不同粘土矿物对赖氨酸的吸附行为对比研究

以皂石、高岭石、绿泥石和伊利石为原材料,分别与赖氨酸进行反应,研究赖氨酸在上述粘土矿物上的吸附行为, 并运用粉末X-射线衍射技术（XRD）、傅里叶变换红外吸收光谱术（FTIR）和热重（TG）等分析方法,表征反应前后粘土 矿物的变化。实验结果表明,不同粘土矿物对赖氨酸的吸附等温线均符合Freundlich等温方程,且不同粘土矿物对赖氨酸的 饱和吸附量大小顺序为：皂石>蒙脱石>绿泥石>高岭石>伊利石;XRD结果表明皂石对赖氨酸的吸附发生在矿物层间,而绿 泥石、高岭石和伊利石对赖氨酸的吸附主要在矿物表面进行;FTIR和TG结果表明赖氨酸主要取代粘土矿物层间吸附水,以 氢键的形式与Si-O-Si(IVAl)键合。实验结果将有助于进一步探明环境中粘土矿物对有机质的吸附机理。     

页岩气储层粘土矿物孔隙特征及其甲烷吸附作用

粘土矿物是页岩的主要组成矿物,与页岩气的赋存和富集密切相关。粘土矿物因其特殊的晶体结构,在晶层之间、矿物内部以及矿物颗粒之间形成了不同类型的孔隙,这些孔隙的大小、形貌和比表面积决定着粘土矿物的甲烷吸附能力。为此,本文综述了粘土矿物的孔隙结构以及孔隙中的水和有机质对甲烷吸附性的影响,指出不同类型的粘土矿物孔隙发育与形貌特征存在差异,蒙脱石中多发育圆形、狭缝状的微孔且总比表面积最大,导致蒙脱石在所有粘土矿物中的甲烷吸附量最大;伊利石与高岭石中多发育中孔与大孔,吸附甲烷的能力低于蒙脱石。粘土矿物孔隙中的水与有机质显著影响到甲烷的吸附能力,水分子会占据孔隙表面,降低了甲烷的吸附能力,但可溶有机质对粘土矿物甲烷吸附能力的具体影响目前尚不明了。同时,根据页岩气勘探需求指出了本方向某些有待深入探讨的问题。     

粘土矿物保存海洋沉积有机质研究进展及其碳循环意义

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。     

海洋粘土矿物与颗石藻Emiliania huxleyi共培养的实验研究

颗石藻是海洋中广泛分布的超微型浮游藻,经生物矿化作用形成的碳酸钙质颗石,在古海洋学研究中具有重要意义。海洋粘土矿物与有机质的有机-无机相互作用在全球碳循环中扮演着重要角色。本文选取广泛分布于海洋的赫氏颗石藻Emiliania huxleyi与海洋粘土矿物中具有代表性的伊利石和蒙脱石共培养。通过对颗石藻生长曲线和Sr/Ca、Mg/Ca元素比值、颗石藻与粘土矿物样品的紫外可见光吸收光谱、红外吸收光谱和矿物物相等分析,研究海洋粘土矿物与颗石藻的相互作用规律。通过研究表明伊利石对颗石藻的影响较小,蒙脱石因对营养元素的吸附和颗石藻的絮凝作用对颗石藻的生长和Sr/Ca、Mg/Ca元素比值影响较大。颗石藻代谢分泌的生物分子未能通过层间插层作用进入伊利石层间,颗石藻分泌的生物分子可通过插层作用进入并储存于蒙脱石层间,海洋粘土矿物中的蒙脱石与海洋微生物的相互作用值得地球微生物家关注,可能有助于对古海洋环境的认识。     

粘土矿物对胡敏酸的吸附行为研究

以蒙脱石和高岭土为吸附剂,分别与胡敏酸反应,研究胡敏酸在蒙脱石和高岭石上的吸附行为,并运用红外光谱、热重和Zeta电位等分析方法,表征分析了吸附前后的粘土矿物.实验结果表明,吸附过程受胡敏酸的初始浓度和pH值等因素影响;胡敏酸对粘土矿物的吸附等温线符合Freundlich等温方程;表征分析表明两种粘土矿物与胡敏酸复合体的红外光谱出现了C-H振动吸收峰;粘土矿物与胡敏酸结合后Zeta电位下降.实验的结果将有助于进一步探明环境中粘土矿物对胡敏酸的吸附机理.     

