Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

Use of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry for the characterization of biodegradation and unresolved complex mixtures in petroleum

A comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) method has been developed for separation of a series of petroleum samples using a polar/non-polar column set configuration. Groups of oils were selected to provide samples from the same oil family to assist in comparison of compositional changes during biodegradation. The groups also represented different sources and ages to allow an assessment of the application of GC × GC for the differentiation of oil source, as well as fluid history. The increased resolution and separation afforded by the GC × GC technique provides more complete compositional information on complex biodegraded oil samples than one-dimensional GC, and improves the ability to study biodegradation trends. Among the components identified, it is proposed that alkyl-decahydronaphthalenes constitute a significant contribution to the UCM.     

吹扫捕集-气相色谱-质谱法测定土壤中挥发酚的方法研究

文章研究了吹扫捕集-气相色谱-质谱法测定土壤中挥发酚的方法,分析了吹扫捕集各参数对挥发酚测定的影响,优化了吹扫捕集条件和气相色谱-质谱条件.通过与索氏提取技术对比,证明吹扫捕集-气相色谱-质谱法在实际样品检测中具有操作简便、分析周期短、试剂用量少、干扰小等优点,适用于测定沸点较低、溶解度较小的挥发酚,推荐选择经典的索氏提取技术测定沸点较高、溶解度较大的挥发酚.     

Identification of steranes and tritepanes in geolipid extracts by high-resolution gas chromatography and mass spectrometry

One method for the analysis of complex organic mixtures from geological sources is the use of high-resolution gas chromatographic data together with mass spectra obtained by combined gas chromatography-mass spectrometry (gc-ms). The present study involved examination of a variety of authentic triterpenoid alkanes (triterpanes) and steroid alkanes (steranes) for reference purposes, by measurement of their Kovats indices on OV-101 and Dexsil 300 liquid phases, and by the recording of their low-resolution mass spectra by gc-ms. These measurements provide reference data for analysis of the triterpenoid alkanes in geological samples and show that mass spectrometry is a valuable technique for triterpane analysis, permitting in many cases gross structural assignments which may be refined by a comparison of Kovats indices with those of authentic standards.     

风化煤及提腐植酸后残渣热解行为与动力学分析

应用热重-质谱(TG-MS)联用技术对风化煤(WC)及其腐植酸提取后残渣(WCR)的热解行为进行了研究,分析了非烃类(H2、H2O、CO和CO2)、低碳烃类(CH4、C3H6和C3H7)和芳烃类(C6H6)的实验结果,并利用Coast-Redfern积分法对其热解和烃类生成动力学进行了探讨,获得了热解过程和烃类生成动力学参数。结果表明:热解过程中风化煤的质量损失率(38.9%)略大于其腐植酸提取后残渣(36.6%);除CO和CO2外,残渣中非烃类、低碳烃类和芳烃类产物的逸出量都稍微或显著多于风化煤中各类组分的逸出量。用Coast-Redfern积分法求得的动力学参数很好地解释了这一结果。     

洞庭湖沉积物腐殖酸的配位性与酸碱性研究

通过电位滴定研究了从洞庭湖沉积物中分离得到的腐殖酸(HA)的酸碱性和配位性,采用修正格兰函数进行了数据拟合.表征了六类可滴官能团含量和分布,pKa数值在2.35~10.50之间,羧基占可电离中心总数的62%,利用铜离子选择电极和汞齐电极(Pb、 Cd 和Zn)研究了腐殖酸与Cu2+、Pb2+、Cd2+和Zn2+配位性质,借助Scatchard方法对数据进行了处理,显示铜和铅为二配体,镉和锌为单配体.平均稳定常数顺序为:logKHA-Pb>logKHA-Cd>logKHAtZn, 配位能力顺序为:Pb>Cu>Cd≈Zn.     

Chemical characterization of fractionated humic acids from lake and marine sediments

Humic acids from Recent lacustrine and marine sediments were divided into five components by extractions with organic solvents and characterized by elementary composition, ultraviolet, visible and infrared absorption spectra and n.m.r. spectra. The results suggest that sedimentary humic acids have a cyclic structure (40–50% of the total carbon), which is considered to be alicyclic rather than aromatic. No marked differences except for an absorption near 410 mμ were observed between humic acids from lake and marine sediments.     

