Evaluation of redox-active iron sites in smectites using middle and near infrared spectroscopy

Redox processes of structural Fe in clay minerals play an important role in biogeochemical cycles and for the dynamics of contaminant transformation in soils and aquifers. Reactions of Fe(II)/Fe(III) in clay minerals depend on a variety of mineralogical and environmental factors, which make the assessment of Fe redox reactivity challenging. Here, we use middle and near infrared (IR) spectroscopy to identify reactive structural Fe(II) arrangements in four smectites that differ in total Fe content, octahedral cationic composition, location of the negative excess charge, and configuration of octahedral hydroxyl groups. Additionally, we investigated the mineral properties responsible for the reversibility of structural alterations during Fe reduction and re-oxidation. For Wyoming montmorillonite (SWy-2), a smectite of low structural Fe content (2.8 wt%), we identified octahedral AlFe(II)-OH as the only reactive Fe(II) species, while high structural Fe content (>12 wt%) was prerequisite for the formation of multiple Fe(II)-entities (dioctahedral AlFe(II)-OH, MgFe(II)-OH, Fe(II)Fe(II)-OH, and trioctahedral Fe(II)Fe(II)Fe(II)-OH) in iron-rich smectites Ölberg montmorillonite, and ferruginous smectite (SWa-1), as well as in synthetic nontronite. Depending on the overall cationic composition and the location of excess charge, different reactive Fe(II) species formed during Fe reduction in iron-rich smectites, including tetrahedral Fe(II) groups in synthetic nontronite. Trioctahedral Fe(II) domains were found in tetrahedrally charged ferruginous smectite and synthetic nontronite in their reduced state while these Fe(II) entities were absent in Ölberg montmorillonite, which exhibits an octahedral layer charge. Fe(III) reduction in iron-rich smectites was accompanied by intense dehydroxylation and structural rearrangements, which were only partially reversible through re-oxidation. Re-oxidation of Wyoming montmorillonite, in contrast, restored the original mineral structure. Fe(II) oxidation experiments with nitroaromatic compounds as reactive probes were used to link our spectroscopic evidence to the apparent reactivity of structural Fe(II) in a generalized kinetic model, which takes into account the presence of Fe(II) entities of distinctly different reactivity as well as the dynamics of Fe(II) rearrangements.     

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。     

Clay minerals in sediments of the hydrothermally active southern trough in the Guaymas Basin (Gulf of California)

The results of the study of clay mineral alterations in Upper Pleistocene sediments of the southern trough in the Guaymas Basin (Gulf of California) due to the influence of hydrothermal solutions and heat produced by sill intrusions are discussed. Core samples from DSDP Holes 477 and 477A were taken for the analysis of clay minerals. Application of the method of modeling X-ray diffraction patterns of oriented specimens of the finely dispersed particles made it possible to establish the phase composition of clay minerals, determine their structural parameters, and obtain reliable quantitative estimates of their contents in natural mixtures. The modeling data allowed us to characterize reliably the transformation of clay minerals in sediments of the hydrothermally active southern trough in the Guaymas Basin. In Upper Pleistocene sandy–clayey sediments of the southern trough, changes in the composition of clay minerals occurred under the influence of a long-living hydrothermal system. Its lower part (interval 170.0–257.5 m) with maximum temperatures (~300°C) was marked by the formation of chlorite. Terrigenous clay minerals are not preserved here. Saponite appears at a depth of 248 m in the chlorite formation zone. Higher in the sedimentary section, the interval 146–170 m is also barren of terrigenous clay minerals. Sediments of this interval yielded two newly formed clay minerals (chlorite and illite), which were formed at lower temperatures (above 180°C and below 300°C, approximately up to ~250°C), while the relatively low-temperature upper part (110–146 m) of the hydrothermal system (from ~140°C to ~180°C) includes the mixture of terrigenous and newly formed clay minerals. Terrigenous illite is preserved here. Illitization of the mixed-layer illite–smectite was subjected to illitization. The terrigenous montmorillonite disappeared, and chlorite–smectite with 5–10% of smectite layers were formed. In the upper interval (down to approximately 110 mbsf), the composition of terrigenous clay minerals remains unchanged. They are composed of the predominant mixed-layer illite–smectite and montmorillonite, the subordinate illite, mixed-layer chlorite–smectite with 5% of smectite layers, mixed-layer kaolinite–smectite with 30% of smectite layers, and kaolinite. This composition of clay minerals changed under the influence of sill intrusions into the sedimentary cover at 58–105 m in the section of Hole 477. The most significant changes are noted in the 8-m-thick member above the sill at 50–58 m. The upper part of this interval is barren of the terrigenous mixed-layer illite–smectite, which is replaced by the newly formed trioctahedral smectite (saponite). At the same time, the terrigenous dioctahedral smectite (montmorillonite) is preserved. The composition of terrigenous clay minerals remains unchanged at the top of the unit underlying the sill base.     

