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1.
原油的有水热解产生低分子量有机酸的研究 总被引：5，自引：0，他引：5
用原油及其族组分加入矿物和不同离子浓度的水进行了有水热解，对热解后的水溶液做了低分子量有机酸分析。实验表明，储集层中的原油在热作用下能产生有机酸，但不同条件下，生成的量有所不同。高浓度的卤水对产酸有利，加入不同矿物，砂岩对热解有微弱催化作用，而氧化性矿物能提高产酸量。就原油中不同族组分而言，沥青质生成有机酸的贡献最大。 相似文献
2.
生油岩产生低分子量有机酸的模拟实验研究 总被引：7，自引：1，他引：7
通过对低成熟的生油岩样岩样品进行有水和无水热解实验，在不同温阶下的水溶液产物中均检测到低分子量有机酸。把这些有机酸的分布与油田水样品相比较，发现两者在组成上很近似。再加入不同矿物的样品，热解后的有机酸组成与干酷根单热解样品有较大差别，这表明产酸过程中水和无机矿物起了重要作用。 相似文献
3.
微生物-矿物的相互作用是地球上广泛发生的一种地质作用，它直接导致矿物的溶解和沉淀，并进而对环境产生重要的影响。微生物-矿物相互作用对环境修复具有重要意义，如金属还原细菌（DMRB）可通过与Fe^3 -氧化物矿物的相互作用催化氧化降解含芳香环的化合物如苯酸盐、苯、甲苯等，或催化还原降解（聚）硝基芳香化合物及四氯化碳等，还可通过表面吸附作用或氧化还原作用使一些重金属元素如U、Np等高毒性的污染物固着或形成不溶的矿物形式，从而有效去除其毒性。另外，微生物亦可催化氧化形成对环境有高度污染的酸性矿山废水（AMD）等，总之，深入研究微生物-矿物的相互作用对环境的影响具有重要意义。 相似文献
4.
综述了大气气溶胶颗粒物的特征、颗粒物的界面反应与矿物协同演化意义;重点介绍了大气颗粒物粒径分布和矿物成分,以及常见有毒有害气体的界面反应产物特征与关键化学过程;总结了矿物颗粒在大气气溶胶形成过程中汇聚、调控、催化的作用,以及颗粒物与大气中SO2、NOx的协同反应机制;分析了微纳米颗粒对二次有机气溶胶形成的影响,以及大气矿物相颗粒界面反应产物组合及协同演化作用.可为进一步研究大气颗粒物与大气中痕量污染气体反应形成二次气溶胶进而影响大气化学组成的过程提供指导,对深入探讨大气矿物颗粒表面特性在复合污染物中多介质反应的微界面化学过程,矿物尘-污染物气溶胶体系在雾-霾形成、转换、新生粒子和阻断行为的复合作用具有重要的环境学意义. 相似文献
5.
微生物矿化成因的铁硫酸盐矿物表面特征初探 总被引：12，自引：1，他引：12
研究表明，生物一矿物相互作用是地球表层系统演化的重要地质营力之一。微生物与矿物岩石之间进行着活跃的物质交换，微生物通过营造微观地球化学环境和提供吸附、成核中心影响着矿物的溶解和结晶，其中生物一矿物界面是物质交换和化学反应最为活跃的场所，矿物表界面记录着丰富的微生物作用信息。在综述前人微生物一矿物相互作用界面研究的基础上，利用气体吸附技术，对比分析了微生物矿化成因和无机合成含水铁硫酸盐矿物的表面积、表面分形和表面吸附能特征，初步讨论了微生物矿化成因铁硫酸盐矿物的表面特征和控制机理。 相似文献
6.
铝硅酸盐矿物溶解作用铝活性研究 总被引：1，自引：1，他引：1
现在愈来愈多的研究表明:硅酸盐、特别是铝硅酸盐矿物在有机质成熟热演化过程中发生溶解形成大量次生孔隙，将是砂岩储集体次生孔隙形成的重要现象之一。有机质成熟热演化发生脱羧作用，进而增强了孔隙水溶液中的有机酸阴离子浓度[1]，有机酸促进铝硅酸盐矿物溶解，溶解的实质是铝活性问题。本文通过实验分析了有机质与无机矿物的相互作用，讨论了有机酸对不同矿物的溶解性，查明了铝活性动力学因素，并对铝硅酸盐矿物次生孔隙形成机理进行了探讨。 相似文献
7.