包气带土壤组成对三氯乙烯的吸附影响研究

有机质和矿物质是包气带土壤中的主要吸附介质,其吸附特性直接影响有机污染物在环境中的迁移、转化等过程。分别采用分析纯石英砂和典型粘土矿物高岭石模拟土壤的原生矿物和粘土矿物,利用批实验的方法研究土壤中各组成部分对三氯乙烯(TCE)的吸附行为。土壤有机质的吸附行为通过全土样和矿物质的对比得出。结果表明,粘土矿物是吸附氯代烃的主要矿物质,原生矿物对氯代烃的吸附量很小;土壤有机质含量和土壤吸附量之间有很好的正相关性;土壤有机碳含量与土壤粘土矿物含量的比值是影响吸附行为的另一重要因素,比值越小,Koc值越大,土壤对TCE的亲和力就越强。由于自然界中的土壤有机质大都与矿物质形成有机质-粘土矿物结合体,据此推测有机质-矿物质结合体会影响有机质的组成和形态,从而对其吸附行为有重要作用。     

环境污染物在蒙脱石层间域中的环境化学行为

天然蒙脱石层间阳离子通常是Ｃａ2 +,Ｎａ+,可以通过离子交换法制备各种阳离子交换蒙脱石。这些不同阳离子对蒙脱石层间域的环境化学行为有着不同的影响。金属阳离子与粘土矿物间的相互作用除了离子交换外 ,粘土的专性吸附作用有时也是非常重要的。目前 ,粘土矿物对重金属离子的专性吸附可概括为 4种机理 :(1)重金属离子与粘土矿物表面或断键基团质子的交换吸附 ;(2 )重金属离子进入粘土矿物硅氧四面体片的复三方空位或八面体片晶格缺陷中 ;(3)以金属络合物形式的专性吸附 ;(4)以金属氧化物或其它不溶性盐类沉淀形式。天然粘土矿物存在着大…     

粘土矿物对形成过渡带气的催化作用研究

本文分析了有机质在粘土矿物中的赋存状态，测定了粘土矿物的表面酸、实验模拟了低演化程度的烃源岩及其抽提物干酪根＋不同粘土矿物的催化机制、并通过粘土催化醇脱水反应对粘土过渡带有机质成气机理进行了探讨。研究结果表明，过渡带气的形成主要是受蒙脱石粘土矿物的催化所致，其原因是成岩过程中蒙脱石向混层矿物转化在蒙脱石晶间发生大量的铝代硅，因此在粘土表面产生电荷不平衡而形成酸性，井以路易斯酸和布郎酸作用于有机质，使碳－碳键发生断裂以形成气态烃。     

