The origin of clay minerals in active and relict hydrothermal deposits

Samples of Fe-oxide-rich hydrothermal sediments were collected from active and inactive portions of the TransAtlantic Geotraverse (TAG) hydrothermal field on the Mid-Atlantic Ridge. Clays separated from TAG metalliferous sediments in this study all consist of Al-poor nontronite. Oxygen isotope thermometry of the clays yields formation temperatures of 54-67°C for samples from the inactive Alvin mound compared with 81-96°C for samples from the active TAG site. The latter are the highest recorded temperatures for authigenic hydrothermal clays. Sr isotope analysis of the clays from the active mound suggests that they precipitated from seawater-dominated fluids, containing less than 15% hydrothermal end-member fluid. In contrast, nontronite from the inactive Alvin mound has ⁸⁷Sr/⁸⁶Sr values that closely resemble that of detrital North Atlantic clays, suggesting a dominantly continental source for the Sr. Rare earth element data are consistent with a significant detrital input to the inactive site but also demonstrate the extent of hydrothermal input to the low temperature fluid. Crystallographic fractionation of the trivalent REE is apparent in the heavy REE enrichments for all nontronite samples. The inferred formation-mechanism for nontronite-rich Fe-oxyhydroxide deposits at the surface of the active mound is by direct precipitation from low temperature fluids. At the inactive Alvin site, in contrast, the deposits form during alteration of pelagic sediments by diffuse fluids and replacement of biogenic carbonate with nontronite and Fe-oxyhydroxide. These two modes of formation are both important in seafloor hydrothermal settings where clay minerals are a significant component of the hydrothermal deposit.     

Composition and origin of clay minerals in Holocene sediments from the south-eastern North Sea

The distribution of clay minerals varies systematically in sediments from Holocene core material taken along a profile from the East Frisian coast to the Doggerbank. The proportion of illite increases with distance from the coast at the expense of kaolinite, whereas slight variations are seen in smectite and chlorite abundances. The chemical composition changes, and the K/Rb ratio and K-Ar isotopic age of illite increase seawards. This trend results from progressive mixing processes of riverine detritus with Pleistocene fluvioglacial material reworked during the Holocene transgression. However, the clay fluvial flux only became dominant during the decreasing rate of sea-level rise in the Late Holocene, especially near the shore. For example, modern sediments in tidal flats contain 75% of river-borne Holocene-supplied clay detritus, whereas this amount is only 10% in modern marine sediments at the Doggerbank.     

Gas-chromatographic investigations on dimethyldioctadecyl ammonium derivatives of different clay minerals

The gas-chromatographic behaviour (selectivity performance for cyclohexanebenzene and m-, p-xylenes pairs separation) of dimethyldioctadecylammonium complexes with kaolinite, fire-clay, halloysite, attapulgite, hectorite and various montmorillonites, nontronites and vermiculites has been investigated. The obtained data indicate the influence of specific surface and charge density on relative retention value (), and of substitution location (tetrahedral versus octahedral sheet) within the clay lattice on selectivity. Hence, derivatives with nontronites and vermiculites, that is the clay minerals where the principal lattice substitutions are predominantly occurring within the tetrahedral sheet and possessing the highest surface charge density, are very effective sorbents for gas-chromatographic use. The application of gas-chromatography as investigation tool of clays surface is suggested.     

Chemical evidence for advection of hydrothermal solutions in the sediments of the Galapagos Mounds Hydrothermal Field

Pore water profiles of Ca, Mg, F, PO₄^?3 and Mn in the Galapagos Mounds Hydrothermal Field are believed to reflect, in part, upwelling of hydrothermal solutions through the sediments. Concentration-depth profiles in a low heat flow area just north of the Mounds Field display diagenetic changes typical of those found in pore waters underlying highly productive surface waters, consistent with the inference of no water flow or very slow downwelling ($\text{w < 5}\text{cm/yr}$) of bottom water through these sediments. Rates of upward advection calculated from Mounds Field pore water profiles of Ca, Mg, and F profiles agree well with each other, averaging about 1 cm/yr in the pelagic sediments near the mounds and 15–30 cm/yr within the hydrothermal mounds themselves. The upward advection also modifies the shape of PO₄^?3 and Mn profiles.Advection rates inferred from the pore water data are generally in reasonable agreement with those made from heat flow data.The higher Ca and lower Mg, F, PO₄^?3 and Mn concentrations in Mounds Field pore waters (compared with those of the low heat flow area) suggest chemical exchange between the solution and basalt prior to upwelling. Li⁺, K⁺, Rb⁺, Sr⁺⁺ and SO₄^? concentrations are indistinguishable from bottom water. This suggests very high effective water/rock ratios during the reactions which produced the upwelling solutions, perhaps due to extensive prior alteration of basalt adjacent to the flow path of water through the crust Inferred reaction temperatures are between 70–150°C.     

