泥质烃源岩不同有机显微组分的原始赋存态

利用密度分组将泥质烃源岩划分为不同的密度组分,通过对各密度组分进行孢粉相分析和激光粒度检测,结果表明:密度分组获得的ρ<1.6 g.cm3组分以游离态生物有机质为主,富集了全岩干酪根中大粒级的形态有机质组分;1.6g.cm-3<ρ<2.2 g.cm-3和ρ>2.2 g.cm-3组分表现为有机质与矿物共生的赋存态特点,富集大量细粒级的颗粒无定形和海绵无定形有机质,说明这些无定形物质通过与矿物(主要是粘土矿物)紧密共生而获得保存.分组结果反映不同有机显微组分在烃源岩中的赋存态存在差异,大量的无定形物质与矿物(主要是粘土矿物)紧密共生,说明有机质与矿物共生组分对于烃源岩油气生成具有十分重要的意义.

淡水和咸水湖相泥质烃源岩不同赋存态有机质的地球化学特征

泥质烃源岩中的有机质存在多种赋存形式,其中与无机矿物结合形成有机—无机复合体是有机质保存的重要方式之一。为了对比研究泥质烃源岩中不同赋存态有机质的地球化学特征,选取东营凹陷沙三下亚段(淡水湖相)和沙四上亚段(咸水湖相)优质烃源岩为研究对象,采用"溶剂抽提—皂化—HCl酸解—HF/HCl酸解"的连续处理实验方法,依次得到烃源岩中的游离态有机质、黏土矿物层间吸附有机质、碳酸盐矿物结合有机质和黏土矿物表面化学吸附有机质。结果表明,烃源岩中的矿物结合态有机质约占可溶有机质总量的10%,矿物结合态有机质与游离态有机质表现出显著的地化特征差异:矿物结合态有机质以非烃、沥青质等极性组分为主要组成,饱和烃中轻烃比例较高;矿物结合态有机质可以补充保存具有生源指示意义的分子标志物,如指示Botryococcus braunii生源的两环倍半萜类分子标志物仅在碳酸盐矿物结合有机质中检出,指示古菌生源的角鲨烷仅在HF/HCl酸解有机质中检出;此外,矿物结合态有机质亦可对沉积环境的差异做出分子响应。因此,在对游离态有机质地化特征分析基础上,如能综合分析不同矿物结合态有机质的地化特征,可以获得更为全面的地质分析结果。

松嫩平原含水层沉积物特征及其对砷赋存态分布的影响

松嫩平原西部地区为中国砷中毒区域,含水层沉积物特征及砷赋存态对地下水砷迁移、转化的影响并不清楚。在对研究区高砷区与低砷区钻孔沉积物进行取样的基础上,运用激光粒度分析、Tessier五步提取法和Keon分步提取法分别确定了不同深度沉积物的粒度分布和不同赋存态砷含量,系统研究了沉积物的水力传导系数、不同赋存态砷的分布及其与高砷地下水形成的关系。结果表明：沉积物5种赋存态砷（包括可交换态、碳酸盐吸附态、铁/锰氧化物吸附态、有机物或硫化物吸附态和基质态）中,铁/锰氧化物吸附态砷含量最高,并且砷含量与铁、锰含量呈明显正相关性;高砷区钻孔沉积物铁/锰氧化物吸附态砷质量分数为（1.18~6.11）×10^-6,低砷区为（0.67-2.60）×10^-6;高砷区钻孔沉积物以粉砂、黏土为主,水力传导系数介于0.004-0.027m·d^-1,低砷区钻孔沉积物以细砂、中砂为主,水力传导系数介于0.005-0.2m·d^-1;沉积物中粉砂或黏土含量越多,则沉积物颗粒越小,其水力传导系数越低,各赋存态砷含量越高,因此,高砷区低水力传导系数有利于还原环境的形成。通过地下水的循环,高砷含水层沉积物的淋滤作用和铁/锰氧化物的还原性溶解形成了研究区高砷地下水。