Determination of hydrocarbon distributions in oils and sediment extracts by gas chromatography—high resolution mass spectrometry

The distributions of steroid and triterpenoid hydrocarbons in crude oils and sedimentary rock extracts can be routinely determined by the direct injection of the sample into a gas chromatograph coupled to a mass spectrometer (GC-MS). The mass spectrometer is operated at a resolution of about 2500 (10% valley), and only the ion intensities at selected accurate mass values, diagnostic of the structural types of interest, are monitored throughout the analysis. The distributions, so obtained, find application in the assessment of the source and thermal maturity of crude oil accumulations in the subsurface. This technique eliminates chromatographic separation steps and combines two analyses in one. Thus, more geological samples and reference mixtures may be analyzed in a given time.     

Analysis of methylated humic acids from fossil fuels by size exclusion chromatography and NMR

Molecular Mass (MM) distributions in humic acids from peat and two lignites have been investigated by high performance size-exclusion chromatography (SEC) after methylation and found to be in the range approximately 300 to more than 5000, with number average NM(M_n) near 800. Values of M_n determined by SEC were in good agreement with those from vapour pressure osmotery. High field¹³C NMR spectra of the methylated humic acids are extremely well resolved, and indicate that the samples are significantly different, despite their similar elemental compositions and MM distributions.     

Spectroscopic characterization of fulvic acids extracted from the rock exudate Shilajit

The present work describes the extraction of fulvic acids (FA) from Shilajit and its spectroscopic and mass spectrometric characterization. The spectral features obtained from FT-IR and ¹HNMR were similar to those reported for humic substances from other sources. The molecular elemental composition analysis by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in electrospray negative ion mode resulted in extraordinary high average O/C ratios (0.55) which might be caused by a significant contribution of carbohydrates in Shilajit. A very high average H/C ratio of 1.27 also points to dominant aliphatic or alicyclic structures and relatively low aromaticity. The average molecular formula of the nitrogen free elemental compositions measured by FT-ICR mass spectrometry is C_18.2H_23.0O_10.0.     

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and Recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.     

Comparison of binding abilities of fulvic and humic acids extracted from recent marine sediments with UO22+

Potentiometric titrations were used to measure conditional stability constants of UO₂²⁺-fulvic acid and UO₂²⁺-humic acid complexes. Both 2:1 and 1:1 COO^-:UO₂²⁺ binding were observed. With decreasing metal concentration (2.5·10⁻⁴-6.25·10⁻⁵ M) increasing amounts of UO₂²⁺ were in the form of 1:1 humate complexes and 2:1 fulvate complexes. Despite the high nitrogen content and the low acidic OH group content, the successive stability constant values were similar to those determined for divalent cations associated with fulvic and humic compounds isolated from soils. Stability constant values increase simultaneously with increasing ionization of the humic (or fulvic) acid polyelectrolytes and with decreasing metal concentration.     

Characterization of aromatic steroids and hopanoids in marine and lacustrine crude oils using comprehensive two dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS)

The distribution of the aromatic steroids and hopanoids in six crude oils was determined using comprehensive two dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) in order to improve their identification and application in geochemical studies. Co-elution between monoaromatic and triaromatic steroids and benzohopanes and their methylated homologues, which are commonly observed in ¹D conventional GC, were resolved, with GCxGC facilitating recognition of the compounds. One important feature was that, despite the oils showing mid-oil window maturity characteristics, the distribution of long chain aromatic steroids decreased in lacustrine samples vs. marine samples. This difference in the distribution of long chain and short chain aromatic steroids may reflect the different origins of these oils although this aspect needs further evaluation.     

Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies

Crude oil samples from two basins were analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC–TOFMS) to better understand the compositional heterogeneity of branched-cyclic hydrocarbons. GC×GC–TOFMS and conventional GC–MS results were compared. GC×GC–TOFMS revealed a wide range of compounds, including tricyclic, tetracyclic and pentacyclic terpane series, rearranged hopanes, methyl hopanes, secohopanes, onoceranes and steranes. Assignment of methyl hopane and 8,14-secohopane series other than onocerane isomers was only possible due to the high peak capacity and sensitivity of GC×GC. The oils comprised a mixture of two end members: non-biodegraded oil with abundant tricyclic terpanes and hopanes, and severely biodegraded oil with abundant 8,14-secohopane and demethylated tricyclic terpanes. A predominance of two distinct series, 3β-methylhopane and onocerane, was detected only in the lacustrine samples (classification based on biomarker parameters). In contrast, the predominance of a 2α-methylhopane series and lack of onocerane were found only for the marine oil sample. The results suggest that the distribution of 3β- and 2α-methylhopane series and the presence or absence of onocerane isomers reflect genetic differences in the source organic matter and that these compounds are new classes of biomarkers that can used as depositional paleoenvironment proxies.     