大西洋洋中脊TAG热液区硫化物铅和硫同位素研究

位于大西洋洋中脊26.08°N的TAG热液区是目前已知的赋存在无沉积物覆盖的洋中脊区的一个最大的海底热液硫化物矿床.新测得来自ODP-158航次钻孔的9件热液硫化物的铅、硫同位素组成;2件铁锰氧化物和1件底盘玄武岩的铅同位素组成.结果表明,矿石硫化物的铅同位素组成206Pb/204Pb为18.2343～18.3181,207Pb/204Pb为15.4717～15.5061,208Pb/204Pb为37.7372～37.8417;它们位于该区底盘玄武岩(206Pb/204Pb=18.1454,207Pb/204Pb=15.4572,208Pb/204Pb=37.6534)和近洋底铁锰氧化物(206Pb/204Pb,207Pb/204Pb,208Pb/204Pb分别为18.6907～18.9264,15.5615～15.6279,38.1164～38.3687)的铅同位素组成之间.三者呈线性相关关系,说明硫化物中铅来源于地幔(玄武岩)与海水(铁锰氧化物)的两端元混合.硫化物的硫同位素组成δ34S为6.2‰～9.5‰,它明显高于地幔玄武岩的硫同位素组成(δ34S=±0‰),也高于东太平洋海隆EPR21°N(δ34S=0.9‰～4.0‰)和大西洋洋中脊MAR23°N(δ34S=1.2‰～2.8‰)等热液活动区硫化物的硫同位素组成,这一特征反映了TAG热液体系中硫来源于地幔玄武岩硫与海水硫酸盐无机还原作用产生的硫的两端元混合.因此,铅硫同位素研究为现代大洋底热液硫化物矿床形成过程中矿质来源及流体混合作用提供了十分有益的信息.     

冲绳海槽Jade热液活动区块状硫化物的铅同位素组成及其地质意义

新测行Ｊａｄｅ热液活动区中５件块状硫化物样品的铅同位素组成,具有较小的变化范围,表现出较均一的铅同位素组成特征。在Ｐｂ－Ｐｂ图解上,块状硫化物的铅同位素数据构成线形排列,与该区沉积物和蚀变火山岩的铅同位素组成一致,而与该区新鲜火山岩相比具较高的放射成因铅,证实了该区海底块状硫化物中的铅是由沉积物长英质火山岩来源铅共同构成的混合铅。不同热液活动区铅同位素组成对比研究表明,地质－构造环境的不同是导致各     

Sulfide minerals in the Menez Gwen nonmetallic hydrothermal field (Mid-Atlantic Ridge)

Mineralogy and geochemistry of the sulfide-bearing rocks and ores discovered in the Menez Gwen field are studied. Samples were taken during the expedition of the Shirshov Institute of Oceanology (cruise 49, R/V Akademik Mstislav Keldysh. The mineral composition of rocks and ores were studied by the traditional methods of optical microscopy, scanning electron microscopy (CAMSCAN), and microprobe analysis (EPMA SX-50). Contents of trace elements were determined by the laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS). The Zn-Cu ore comprises zonal sulfide chimney intergrowths. Numerous Se-rich copper ore fragments occur in the volcanomictic layered gritstones and/or barite slabs. The mineral composition, zonality, and association of trace elements in ore are typical of “black smokers” formed at the basalt base near the Azores Triple Junction in the MAR. The results obtained make it possible to reconstruct formation history of the Menez Gwen hydrothermal field into the high-temperature (Cu-Se association in ore clasts), medium-temperature (Zn-Cu-As association in ore), and recent (Ba-SiO₂ association) stages.     