泥页岩中水的赋存态研究进展及其意义

泥页岩中的水具有多种赋存态,明确其赋存形式、各赋存态水的含量及其分布特征,有利于进一步理解“油(气)—水—岩石”之间的内在联系,对页岩油气的生成、存储、运移和勘探开发具有重要的指导意义。目前关于泥页岩中不同水的分类繁杂且不统一,综合现有的划分方法,提出基于水的赋存态将其划分为自由态的可动水、体积充填态的毛管束缚水、表面吸附态的水膜束缚水以及离子态的结构水4种类型。其中,束缚水是油气存储空间的“竞争者”和运输通道上的“障碍物”,水膜束缚水主要占据页岩油气的有效吸附位,而毛管束缚水则会堵塞部分小孔道。同时,水的赋存态会随矿物和有机质的自身变化而发生改变,从而影响储层的润湿性和页岩油气的勘探开发。此外,探讨泥页岩中矿物、有机质和孔隙性质对水的赋存机制的影响,并调研热分析和核磁共振等检测方法以研究泥页岩中不同赋存态水的含量、位置以及微观分布特征,以期为页岩油气的高效开发提供理论基础。

东海表层沉积物黏土粒级中多态脂肪酸组成与地球化学特征

对东海陆架泥质沉积区两个代表性站位表层沉积物开展了黏土粒级分离提取,并对其依次进行溶剂萃取、碱解和酸解处理,得到结合程度不同的三种脂肪酸组分:有机溶剂抽提的游离态脂肪酸、碱解得到的碱解酸和酸解得到的酸解酸。三种赋存态酸的存在表明它们所联结的宏观分子的结构不同或所吸附黏土矿物的保护作用不同。不同赋存态酸的数量、组成和分布有一定差异,两站位相同赋存态酸的数量与组成也存在明显差异。组成与分布特征表明东海陆架泥质区超细颗粒物中脂肪酸以海洋内源藻类来源为主(>70%),陆源高等植物贡献相对较低,并有少量的细菌源贡献。各赋存态酸的降解程度为碱解酸高于酸解酸高于游离酸,可能与其在黏土中的赋存状态和吸附过程有关。靠近长江河口的表层沉积物样品(24站)海洋内源藻类贡献略低于远离河口的站位(30站),陆源高等植物的输入稍高于后者,是受两泥质区沉积环境综合影响的结果。

我国高岭土矿中铁杂质特征及除铁技术研究进展

在我国产业转型升级的背景下,高岭土消费量迅猛增长,需求结构快速向中高端演化。然而,以煤矸石为代表的富铁高岭土资源加工利用难度大,优质高岭土产品的短缺问题已经出现,加快推进绿色高效除铁技术的发展迫在眉睫。在明确现代工业对高岭土含铁量要求的基础上,概述了我国高岭土资源的特点,分析了典型高岭土资源中铁杂质含量与赋存形态,系统介绍了物理法、化学法、生物法等除铁技术的原理与进展情况,并通过对比分析指出了未来除铁技术可能的发展方向,以期为我国高岭土产业链的提质升级提供参考。

东营凹陷沙河街组Es_3/Es_4烃源岩热解特征及生烃差异研究

选取东营凹陷沙河街组Es3的下亚段(沙三下)与Es4的上亚段(沙四上)两套烃源岩样品,开展岩石热解检测,探讨其热解特征及生烃的差异性。结果表明,沙三下和沙四上的成熟度相近,但沙三上的常规热解参数(TOC、干酪根类型和生烃总量)要优于沙四上,这表明沙三下相比沙四上是更优质的烃源岩。进一步分析发现,沙四上的游离烃(S1)以及S1/PC值高于沙三下,而沙三下的热解烃(S2)与S2/PC值相对更高,表明两者的生烃能力存在差异。结合前人对有机质赋存态和热解参数关系的理解,沙三下较高的S2值和丰富的伊蒙混层矿物意味着沙三下拥有更多的蒙脱石层间吸附有机质。同时,沙四上咸水环境和沙三下淡水环境的差异,使得沙四上的蒙脱石伊利石化进程提前于沙三下。蒙伊化这一矿物转化过程致使蒙脱石层间吸附有机质排出并早期生烃,造成沙四上的S1值高于沙三下,这可能是造成已探明储量中沙四上生烃贡献量远大于沙三下的原因。因此,深入剖析S1、S2等热解参数与有机质赋存的关系,能更深刻了解烃源岩的有机质特征和生烃差异。

