The molecular composition of ambers

Bulk (elemental composition, IR, CP/MAS ¹³C NMR) and molecular (GC-MS) analyses have been performed on a series of ambers and resins derived from different locations (Dominican Republic, Philippines, Canada, Israel, New Zealand, Chile) having diverse botanical affinities (Araucariaceae, Hymenaea) and variable age (from Holocene to Early Cretaceous). No major differences have been observed from the elemental composition and the spectroscopic data; however, the molecular analyses of the solvent extractable fraction show that a specific mixture of components is present in each sample. These are mainly diterpenoid products that in general are also found abundantly in the higher plants from which the ambers and resins originate. Nevertheless, a direct relationship between major terpenoid constituents in fossil resins and precursor plant materials can only be established for the younger samples.Irrespective of the geographical or botanical origin of the ambers and resins, several common age-dependent molecular transformation trends can be recognized: (1) progressive loss of olefinic bonds (especially those located in exocyclic positions), (2) decrease of functionalized products, and (3) increasing proportion of aromatized components. However, even in the samples of older age (Cretaceous) the degree of aromatization is very low when compared with that of other higher-plant related materials such as fossilized woods or low rank coals. This indicates that maturation must involve essentially olefin polymerization processes instead of extensive aromatization.     

Chemical structural units of macromolecular coal components

Chemical degradations of coal resins, coal asphaltenes and coal residues have been performed with selective, non-oxidative reagents. The coal comprise samples a rank interval 0.30–1.21 %R_m. Degraded low-molecular-weight compounds were analyzed by GC-MS. The distributions of pentacyclic terpanes, isoprenoids, n-alkanes, acids and alcohols obtained as degradation products illustrate a considerable variability between the macromolecular coal fractions. A structural study on the molecular level of the degraded compounds from coal resins and coal asphaltenes show their potential to generate hydrocarbons during coalification process.     

Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation

Structural studies of a sulphur-rich kerogen and macromolecular oil fractions from the Monterey Formation were performed by selective sequential chemical degradation. The method provides low-molecular weight compounds as former building blocks of the network which allow detailed analyses on a molecular level. The degradation sequence is based on three subsequently performed reactions—a selective cleavage of sulphur bonds in the first step carried out with Ni(0)cene/LiAlD₄, an ether and ester bond cleavage (BCl₃), and an oxidation of aromatic entities by ruthenium tetroxide as a final step. Each step of this sequence afforded a considerable amount of low-molecular weight material which was separated chromatographically and studied by GC and GC/MS, while the high-molecular weight or insoluble fractions were subjected to the next reaction step.The chemical degradation products—hydrocarbons and carboxylic acids—are discussed in terms of incorporation into the macromolecular structure, distribution of heteroatomic bridges and the genetic relationships between the different macromolecular crude oil fractions and kerogen.Labelling experiments with deuterium provided evidence for a simultaneous linkage by oxygen and sulphur functionalities or by aromatic units and sulphur bonds of cross-linking macromolecular network constituents.The determination of sulphur positions in the macromolecule suggests early diagenetic sulphur incorporation into the biological precursor compounds and subsequent formation of a cross-linked network.     

Application of Non-Ionic Solid Sorbents (XAD Resins) for the Isolation and Fractionation of Water-Soluble Organic Compounds from Atmospheric Aerosols

A detailed procedure using non-ionic macropourous XAD-8 and XAD-4 resins is presented for the isolation and fractionation of aerosol water-soluble organic compounds (WSOC) from aerosol samples. The procedure entails adsorption of WSOC fraction onto XAD-8 and XAD-4 resins, desalting of the adsorbed organic material with ultra-pure water, elution of the retained organic matter with 40% MeOH solution and freeze-drying. Due to resin’s different properties and to certain hydrophobic/hydrophilic interactions between the resin polymers and the organic matter, two major fractions were obtained; namely the XAD-8 and the XAD-4 eluates. The XAD-8 eluate, which accounts for 55–60% of total aerosol WSOC, is represented by partially acidic compounds with significant hydrophobic moieties. The XAD-4 fraction holds few conjugated systems and a higher content of hydrophilic structures with low molecular size, and accounts for 9% of total WSOC. The isolated WSOC sub-fractions were nearly free from inorganic species, and successful recoveries of organic matter from the resins were accomplished. With this procedure the XAD-8 eluate yields a mixture representative of those WSOC that are highly conjugated compounds in atmospheric aerosols. It also allows a successful characterisation of the organic material by advanced analytical techniques without the interference of inorganic species present in the original sample of atmospheric particles.     