Chemical and isotopic constraints on water/rock interactions at the Lost City hydrothermal field, 30°N Mid-Atlantic Ridge

Low temperature vent fluids (<91 °C) issuing from the ultramafic-hosted hydrothermal system at Lost City, 30°N Mid-Atlantic Ridge, are enriched in dissolved volatiles (H₂,CH₄) while attaining elevated pH values, indicative of the serpentization processes that govern water/rock interactions deep in the oceanic crust. Here, we present a series of theoretical models to evaluate the extent of hydrothermal alteration and assess the effect of cooling on the systematics of pH-controlled B aqueous species. Peridotite-seawater equilibria calculations indicate that the mineral assemblage composed of diopside, brucite and chrysotile likely dictates fluid pH at moderate temperature serpentinization processes (<300 °C), by imposing constraints on the aCa⁺⁺/a²H⁺ ratios and the activity of dissolved SiO₂. Based on Sr abundances and the ⁸⁷Sr/⁸⁶Sr isotope ratios of vent fluids reported from Lost City, estimated water/rock mass ratios (w/r = 2-4) are consistent with published models involving dissolved CO₂ and alkane concentrations. Combining the reported δ¹⁸O values of vent fluids (0.7‰) with such w/r mass ratios, allows us to bracket subseafloor reaction temperatures in the vicinity of 250 °C. These estimates are in agreement with previous theoretical studies supporting extensive conductive heat loss within the upflow zones. Experimental studies on peridotite-seawater alteration suggest that fluid pH increases during cooling which then rapidly enhances boron removal from solution and incorporation into secondary phases, providing an explanation for the highly depleted dissolved boron concentrations measured in the low temperature but alkaline Lost City vent fluids. Finally, to account for the depleted ¹¹B composition (δ¹¹B ∼25-30‰) of vent fluids relative to seawater, isotopic fractionation between tetrahedrally coordinated aqueous boron species with BO₃-bearing mineral sites (e.g. in calcite, brucite) is proposed.     

鸡西盆地下白垩统城子河组-穆棱组露头砂岩中的黏土矿物成因探讨

对鸡西盆地下白垩统城子河组—穆棱组露头砂岩中的黏土矿物进行了X-衍射分析。研究结果表明,黏土矿物主要由伊利石,高岭石和伊/蒙混层组成,组合可分为高岭石型与伊/蒙混层和伊利石型两种,根据黏土矿物组合判断露头砂岩处于中成岩阶段A期。下白垩统城子河组—穆棱组煤系地层和泥岩成岩过程中析出的有机酸是高岭石型黏土矿物组合发育的重要原因,而沉积相带水动力条件弱导致砂岩渗滤条件的变差则是伊/蒙混层和伊利石型黏土矿物组合形成的原因。     

Paleoenvironmental reconstruction from chemical and isotopic compositions of Permo-Pennsylvanian pedogenic minerals

Mineralogical and chemical analysis of Late Pennsylvanian and Early Permian paleosols from the eastern shelf of the Midland basin, north-central Texas, USA, are used to test hypothesized climate change in Late Paleozoic western equatorial Pangea, previously defined independently on the bases of sedimentologic and paleontologic proxies and climate models. The <0.2-μm size phyllosilicate fraction in the studied paleosols exhibits down-profile trends in mineralogy and chemical composition that are consistent with modern weathering profiles suggesting a dominantly pedogenic origin. A stratigraphic trend from kaolinite-dominated profiles in Upper Pennsylvanian paleosols to profiles dominated by smectite and hydroxy-interlayered 2:1 phyllosilicates in Lower Permian paleosols indicates a relatively rapid decrease in soil weathering and leaching in the latest Pennsylvanian followed by a more gradual decrease in leaching throughout the Early Permian. The chemical composition (cation ratios and exchange capacity) of these phyllosilicates further corroborates this shift toward less intensive leaching, presumably in response to climate change from humid to progressively more arid conditions.The phyllosilicates in the <0.2-μm size fraction and contemporaneous pedogenic calcites from the Permo-Pennsylvanian paleosols exhibit a long-term stratigraphic increase in their δ¹⁸O values of as much as ∼3.2‰ and ∼5.2‰, respectively. This long-term trend is consistent with a transition throughout the latest Pennsylvanian through Early Permian toward progressively more evaporatively enriched soil waters. Superimposed on the long-term trend is an apparent rapid enrichment (1.5 to 2‰) in phyllosilicate δ¹⁸O values immediately above the Pennsylvanian-Permian boundary. Observed oxygen isotope fractionation between the phyllosilicates and calcites within individual paleosols indicate isotopic disequilibrium between mineral pairs. This is attributed to a minor detrital component in the pedogenic clay-dominated phyllosilicate fraction coupled with the effects of seasonality of mineral formation. Inferred δ¹⁸O compositions of Late Paleozoic meteoric water (−2‰ to +4‰) are compatible with less intensive soil leaching under conditions of increasing aridity, possibly coupled with a shift in local precipitation from a continental source to a marine source.     