矿物环境属性与无机界天然自净化功能 总被引：7，自引：11，他引：7
鲁安怀 《矿物岩石地球化学通报》2002,21(3):192-197
本将矿物学研究从岩石圈拓展到水圈、大气圈、生物圈与土壤圈之间交互作用的矿物环境属性范畴，研究表明，矿物可成为记录环境演变信息的载体；防止矿物的破坏与分解有可能减少甚至避免由此所造成的对人体健康的影响与生态环境的破坏；矿物与生物交互作用的研究与天然矿物治理污染物的是建立在充分利用自然规律的基础之上，体现了天然自净化作用的特色。天然矿物对污染物的净化功能主要体现在环境矿物材料基本性能方面。天然铁的硫化物，铁的氧化物，锰的氧化物、钛的氧化物。蛭石，有机蒙脱石和含高价阳离子蒙脱石，以及黄钾铁矾等均在处理无机与有机污染物方面展现出良好效果，矿物与其环境界面原子尺度相互作用过程研究，矿物内部结构缺陷影响矿物表面活性规律研究，矿物晶体结构中不同维次连通性孔道效应研究,矿物化学活性作发化污染物方法研究，以及矿物晶芽与生物细胞层次上交互作用净化污染物机理研究等，将是近期着力开发无机界矿物天然自净化功能的重点研究内容。 相似文献
8.
H+和有机酸对可变电荷土壤铝释放的动力学研究 总被引：4，自引：0，他引：4
利用流动搅动法研究了在模拟酸雨和低分子量有机酸条件下可变电荷土壤铝释放的动力学特征,结果表明,在pH3.5的模拟酸雨作用下,红壤和黄壤中流出液铝的浓度范围约为15～40μmol/L,铝的释放快反应来源于土壤交换性铝和有机络合态铝,铝的释放慢反应对应于含铝矿物的溶解。赤红壤和砖红壤上在0～300min内流出液铝的浓度范围约为1～5μmol/L,流出液pH值大于4.5,对H 的缓冲作用表现为阳离子交换、SO24-的专性吸附释放OH-和矿物表面的质子化;当流出液pH值小于4.5时,H 开始溶解土壤中的含铝固相,铝释放的最后浓度为20～30μmol/L。用相近pH值的有机酸溶出土壤铝的浓度比pH3.5的模拟酸雨要高,特别是在砖红壤上,开始就有大量铝的释放,其浓度为20～75μmol/L,红壤上是70～150μmol/L,随时间延长,流出液中的铝浓度分别为10～20μmol/L和20～30μmol/L。有机酸作用下铝的释放机制主要是有机酸被土壤吸附后,有机酸与位于表面晶格中的铝原子形成络合体,促进了铝的溶解;其次是有机酸的吸附掩盖了土壤表面的质子化过程,增强了酸的溶解,以及有机配体对铝的络合作用,增加了铝的释放量。不同有机酸对铝的溶出能力也有不同,其释放铝能力的大小为:柠檬酸>酒石酸>苹果酸,这取决于有机配体与铝的络合能力。 相似文献
9.
铝硅酸盐矿物成岩演化对形成过渡带气的影响 总被引：1，自引：0，他引：1
生油成气的过程不只是简单的有机物之间的转化，而是无机和有机两个系统综合运动的产物，它们之间相互联系相互制约。成岩作用伊始，两系统独立演化，均受成岩环境的制约。一旦环境适合于有机物裂化分解，两系统就共同发挥作用，通过质子的转移而相互作用。由于生物热催化过渡带气埋藏浅、热演化程度不高等特点，铝硅酸盐矿物成岩作用主要表现为:砂质岩以机械压实作用、胶结作用、溶解作用、矿化交代、自生矿物充填作用为主，泥质岩最显著的变化就是矿物的成岩演化，即蒙脱石→伊／蒙混层→伊利石，及蒙脱石→绿／蒙→绿泥石的成岩演化，其实质是有机与无机相互作用，即赋存在粘土中有机质的有机酸使砂质岩发生溶解，和碎屑岩溶解孔隙水中的Ａｌ３＋替代蒙脱石晶层间的Ｓｉ４＋，形成质子酸，对有机质形成过渡带气起着催化作用。 相似文献
10.