追溯最古老的琥珀——树脂植物的起源与演化

琥珀是一类有机宝石,其经济价值和科学意义日益受到重视.琥珀是植物树脂的化石形式.本文综述了现代的和已绝灭的产树脂植物的种类与地史分布.现代的产树脂植物包括松柏类和诸多被子植物科,现代松柏类如南洋杉科的琥珀最早可追溯至晚三叠世—早侏罗世,但在白垩纪中期至中新世的地层中更为丰富.始新世以来,热带和亚热带被子植物来源的琥珀开始占优势地位.绝灭的产树脂植物包括繁盛于石炭—二叠纪的科达类和髓木类种子蕨以及石炭纪以来出现并已绝灭的一些松柏类裸子植物.目前已知最早的琥珀产自晚石炭世地层(距今约3.2亿年).琥珀中含丰富的动植物化石,为研究地球生命的演化历史提供了重要材料.     

Preconcentration of trace multi-elements in water samples using Dowex 50W-x8 and Chelex-100 resins prior to their determination using inductively coupled plasma atomic emission spectrometry (ICP-OES)

This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace elements in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The optimum sample pH, eluent concentration and sample flow rates were found to 6, 3.0 mol L⁻¹ and 3.0 mL min⁻¹, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8 appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However, Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under optimized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%. The limits of detection and limits of quantification ranged from 0.01–0.39 μg L⁻¹ and 0.05–0.1.3 μg L⁻¹, respectively. The accuracy of the preconcentration method was confirmed by spike recovery test and the analysis of certified reference materials. The SPE method was applied for preconcentration of the analyte ions in tap water, bottled water and wastewater samples.     

金橙G螯合形成树脂分离富集地质样品中微量贵金属研究Ⅱ——铑的分离富集测定

主要报道了用金橙Ｇ螯合负载形成树脂分离富集地质样品中贵金属Ｒｈ的方法。在最佳试验条件下Ｒｈ的回收率可达９５％～１０５％之间；其相对标准偏差为４．４９％；百分相对误差较小，为－２．４％；方法无系统误差；用硫脲洗脱，该负载形成树脂不被破坏，重复使用５次，树脂均未见异常，均能定量回收，回收率在９８．５％～１０４％之间，符合要求。说明，这种负载形成树脂也较稳定，也可用于实际地质样品中微量贵金属的分离富集     

The geochemistry of exinites—1. Evaluation of spectral fluorescence of a series of modern resins and fossil resinites

A series of six fossil resins and four modern resins have been analysed using microscope-based spectral fluorescence methods, in addition to a preliminary study of the chemical composition of these samples using infrared spectroscopy and pyrolysis-gas chromatography. This study illustrates problems encountered during the measurement of spectral fluorescence of resins and resinite kerogens using conventional microscopy methods. Most notable, alteration of fluorescence significantly influences spectral measurements. Further, fossilized resins within rocks are complex mixtures of resinite and bitumen. Pre-extraction of resinites prior to petrographic analysis resulted in somewhat more uniform spectral fluorescence results.Spectral fluorescence of recent resins used in this study could be used to distinguish angiosperm from gymnosperm derived resinite kerogens. Distinction of plant class source of resinite kerogens, however, is more difficult using this method and is considered genarally unreliable.     

离子交换树脂法分离沉积物中锶和钕的影响因素研究

Sr和Nd同位素是地质学研究中经典的同位素定年和示踪体系。传统沉积物中Sr和Nd分离方法通常是利用AG50W-X8树脂分离Sr与稀土元素(REEs),再用Sr和Ln特效树脂分别对Sr和Nd纯化,但对于Fe元素含量较高的沉积物样品,该方法对REEs的洗脱率偏低,仅有50%。另外,AG50W-X8树脂高度、洗脱酸种类、Sr特效树脂淋洗酸体积以及Ln特效树脂过柱方式对Sr和Nd分离都有影响。为分析上述因素对Sr和Nd分离效果的影响,本文以水系沉积物标准物质GBW07309为例进行了研究,结果表明:(1)高含量的Fe会显著影响Sr和Nd的分离效果,而AG1-X8树脂可以有效去除Fe;(2)当AG50W-X8树脂高度为1 m L,硝酸作为洗脱酸时,Sr和REEs的分离效果较好;(3)Sr特效树脂淋洗酸中硝酸淋洗体积达到15 m L时可以有效分离Sr和Rb;(4)Ln特效树脂采用重力过柱方式时Sr和Nd分离效果较好,没有拖尾现象。本研究解决了Fe对分离Sr和Nd的干扰,K、Na、Ca、Mg、Fe、Rb、Sm去除率达到99%以上,完全满足Sr和Nd同位素分析的要求,为离子交换树脂法分离沉积物中Sr和Nd提供了较详细的前处理经验数据。