微生物降解蒙脱石层间吸附有机质的实验研究

近年来,国内外学者意识到,有机质在蒙脱石结构层间的吸附是有机质保存的重要机理之一,然而,目前关于微生物能否降解蒙脱石层间吸附有机质以及降解的程度等尚没有任何实验数据的支撑。本文试图通过人工合成含有层间吸附有机质的蒙脱石,利用海洋和湖泊沉积物中常见的降解有机质的微生物对其进行降解实验,据此探讨有机质的蒙脱石层间吸附在沉积物埋藏过程中对有机质保存的贡献。有机质选择半胱氨酸和甲苯,前者是生物生长所需的一种重要氨基酸,后者大量存在于土壤和沉积物中,多种细菌可以在有碳氢化合物的环境下将其降解。实验菌种选择恶臭假单胞杆菌(Pseudomonas putida)和腐败希瓦氏菌(Shewanella putrefaciens CN32)2种细菌,它们均为海洋和湖泊沉积物中的主导微生物,前者有较强的有机质降解能力,后者为铁的还原菌,厌氧代谢过程中能将蒙脱石结构中的Fe(III)还原为Fe(II)。通过上述不同菌种对蒙脱石层间吸附不同性质有机质的降解实验,结果显示,微生物对蒙脱石层间吸附的有机质的降解方式主要有分泌有机酸直接降解和破坏层间结构释放有机物从而进行降解。代表菌种假单胞菌和希瓦氏菌对半胱氨酸绿脱石及甲苯绿脱石的作用表明,微生物通过分泌有机酸的形式对蒙脱石层间吸附的有机质降解作用很有限,该结构在恒定的有氧和无氧条件下对保存有机质有利;希瓦氏菌在严格无氧条件下通过还原Fe(III)进行代谢,实验表明,无氧条件下,希瓦氏菌可以一定程度破坏矿物结构,释放并消耗有机物,因此,铁还原微生物对蒙脱石层间吸附有机质的保存有一定的影响,但由于微生物对矿物晶体结构的破坏能力有限,故其对层间吸附有机质降解的能力也有限;不同有机物对生物降解过程也有影响,这些影响取决于有机质的特性及有机质与细菌之间的相互作用。绿脱石层间吸附的半胱氨酸对生物生长有利,从而可能促进生物还原Fe(III)作用。相反,甲苯却很明显的抑制了Fe(III)的还原。由此可见,有机质的蒙脱石层间吸附是有机质保存的重要方式之一。     

几种粘土矿物对Pb^2＋的吸附作用及其主要影响因素的探讨

对土壤中常见的三种粘土矿物对Ｐｂ＾２＋的附作用及其主要影响因素进行了探讨。结果表明，三种粘土矿物对Ｐｂ６２＋的吸附能力顺序为：蒙脱石－伊利石－高岭石．蒙脱石对Ｐｖ＾２＋的吸附受ＰＨ的强烈影响，ＰＨ高有利于Ｐｂ＾２＋的吸附。与蒙脱石形成复合体形式的有机化合物的存在不利于蒙脱石对Ｐｂ＾２＋的吸附。     

Impact of Montmorillonite and Calcite on Release and Adsorption of Cyanobacterial Fatty Acids at Ambient Temperature

Minerals might act as important sorbents of sedimentary organic matter and reduce biodegradation, which favors the formation of hydrocarbon source rocks in the earth's history. Since most organic matter is degraded during the sinking process, at ambient temperature, it is important to investigate the adsorption capacity of different minerals during this process, to assess the organic loss from primary productivity to sedimentary organic matter. In this study, montmorillonite and calcite have been selected to study the impact of different minerals on the release, adsorption, and deposition of cyanobacterial (Synechococcus elonpata) fatty acids (FAs) at ambient temperature. Gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS) have been utilized to detect the variation in fatty acids. Primary results suggest that minerals have a different impact on dissolved organic matter. Montmorillonite can specifically enhance the release of fatty acids from cyanobacterial cells by lowering the pH values of the solution. The adsorption of the dissolved organic matter by montmorillonite will also be enhanced under a lower pH value. Conjunction of fatty acids with montmorillonite to form a complex will favor the sinking and preservation of these organics. Selective adsorption is observed among fatty acids with different carbon numbers. In contrast, calcite does not show any impact on the release and adsorption of organic matter even though it is reportedly capable of acting as a catalyst during the transformation of organic matter at high temperature. The primary data bridge a link between primary productivity and sedimentary organic matter, suggesting the relative importance of claystones in the formation of hydrocarbon source rocks in the earth's history.     