从生物矿化作用衍生出的有机矿化作用：地球生物学框架下重要的研究主题 总被引：6，自引：0，他引：6
早期"生物矿化作用"的概念,被定义为生物形成矿物的作用,并进一步分为生物控制和生物诱导两大类型。这个宽泛的概念,被修订为生物以生命活型(living form)影响矿物物质的沉淀作用;相应地,"生物矿物"是在严格的生物控制下、从局部环境中选择性地吸收元素并融合成具有生物功能构造的矿物。"有机矿化作用",则被定义为"与那些无生命活力的有机物质相关联的矿物形成作用"。与生物矿化作用相对应,有机矿化作用的产物被定义为"有机矿物",用来指那些通过有机聚合物、生物的和(或)非生物的有机化合物所导致的矿物沉淀作用,但是,有机矿物并非活着的细胞所直接形成。有机矿物与生物矿物的重要区别是,有机矿物没有被融合成受到生物严格控制的功能性构造。生物学家和化学家将生物矿化作用作为关注"生命体系中复杂的化学过程"的研究主题,超越了地质学范畴并使生物矿化作用的研究成为多学科关注的迷人领域,也大大促进了有机矿化作用的研究;考虑到有机矿物是沉积岩的重要组成,而且与生物的出现同步,还是潜在性的地外生命的遗迹,因此,从生物矿化作用衍生出的有机矿化作用的研究,自然就成为与生物矿化作用存在紧密关联的、地球生物学框架下又一个重要的研究主题 相似文献
11.
烃源岩中的有机酸来源于有机质,但有机质具有不同的赋存形式,有机酸具有不同性质,这将影响有机酸与不同赋存有机质的关系,进而影响分离和检测方法。文章在总结前人对有机质赋存形式和有机酸性质等特征的基础上,提出烃源岩中的有机酸并以非单一的形式存在,具有水溶性、脂溶性和难溶性有机酸三种类型,游离有机质中存在水溶性和脂溶性有机酸,而结合有机质中存在水溶性、脂溶性和难溶性有机酸。因此在检测方法上需采取分步分离的方法,且根据有机酸的性质选取合适的检测方法,即水溶性有机酸利用离子色谱检测,索氏抽提得到的脂溶性有机酸利用气相色谱—质谱检测,通过酸解抽提残渣得到的难溶性有机酸利用红外光谱检测,全面系统地认识烃源岩中有机酸含量和类型等特征。这对进一步探讨烃源岩各种类型有机酸特征和演化规律,深化烃源岩有机质生烃以及有机—无机相互作用等机理都具有重要意义。 相似文献
12.
13.
粘土矿物保存海洋沉积有机质研究进展及其碳循环意义 总被引：3，自引：0，他引：3
海洋沉积物吸附有机质的量和有机质循环周期与粘土矿物类型和吸附方式密切相关,并在全球碳循环中扮演着不同的角色。粘土吸附有机质有物理吸附和化学吸附之分,前者主要存在于粘土的微孔隙中,参与年、十年或百年尺度的循环;后者主要存在于粘土矿物层间和外表面,稳定性较好,有机质易于保存,可参与百万年或更长时间的循环,这种不同时间尺度内的碳循环,将会改写海洋沉积物有机碳“源”、“汇”的关系。不同类型粘土矿物的性质存在差异,决定了吸附有机质量的多寡,蒙脱石的吸附量远大于伊利石的吸附量,这可能是造成全球不同海域中有机碳“源”、“汇”变化的原因。海洋沉积物处于水圈、生物圈和岩石圈的交汇地带,有机碳的差异和变化,都会对全球碳循环及气候变化产生重要的影响。 相似文献
14.