泥质烃源岩酸解有机质中两环倍半萜的检出及其意义

以东营凹陷沙三下亚段和沙四上亚段主力烃源岩为研究对象,采用有机溶剂抽提—HCl酸解连续处理实验方法,对泥质烃源岩黏粒级组分的游离态有机质和碳酸盐矿物结合态有机质进行地球化学表征。结果表明:游离态有机质可以提供沉积环境、热成熟度、有机质生源等地化信息,碳酸盐矿物结合态有机质能补充有机质生源信息;碳酸盐矿物结合态有机质能更好地保存烃类组分的轻质端,可以指示Botryococcus braunii生源的两环倍半萜类生物标志化合物仅在赋存态中检出。此外单质硫具有相对较高的丰度,相对封闭的矿物晶格赋存环境使有机质的原生地质信息更好地保留下来。对烃源岩中游离态有机质和矿物结合态有机质的综合分析,可以得到更为真实客观的地质推断结果。

Gold occurrence of Jiaojia gold mine in Shandong province

The microscopy and scanning electronic microscopy （SEM） were used to study the gold occurrence of Jiaojia gold mine, Shandong province. The results show that the gold-bearing minerals are composed of pyrite, chalcopyrite, gangue, sphalerite and galena. 77.12% of gold minerals are the sulphides and 22.88% are the gangues. The gold occurrence is composed of 60.28% fissure gold, 21.63% inclusion gold and 18.09% crystal fractured gold. The morphology of gold mineral is composed of sphere, triangle, rectangle, strip and erose. The Jiaojia gold mineral owns large grain size range from 3-5 μm to 100 μm. 1.5% of gold grains is more than 0.104 mm, 5.26% is 0.074-0.104 mm, 23.31% is 0.043-0.074 mm, 3.76% is 0.043-0.037 mm and 64.29% is less than 0.037 mm. The occurrence of gold mineral is composed of native gold, electrum, native silver, iron-bearing native silver, goldcuprid and acanthite. Electrum is the most important mineral, accounting for 71.56%. The average quality is 641.26‰ for gold and silver mineral.

Mineralogy and crystal chemistry of a low grade nickel laterite ore

To acquire understanding of Ni enrichment from laterite ore,the mineralogy and crystal chemistry of a low grade limonite type nickel laterite ore sample assaying 0.97% Ni from Indonesia were studied using optical microscopy,X-ray diffraction（XRD）,scanning electron microscopy（SEM） and electron probe microanalysis（EPMA）.According to EPMA results,the mineral includes 80% goethite（（Fe,Ni,Al）O（OH）） with 0.87% Ni,15% silicate minerals with lizardite（（Mg,Fe,Ni）3Si2O5（OH）） and olivine（（Mg,Fe,Ni）2SiO4）,and 1.19% Ni,and other minor phases,such as hematite,maghemite,chromite and quartz,and no Ni was detected.The mineralogy of the laterite ore indicates that due to the complicated association of the various phases and the variable distribution of Ni,this refractory laterite ore can not be upgraded by traditional physical beneficiation processes.

烃源岩不同性质有机酸的分离及其检测方法

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。

新疆东戈壁钼矿弱胶结层元素分布规律研究

以新疆东戈壁钼矿为例,研究矿体上方弱胶结层不同粒级土壤中元素分布规律及成因,主成矿元素活动态赋存形式,为金属活动态测量法在戈壁荒漠区寻找钼矿提供依据。本次研究发现,Mo、Cu等成矿及伴生元素在弱胶结层(10~40 cm)中倾向于向两"极"富集,即最粗粒级(-4^+20目)和最细粒级(-160目)含量较高。在粗粒级中富集与粗粒岩屑保留了原岩矿化信息有关;在细粒级中富集与细粒土壤中粘土矿物、铁锰氧化物能有效捕获从深部矿体迁移上的活动态金属元素,形成元素含量二次叠加有关。活动态Mo、W元素主要赋存于水提取态中,活动态Cu主要赋存于铁锰氧化物态中。在大面积基岩出露的剥蚀戈壁区,采集弱胶结层粗粒岩屑样品即能反映异常;在覆盖区进行钼矿地球化学调查时,采集弱胶结层中细粒级样品为佳,能有效捕捉深部含矿信息。

Effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores

The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.