Role of the Interlayer Space of Montmorillonite in Hydrocarbon Generation: A Combined Study by TG-FTIR and High Temperature-Pressure Pyrolysis

The interlayer clay-organic complex is an important clay-organic association in sedimentary environments. The interlayer region of clay minerals not only provides storage space for organic matter, but also possesses solid acid sites; and these acid sites were proposed to be involved with the transformation of organic matter into liquid and gaseous hydrocarbons. However, the effect of the organic matter storage in the interlayer space of clay minerals on the hydrocarbons generation has not been made clear. In this study, the interlayer complex of 12-aminolauric acid (ALA) and Na+-montmorillonite (Na+-Mt), labeled as ALAinter-Mt (Na), was synthesized to investigate the role of the interlayer space of montmorillonite in hydrocarbon generation. Simply mixed ALA-Mt complex [ALA-Mt (Na)] was also prepared for comparison. The pyrolysis of ALA and ALA-Mt complexes was studied using thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) and a high temperature-pressure system (a confined gold capsule-autoclave system).     

Factors affecting the association of fatty acids with mineral particles in sea water

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.     

Parameters controlling the partitioning of tributyltin (TBT) in aquatic systems

In the present study the distribution of TBT between solid and water phase as a function of several parameters was determined. Two types of clay minerals (Na-montmorillonite SWy and kaolinite KGa) and quartz sand were used as sorbents in conventional batch experiments. Sorption coefficients (K_d) followed the order montmorillonite (89 l/kg) > kaolinite (51 l/kg) > quartz (25 l/kg), while for sorption coefficients normalized to the surface area (Kd′) an opposite trend was observed, with the lowest value determined for montmorillonite (2.79 × 10⁻³ l/m²) and the highest for quartz sand (8.04 × 10⁻² l/m²). The results demonstrate that numerous environmental parameters influence the adsorption process of TBT, such as solid/solution ratio, clay content and salinity. Another important factor governing TBT adsorption is pH, because it affects both the TBT species in the water phase as well as the surface properties of the mineral phase. The maximum of TBT adsorption onto clays was always around pH 6–7. According to the data, it is evident that the content of organic matter in the solid phase plays an important role on TBT adsorption, either as particulate organic matter (POM) or organic matter adsorbed to mineral particles (AOM). Experiments were carried out with well characterized organic matter and the results showed a linear increase of K_d from 51 up to 2700 l/kg upon the addition of 5% of particulate organic matter to pure phased kaolinite. TBT adsorption onto mineral surfaces, which were previously enriched with adsorbed organic matter, was investigated at different pH. The present study points to the importance of identifying and characterizing sorbents and envrionmental conditions, in order to predict and model TBT distribution in natural systems.     

天然黏土矿物和腐殖酸对纳米乳化油吸持的实验研究

为探讨天然黏土矿物及有机质对纳米乳化油在多孔介质中迁移滞留的影响，本文选取高岭石和蒙脱石这两种黏土矿物以及有机质的典型代表腐殖酸，开展了单一矿物、有机质及有机矿质复合物对纳米乳化油的吸持批实验研究，并运用比表面积全分析、扫描电镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射(XRD)等技术手段探讨了吸持机理。实验结果表明，介质对纳米乳化油的吸持均符合Freundlich模型；单一矿物及腐殖酸对纳米乳化油的吸持能力表现为：蒙脱石>腐殖酸>高岭石，有机矿质复合样品的吸持能力表现为：蒙脱石-腐殖酸>高岭石-腐殖酸，且均大于其对应的单一样品，出现了“1+1>2”的现象，表明介质组成越复杂，对纳米乳化油的吸持滞留程度越大。进一步分析证实，纳米乳化油主要通过氢键和疏水作用吸持在矿物和腐殖酸表面，表面结构性质是高岭石和蒙脱石吸持过程中的主导因素，因此蒙脱石具有更强的吸持能力，而腐殖酸的吸持主要通过颗粒间聚集作用来实现；对于复合样品，吸持主要通过氢键、配体交换和疏水作用结合来实现。腐殖酸与矿物的复合会增加吸持位点并且增强矿物表面疏水性，从而促进吸持。腐殖酸与纳米乳化油的共吸...     