Certain factors influencing the incorporation, transport and release of fatty acids by clay minerals, calcite and marine sediments have been investigated.Salinity was found to be an important factor. The adsorption of heptadecanoic acid by bentonite clay at 4%. was nearly triple that at 0%.. However, from 4%. to 35%., only a minor adsorption increase occurred. This behavior is believed to be related to flocculation of the clay at the lower salinity range. The pH over the range of 6.0–8.5 has a small influence on fatty acid-clay association, depressing it somewhat as the basicity increases.When the temperature of the fatty acid solution was increased from 0°C to 50°C, a decrease in adsorption on to clay was found. This effect may be due to increased water solubility of the acid at higher temperatures, since solubility is very important in controlling the degree of fatty acid-mineral interaction. Furthermore, apparent solubilization of fatty acids by indigenous dissolved organic matter in sea water reduces adsorption on to clay minerals.Based upon the heat of adsorption of ?14.6 kcal/mole, fatty acids are physically bound to clay minerals by weak van der Waals forces and hydrogen bonds.Bentonite and kaolinite were found to be the most adsorptive minerals investigated, followed in order by illite, montmorillonite and calcite. Sediments from Narragansett Bay were found to lie between illite and montmorillonite in adsorptive capacity after indigenous sediment organic matter had been removed. Sediment organic matter reduced fatty acid uptake by a factor of 1.6. 相似文献
15.
Robert F Dias Katherine H FreemanMichael D Lewan Stephen G Franks 《Geochimica et cosmochimica acta》2002,66(15):2755-2769
Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing 13C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ13C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ13C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ13C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ13C values of the organic acids. 相似文献
16.
A review with 227 references of the title subject is presented. It is divided into two main sections, viz., nature and properties of humic matter, and water—metal—sediment interactions.The first section deals with the essential properties of organic matter which occurs naturally in drainage sediments and waters. Discussion of the basic molecular structure of humic and fulvic acids is followed by some details of the chemical nature of functional groups within these structures which are important in metal-ion adsorption and complexing reactions which these materials can undergo. Information is also presented for colloidal and polyelectrolyte properties, complexation properties, and finally a summary discussion of metal-ion—humic-acid, metal-ion—fulvic-acid stability constants for both single ligand and mixed ligand systems completes the section.The second section comprises discussions of some specific aspects of interactions between metals, sediments and waters, including metal and organic speciation studies; sorption interactions between organic matter, clays and humic acids; chemical reaction between humic acids, heavy-metal minerals, clays and other silicate minerals; metal-ion adsorption—desorption studies, oxidation—reduction reactions between metal ions and humic acids; effects of sulphide ion on some of the above interactions and finally a summary of some relevant field geochemical dispersion studies.This second section describes both laboratory and field studies for each aspect. 相似文献
17.
John I. Hedges 《Geochimica et cosmochimica acta》1977,41(8):1119-1123
The uptake of dissolved organic molecules by kaolinite and montomorillonite clay minerals was measured in distilled water and saltwater solutions. Glucose and valine exhibited low affinities for both clay minerals over a wide range of concentrations in distilled water and seawater solutions. Stearic acid was efficiently removed by both clay minerals from all solutions over the concentration range 10–1000 ppb. These experiments suggest that some dissolved organic molecules may be preferentially removed by clay minerals in natural waters. It is unlikely, however, that the partitioning of simple organic molecules between natural waters and suspended clay minerals could produce the high concentrations of organic matter that occur in most fine-grained sediments. 相似文献
18.
矿物-腐殖质间的交互作用是土壤和水体沉积物及悬浮颗粒物中环境物质的重要界面过程。不管是氮、磷植物性营养元素还是有毒的重金属、有机物，它们在表生环境中的迁移转化与归趋受到矿物、腐殖质及其复合体的表面活性和迁移性的调控。矿物-腐殖质体系的界面作用研究是前沿性的研究领域，主要目的是揭示矿物-腐殖质复合体的结构特性(例如颗粒物的圈层结构与表面微形貌)及其与颗粒物表面活性的关系，进而揭示土壤和水体环境中矿物-腐殖质间的交互作用规律。本文对该领域的研究现状进行评述，并提出未来可能的发展趋势。 相似文献
19.