Mode of occurrence of arsenic in high-As coals from endemic arsenosis areas in southwestern Guizhou Province, China

The use of high As-bearing coals has caused more than 3,000 cases of arsenosis patients in southwest Guizhou Province, China. The mode of occurrence of arsenic in coal is an important key role in understanding its behavior during usage and damage pathway to human health. Coal samples from endemic arsenosis areas were analyzed with INAA, EMPA, SEM-EDX, LTA, XRD, XAFS, and sequential leaching experiment. Arsenic in pyrite is from under the limit of EMPA to 1.75%, and in most cases, the content of arsenic is lower than 0.5%. Besides pyrite and arsenopyrite, SEM-EDX combined with LTA and XRD find that sulfates, clay and phosphates also contain arsenic. XAFS shows that arsenic mainly exists in the form of As^5＋. More than 50% of arsenic stayes in residual solid and combined with organic matrix in two samples, but most arsenic is leached out in other samples. The occurrence of such exceptionally high As contents in coal and the fact that the arsenic is dominantly organically associated are unique observations.

^(15)N NMR Spectroscopic Study on Nitrogen Forms in Humic Substances of Soils

Nitrogen forms of humic substances from a subalpine meadow soil, a latentic red soil and a weathered coal and the effect of acid hydrolysis on N structures of soil humic substances were studied by using 15N cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy. Of the detectable 15N-signal intensity in the spectra of soil humic substances 71%-79% may be attributed to amide groups, 10%-18% to aromatic/aliphatic amines and 6%~11% to indole- and pyrrole-like N. Whereas in the spectrum of the fulvic acid from weathered coal 46%, at least, of the total 15N-signal intensity might be assigned to pyrrole-like N, 14% to aromatic/aliphatic ammes, and the remaining intensities could not be assigned with certainty. Data on nonhydrolyzable residue of protein-sugar mixture and a 15N-labelled soil fulvic acid confirm the formation of nonhydrolyzable heterocyclic N during acid hydrolysis. Project (No. 39790100) supported by the National Natural Science Foundation of China.

Characterization of Humic Fractions in a ^(15)N-labelled Soil by Solid-State ^(13)C and ^(15)N NMR

Five humic fractions were obtained from a uniformly 15N-labelled soil by extraction with 0.1 mol L-1 Na4P207, 0.1 mol L-1 NaOH, and HF/HCI-0.1 mol L-1 NaOH, consecutively, and analyzed by 13C and 15N CPMAS NMR (cross polarization and magic angle spinning nuclear magnetic resonance). Compared with those of native soils humic fractions studied as a whole contained more alkyls, methoxyls and O-alkyls, being 27%-36%, 17%-21% and 36%-40%, respectively, but fewer aromatics and carboxyls (being 14%-20% and 13%-90%, respectively). Among those humic fractions, the humic acid (HA) and fulvic acid (FA) extracted by 0.1 mol L-1 Na4P207 contained slightly more carboxyls than corresponding humic fractions extracted by 0.1 mol L-1 NaOH, and the HA extracted by 0.1 mol L-1 NaOH after treatment with HF/HCI contained the least aromatics and carboxyls. The distribution of nitrogen functional groups of soil humic fractions studied was quite similar to each other and also quite similar to that of humic fraction from native soils. More than 75% of total N in each fraction was in amide form, with 9%-13% present as aromatic and/or aliphatic amines and the remainder as hoterocyclic N.