云南南秧田钨矿床电气石的成分和硼同位素特征及成矿意义

南秧田矿床是滇东南地区最大的以钨为主的金属矿床。文章以含电气石花岗片麻岩、无矿电气石石英脉和白钨矿矿化电气石石英脉样品为研究对象,结合地质特征、电气石元素地球化学及B同位素,对电气石成因开展研究。研究显示三类电气石均属于碱性电气石中的镁电气石,以富Mg及Y位中无Al或低Al为特征,具有相对高的FeO/(FeO+MgO)比值(平均0.53);其稀土元素(REE)配分曲线与晚白垩世花岗岩稀土元素配分曲线相似;δ~(11)B值集中在-14‰,与地壳平均值非常接近,这些特征表明其与岩浆期后热液成因的电气石特征一致。电气石石英脉中广泛的钨矿化表明晚白垩世岩浆期后热液对矿区主矿体的叠加富集作用明显,据此提出距晚白垩世花岗岩体数百米至一千米的中源距离为有利矿化区,为矿区外围及深部勘查评价指明了找矿方向。     

Effects of clay minerals and biosurfactants on isotopic and molecular characteristics of methane encaged in pressure vessel gas hydrates

The stable isotope values of carbon (δ¹³C_methane) and hydrogen (δ²H_methane) from methane molecules trapped in gas hydrates are useful for differentiation of methane from microbial and thermal origins, providing valuable information during hydrocarbon exploration. Recent studies have reported catalysis of methane hydrates when smectite clays and biosurfactants are present in hydrate-hosting sediments, but catalytic influences on the values of δ¹³C_methane and δ²H_methane are not well documented. In this study, pressure vessel methane hydrates were formed from solutions in contact with smectite clays (montmorillonite and nontronite) and biosurfactants (rhamnolipids and surfactin). Experiments show less than 1‰ differences in values of δ¹³C_methane between free and encaged molecules and up to 10‰ variations in values of δ²H_methane between free and encaged molecules. Notably, methane consumption increased in methane hydrates formed from solutions containing biosurfactants and biosurfactant–smectite mixtures. Results presented here indicate that a hydrate formed in the presence of smectite clays and biosurfactants are characterized by small shifts in free and encaged values of δ¹³C_methane and δ²H_methane and do not complicate interpretation of gas origin. In contrast, methane consumption in hydrates formed under the catalytic effect of smectite clays and biosurfactants modifies gas wetness, obscures gas origin and complicates interpretation of thermal maturity.     

Lime stabilization of clay minerals and soils

Clay soil can be stabilized by the addition of small percentages, by weight, of lime, thereby enhancing many of the engineering properties of the soil and producing an improved construction material. In order to illustrate such improvements, three of the most frequently occurring minerals in clay deposits, namely, kaolinite, montmorillonite and quartz were subjected to a series of tests. As lime stabilization is most often used in relation to road construction, the tests were chosen with this in mind. Till and laminated clay were treated in similar fashion. With the addition of lime, the plasticity of montmorillonite was reduced whilst that of kaolinite and quartz was increased somewhat. However, the addition of lime to the till had little influence on its plasticity but a significant reduction occurred in that of the laminated clay. All materials experienced an increase in their optimum moisture content and a decrease in their maximum dry density, as well as enhanced California bearing ratio, on addition of lime. Some notable increases in strength and Young's Modulus occurred in these materials when they were treated with lime. Length of time curing and temperature at which curing took place had an important influence on the amount of strength developed.     