Adams和Couch法古盐度恢复结果的可靠性检验——以青海湖布哈河口区沉积物为例

Adams公式和Couch公式是利用沉积物中硼元素浓度对沉积水体古盐度进行定量恢复的常用方法,但由于两种方法的恢复结果经常存在较大差异,古盐度的计算结果常难以让人信服。为了验证Adams公式和Couch公式的可靠性,本次研究采集了青海湖布哈河口区不同沉积环境的表层沉积物和底层水体样品,处理后分别分析了沉积物中硼元素浓度、总有机碳（TOC）含量及矿物组成,同时对水体盐度及其硼浓度进行了测量,结果表明:湖泊水体中硼浓度与盐度存在极好的线性正相关性,但沉积物中硼元素的浓度与沉积水体中硼的浓度并无直接联系。根据沉积物中硼的浓度及黏土矿物含量和组成,分别采用Adams公式和Couch公式对水体盐度进行计算,盐度计算值均远高于水体盐度实测值,其中Adams公式的计算结果与实测值差别最大,盐度计算值与沉积物中硼含量呈正相关关系。沉积物中的硼元素主要由继承自母岩的硼、黏土矿物吸附硼和有机质中富集的硼三部分组成,只有黏土矿物中的吸附硼能够反映水体盐度。青海湖布哈河口区沉积物富含有机质,有机质对硼强烈的富集作用是导致Adams公式和Couch公式盐度恢复结果失效的重要原因,同时不同类型黏土矿物对硼吸附能力的差异也对恢复结果有重要影响:黏土矿物在盐水中的浸泡试验表明蒙脱石对硼的吸附能力最强,次为伊利石,高岭石吸附能力最差,推翻了Couch关于伊利石对硼吸附能力最强的认识。原Adams公式和Couch公式仅没有考虑有机质对硼的影响,对不同类型黏土矿物吸附能力的认识有误,不适合陆相沉积物沉积水体古盐度的恢复。沉积物黏土矿物中吸附硼浓度仍是反映沉积水体盐度的可靠指标,古盐度的恢复首先必须消除沉积物中有机质对硼的影响,然后根据一系列的浸泡试验确定不同类型黏土矿物对硼的吸附系数,并建立新的计算公式。     

松辽盆地西南部DL铀矿带铀赋存状态及矿物组成特征

DL铀矿带是松辽盆地近年找矿的新发现。文章利用扫描电镜、电子探针和自动矿物参数定量分析系统等测试手段对该区矿石样品进行了铀赋存状态研究,结果表明:研究区铀主要以沥青铀矿、含锆铀矿物、含钛铀矿物等独立铀矿物以及黏土吸附、有机质吸附、锐钛矿吸附等吸附铀形式存在,铀矿物呈微粒状、细脉状、块状和团块状产出,空间上与磷灰石、硒铅矿、黄铁矿、有机质和碳酸盐等关系密切,与周边铀矿床的铀存在形式略有差别,其中含锆铀矿物在砂岩型铀矿中属首次发现。矿物组成以石英、长石、黏土矿物和碳酸盐为主,此外还有一定量的钛铁氧化物、重晶石、铁氧化物和少量独居石、磷钇矿、硒铅矿等副矿物。利用电子探针的铀定量分析数据和自动矿物参数定量分析系统的铀矿物定量分析数据,首次定量计算了不同存在形式铀的分布率,结果显示:独立铀矿物中沥青铀矿和含锆铀矿物的分布率最高,吸附铀以黏土矿物吸附占优势,有机质和锐钛矿吸附次之。铀赋存状态及矿物组成的精细厘定对矿床成因与选冶工艺研究等具有重要意义。     

粘土固体酸的表面酸性调控及其催化活性

固体酸是７０年代末发展起来的一类新型的催化材料,对有机反应具有较强的催化活性,且副反应少,产物易分离,污染少［１］。粘土固体酸是以蒙脱石类粘土为基质材料,通过采用不同的物理或化学方法在不同的条件下调控层间域而制备的,其催化活性和选择性与其表面酸的类型、浓度及强度等有关［２］,为此我们采用离子交换法,以不同类型的阳离子为取代剂,在不同条件下取代交换进入蒙脱石层间,研究制备方法及条件对表面酸性的影响,并考察了催化性能。１　实验部分１－１　原料与试剂钠基膨润土（浙江临安产,主要成分为蒙脱石,用沉降法提…