Application of a continuous distribution model for proton binding by humic acids extracted from acidic lake sediments

The proton binding characteristics of humic acids extracted from the sediments of Cranberry Pond, an acidic water body located in the Adirondack Mountain region of New York State, were explored by the application of a multiligand distribution model. The model characterizes a class of proton binding sites by mean logK values and the standard deviations of logK values about the mean. Mean logK values and their relative abundances were determined directly from experimental titration data. The model accurately predicts the binding of protons by the humic acids for pH values in the range 3.5 to 10.0.     

Sample preparation for analyzing polycyclic aromatic hydrocarbons and polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment by gas chromatography/mass spectrometry

A sample preparation technique was developed to isolate and separate two classes of combustion-produced pollutants: three- to six-ring polycyclic aromatic hydrocarbons (PAH) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), from sediment samples for interference-free analyses by gas chromatography/mass spectrometry (GC/MS). The method involves soxhlet extraction with methylene chloride, sulfur removal with activated copper powder, gel filtration chromatography with Sephadex LH-20, polarity separations of PAH and PCDD/F with prepacked silica gel solid-phase extraction columns, and isolation of PCDD/F from polychlorinated biphenyls with microalumina columns. Stringent procedural controls were established to achieve clean isolations and recoveries of 70% or better for each step in the method. The prepared sample extracts were analyzed by capillary GC and GC/MS. Electron impact ionization was used for PAH, and negative chemical ionization with methane as a reagent gas was used for PCDD/F. Reproducible results were obtained. The method is simple and has the advantage of conserving sample consumption since two classes of compounds can be analyzed from the same sample. This can be critical in sediment core analyses where sample size is usually limited.     

在线PYGC分析技术在气源岩评价中的应用

为了研究高演化地区气源的生成特征与生气潜力，分别采用热解温度为560℃不加内标、CDS2000热解系统，700℃加内标（聚苯乙烯）、由实验室自制热解系统的在线热解气相色谱分析技术，对不同气源岩（代表性的煤、固体沥青及四川地区以下古生界碎屑岩为主的全岩）进行5s的快速热解分析。在对实验系统加内标定量的可行性进行了认真研究后，提出了产烃定量公式。560℃的热解谱图可清楚地将烃源岩分为生油、生气和生凝析油三种类型，并可根据谱图计算出油气比（GOGI）。根据700℃加内标的热解测试结果，计算了气源岩的热解烃总量和C1－5－C5－C15组分的相对含量。热解烃总量随热演变程度增高而递减，其中以碎屑岩的热解烃量减低最快。相同样品的热解烃量与TOC和Rock-Eval测定结果具有很好的可比性。对比不同演化阶段热解产物的相对组成，显示低演化阶段的烃源岩热解产物以C1－5组分为主。由此表明，在高演化阶段，好的油源岩就是好的气源岩。较高演化阶段（测试前R^0为2．5％－4．2％）烃源岩的热解烃中C5－15含量呈增加趋势，这一结果与前人资料吻合，它除了表明C5-15 分的含量可能与烃存在的载体，如无机矿物或固体有机质对早期轻烃的包裹与吸附有关外，可能还揭示了有机质在石墨化过程中高演化阶段有着与低演化阶段不同的特性。固体沥青广泛分布在四川地区下古生界地层中，PY－GC测试结果也表明，固体沥青比相同演化阶段的碎屑岩热解产物多数倍到一个数量级，因此，在高演化地区固体沥青是不可忽视的气源岩。     

Comparison of binding abilities of fulvic and humic acids extracted from recent marine sediments with UO2

Potentiometric titrations were used to measure conditional stability constants of UO₂²⁺-fulvic acid and UO₂²⁺-humic acid complexes. Both 2:1 and 1:1 COO^-:UO₂²⁺ binding were observed. With decreasing metal concentration (2.5·10⁻⁴-6.25·10⁻⁵ M) increasing amounts of UO₂²⁺ were in the form of 1:1 humate complexes and 2:1 fulvate complexes. Despite the high nitrogen content and the low acidic OH group content, the successive stability constant values were similar to those determined for divalent cations associated with fulvic and humic compounds isolated from soils. Stability constant values increase simultaneously with increasing ionization of the humic (or fulvic) acid polyelectrolytes and with decreasing metal concentration.