Geochemical characteristics and mode of occurrence of trace elements in coal at West Bokaro coalfield

The mineralogy and trace element contents in coals from the West Bokaro coalfield, which is the one of the biggest Gondwana coalfields of India, were studied to delineate enrichment of trace elements and their modes of occur- rence. Elemental concentrations with reference to their crustal abundances indicated that coals are relatively enriched in As （4.4-15.5 mg/kg）, Cd （0.3-3.0 mg/kg）, Cu （28.0-68.1 mg/kg） and V （46.6-178.0 mg/kg）; depleted in Co （10.8-28.4 mg/ kg）, Mn （7.6-483.4 mg/kg）, Ni （13.0-31.6 mg/kg）, Cr （14.2-85.5 mg/kg） and Zn （5.25-70.4 mg/kg）. The concentration of As, Cd, Co, Cu and V were higher than the average values of world and Indian coals. Mineralogical study carried out by X-ray diffraction shows that quartz and kaolinite occur as dominant mineral phases in this coal. Fourier transform infrared spectroscopy pattern suggests organic structures primarily containing aromatic nuclei, aliphatic side chain and some oxygen containing groups. The modes of occurrence of trace elements present in these coals have been determined through statistical approach. Both Cu and Cr are more closely associated with mineral matter, whereas Co is dominantly present with its organic form. The concentrations of Cd, Mn, Ni, Zn, As and V have apparently occur in both organic and inorganic constituents. This study would be helpful to assess the potential environmental impacts during mining and combustion of this coal.

Effect of Fertilizer N Forms on Physiological Metabolism and Potassium Uptake of Flue-Cured Tobacco

The growth, chlorophyll composition, photosynthesis, respiration, K uptake and root K+ secretion offlue-cured tobacco as thected by different concentrations of N supplied as urea, NaNO3 and NH4NO3 werestudied under the experimental condition of sand culture. The results showed that the content of K in thefiue-cured tobacco was not merely related with root vitality and uptake but also closely related with root cellmembrane structure and K+ secretion.

Sequential Extraction of Aluminum and Iron from Acidic Soils by Chemical Selective Dissolution Methods

Potassium chloride, Na-pyrophosphate, CuCl2, NH4-oxalate, dithionite-citrate-bicarbonate (DCB) and Na-citrate solutions were employed to extract aluminum (Al) and iron (Fe) sequentially and separately from 15 acidic soils located at the Mangshan Mountains, Hunan Province, China. Many evidences showed that separate pyrophosphate extracted mainly KCI-extractable Al, organo-Al complexes and some inorganic Al compounds, whereas separate CuCl2 extracted KCl-extractable Al and some organo-Al complexes. CuCl2 extracted much less amounts of Al than pyrophosphate did from the soils. Separate oxalate did not extract all KCl-Pyrophosphate- CuCl2 -oxalate sequentially extractable Al and Fe. Also, separate DCB did not extract all KCl- pyrophosphate- CuCl2 -oxalate- DCB sequentially extractable Al. The forms of Al extracted by oxalate and DCB from the soils were majorly noncrystalline. The interlayered materials of 1.4-nm intergrade minerals of the soils were attributed mainly to hydroxy Al polymers.

Mechanism of stepwise tectonic control on gas occurrence: A study in North China

To gain an understanding of gas occurrence, distribution is the fundamental basis for preventing gas disasters. Presently, how tectonic structures control gas occurrence remains problematic. This study proposes the theory and elucidates the mechanism of stepwise tectonic control on gas occurrence according to the characteristics of gas occurrence and the patterns of gas distribution in coal mines in North China. On the one hand, tectonic compression and shearing lead to stress concentration and thus deform the coal and reduce the coal seam permeability, further contributing to gas preservation. On the other hand, tectonic extension and rifting lead to stress release and thus improve the coal seam permeability, further contributing to gas emission. Therefore, the distribution zones of tectonic compression, ubiquitous coal deformation, and gas accumulation have been step-wisely revealed, and the coal-gas outburst proneness zones are finally identified. The proposed theory of step-wise tectonic control on gas occurrence is of practical significance for gas prediction and control.