上新世以来伊豆-小笠原海脊黏土矿物的来源与古气候意义

对伊豆-小笠原海脊(ODP 782A孔)上新世以来沉积物中黏土矿物的组成、含量及矿物学特征进行了分析,结果表明:黏土矿物以伊利石(42%)和蒙皂石(42%)为主,绿泥石的平均含量为14%,高岭石的含量最低,平均仅为2%。伊利石的结晶度较好,平均为0.25°Δ2θ;化学指数较低,平均为0.31;表明伊利石主要形成于干冷的气候环境。通过将ODP 782A孔黏土矿物组合特征和含量与周边可能源区对比,并结合伊利石和蒙皂石的矿物学参数特征,我们认为蒙皂石主要来源于伊豆-小笠原海脊周边岛弧火山物质;伊利石、绿泥石和高岭石主要来自亚洲大陆风尘。上新世以来(伊利石+绿泥石)/蒙皂石比值总体上呈增加的趋势,并且在5.3~3.6、3.6~1.6、1.6~0 Ma的三个阶段表现出不同的变化特征,该比值与全球深海δ¹⁸O值所记录的全球变冷、北太平洋ODP 885/886孔风尘通量和灵台黄土沉积速率,以及日本海U1430站伊利石/蒙皂石比值所指示的亚洲内陆干旱变化的总体变化趋势和阶段性变化的时间点大致同步,表明该比值敏感地响应了全球变冷和亚洲内陆的干旱。上新世以来(伊利石+绿泥石)/高岭石比值表现为高/低交替变化,分别与中国灵台黄土磁化率高/低变化相对应,由于黄土磁化率记录了亚洲内陆干/湿变化,因此该黏土矿物比值敏感地响应了亚洲内陆的古气候变化,因而可以作为可靠的亚洲大陆干/湿变化示踪指标。     

Transformational changes of clay minerals, zeolites and silica minerals during diagenesis

Diagenetic transformation of clay minerals, zeolites and silica minerals in Cretaceous and Tertiary argillaceous rocks from deeply drilled wells in Japan were studied. Transformations of these minerals during diagenesis were as follows: in clay minerals, montmorillonite → montmorillonite-illite mixed-layer mineral → illite; in zeolites, volcanic glass → clinoptilolite → heulandite and/or analcite → laumontite and/or albite; in silica minerals, amorphous silica → low-cristobalite → low-quartz. Maximum overburden pressures and geothermal temperatures corresponding to these transformations in each well studied were calculated. For clay minerals, a pressure of approximately 900 kg cm^?2 and a temperature of about 100°C are necessary for the transformation from montmorillonite to mixed-layer mineral and 920 kg cm^?2 and 140°C for mixed-layer mineral to illite. Transformation from kaolinite to other minerals requires much higher pressures and temperatures than from montmorillonite to mixed-layer mineral. For zeolites, 330 kg cm^?2 and 60°C are required for the transformation from volcanic glass to clinoptilolite, 860 kg cm^?2 and 120°C for clinoptilolite to heulandite and/or analcite, and 930 kg cm^?2 and 140°C for heulandite and/or analcite to laumontite and/or albite. For silica minerals, 250 kg cm^?2 and 50°C are necessary for the transformation from amorphous silica to low-cristobalite and 660 kg cm^?2 and 70°C for low-cristobalite to low-quartz. Based on these diagenetic mineral transformations, seven mineral zones are recognized in argillaceous sediments. On the other hand, from the porosity studies of argillaceous sediments in Japan, the process of diagenesis is classified into the following three stages. The early compaction stage is marked by shallow burial and viscous rocks with more than 30% porosity. The late compaction stage is characterized by intermediate burial and plastic rocks with 30-10% porosities. The transformation stage is marked by deep burial and elastic rocks with less than 10% porosity.