storm runoff from managed grassland using flow field-flow fractionation

This paper reports the use of flow field-flow fractionation (FlFFF) to determine the temporal variability of colloidal (<1 μm) particle size distributions in agricultural runoff waters in a small managed catchment in SW England during storm events. Three storm events of varying intensity were captured and the colloidal material in the runoff analysed by FlFFF. The technique had sufficient sensitivity to determine directly the changing colloidal profile over the 0.08–1.0 μm size range in the runoff waters during these storm events. Rainfall, total phosphorus and suspended solids in the bulk runoff samples were also determined throughout one storm and showed significant correlation (P < 0.01) with the amount of colloidal material. Whilst there are some uncertainties in the resolution and absolute calibration of the FlFFF profiles, the technique has considerable potential for the quantification of colloidal material in storm runoff waters.