蚯蚓肠道内小分子有机酸与摄入的土壤矿物相互作用,加速矿物溶解。摄入的土壤在蚯蚓肠道内平均停留时间约为12 h,不足以使土壤矿物产生显著的溶解特征,因此这一过程难以在蚯蚓体内进行评估。本研究通过体外实验控制pH值和有机酸浓度,模拟蚯蚓肠道中有机酸对土壤中常见矿物的溶解反应,探讨了方解石和钾长石在蚯蚓肠道环境中的初始溶解动力学。研究发现,矿物在混合有机酸中的溶解速率比在纯水中高一个数量级,说明有机配体和质子促进了矿物溶解。溶解速率及粒度分析表明,方解石(CaCO3)溶解速率不受溶解过程中粒度变化的影响,而钾长石(KAlSi3O8)粒度在溶解期间未出现显著变化。在此基础上,采用初始速率法模拟了钾长石的初始溶解动力学,计算得出的溶解速率表明钾长石在溶解初期主要为表面K~+的释放。使用缩核模型(shrink core model)和Hixson-Crowell模型对方解石溶解过程进行动力学解析,发现方解石的溶解主要受溶液中反应物内扩散的速率影响。这定量描述了两种矿物在有机酸溶液和纯水中的溶解差异。现有研究表明,有机配体和质子协同促... 相似文献
20.
Robert Mikutta Klaus Kaiser Antje Vollmer Jon Chorover Georg Guggenberger 《Geochimica et cosmochimica acta》2010,74(7):2142-3154
Large portions of organic N (ON) in soil exist tightly associated with minerals. Mineral effects on the type of interactions, chemical composition, and stability of ON, however, are poorly understood. We investigated mineral-associated ON along a Hawaiian soil chronosequence (0.3-4100 kyr) formed in basaltic tephra under comparable climatic, topographic, and vegetation conditions. Mineral-organic associations were separated according to density (ρ > 1.6 g/cm3), characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge fine structure (NEXAFS) and analyzed for amino acid enantiomers and amino sugars. The 14C activity of mineral-bound OC was estimated by accelerator mass spectrometry. The close OC-ON relationship (r = 0.96) and XPS results suggest that ON exists incorporated in bulk mineral-bound OM and likely becomes associated with minerals as part of sorbing OM. The youngest site (0.3 kyr), with soils mainly composed of primary minerals (olivine, pyroxene, feldspar) and with little ON, contained the largest proportion of hydrolyzable amino sugars and amino acids but with a small share of acidic amino acids (aspartic acid, glutamic acid). In soils of the intermediate weathering stage (20-400 kyr), where poorly crystalline minerals and metal(hydroxide)-organic precipitates prevail, more mineral-associated ON was present, containing a smaller proportion of hydrolyzable amino sugars and amino acids due to the preferential accumulation of other OM components such as lignin-derived phenols. Acidic amino acids were more abundant, reflecting the strong association of acidic organic components with metal(hydroxide)-organic precipitates and variable-charge minerals. In the final weathering stage (1400-4100 kyr) with well-crystalline secondary Fe and Al (hydr)oxides and kaolin minerals, mineral-organic associations held less ON and were, relative to lignin phenols, depleted in hydrolyzable amino sugars and amino acids, particularly in acidic amino acids. XPS and NEXAFS analyses showed that the majority (59-78%) of the mineral-associated ON is peptide N while 18-34% was aromatic N. Amino sugar ratios and d-alanine suggest that mineral-associated ON comprises a significant portion of bacterial residues, particularly in the subsoil. With increasing 14C age, a larger portion of peptide N was non-hydrolyzable, suggesting the accumulation of refractory compounds with time. The constant d/l ratios of lysine in topsoils indicate fresh proteinous material, likely due to continuous sorption of or exchange with fresh N-containing compounds. The 14C and the d/l signature revealed a longer turnover of proteinous components strongly bound to minerals (not NaOH-NaF-extractable). This study provides evidence that interactions with minerals are important in the transformation and stabilization of soil ON. Mineral-associated ON in topsoils seems actively involved in the N cycling of the study ecosystems, accentuating N limitation at the 0.3-kyr site but increasing N availability at older sites. 相似文献