Mineralogical characterization of acid weathered phyllosilicates with implications for secondary martian deposits

The detection of phyllosilicates and sulfates on Mars has revealed a complex aqueous history which suggests distinct geochemical environments separated temporally and spatially. Recent observations by MRO CRISM in Mawrth Vallis have shown that phyllosilicate deposits exhibit a specific stratigraphy, which remains incompletely understood. Moreover, MER Spirit has evidenced association between phyllosilicates, amorphous silica and sulfates. We investigated the hypothesis that these parageneses resulted from the acidic weathering of older phyllosilicate deposits. We exposed nontronite (Fe-rich smectite), montmorillonite (Al-rich smectite) and kaolinite to H₂SO₄ solutions at pH 0, 2 and 4, and at a temperature of 60 °C. After the acid treatment, a combination of mineralogical techniques was used to assess the degree of alteration of the three phyllosilicate minerals. XRF, XRD and ESEM measurements show that nontronite was the most unstable when acid leached, followed by montmorillonite and then kaolinite. Progressive acidic leaching of nontronite leads to alteration of the phyllosilicate to amorphous silica, along with Fe-sulfate and anatase, and the formation of an acidic Al,Fe-rich solution. Alteration of montmorillonite resulted in the formation of Fe-, Al-, Ca- and Mg-sulfates, and a Al-rich leaching solution. Comparatively, leaching of kaolinite resulted in the formation of Al-sulfates and a Al-rich solution as well, with only slight alteration of the primary mineralogical features. The effects of acid leaching of the phyllosilicates were also observed in NIR reflectance spectra, allowing a comparison with CRISM spectra from Mawrth Vallis. Based on our results, we propose a new model where acid leaching of mixed phyllosilicate deposits leads to kaolinite overlaying montmorillonite, which in turn caps Fe,Mg-smectites. Leaching of cations and subsequent evaporation leads to sulfate deposits, as supported by geochemical modeling, while amorphous silica remains as a residue. Depending on the intensity (pH) and length of exposure of acidic leaching, our model can explain the stratigraphic distribution of phyllosilicates, and the association of sulfates, silica and smectites.     

Magnetic properties of oxidized and reduced smectites

 Four smectites with different total Fe contents (two nontronites, one ferruginous smectite, and one montmorillonite) were reduced to obtain a range of Fe(II)/Fe(III) ratios and their magnetic properties measured with a SQUID (superconducting quantum interference device) as a function of applied magnetic field strength at 5 K and as a function of temperature in a field of 0.1 T. The unaltered nontronite and ferruginous smectite specimens showed antiferromagnetic coupling, whereas the coupling in the reduced samples was ferromagnetic; the paramagnetic Curie temperature increased with increasing Fe(II) content. Data collected after cooling samples in both the presence and absence of an external magnetic field of 0.1 T showed that at low temperatures the reduced (ferromagnetic) nontronite and ferruginous smectite samples exhibit a memory effect of previous magnetic field exposure consistent with superparamagnetic or spin glass behavior. The superparamagnetic/ferromagnetic transition temperature, T _f , increased linearly with increasing Fe(II) content for each of the nontronites, but the relationship between T _f and Fe(II) content differed for different clays, thus demonstrating that T _f is sensitive to isomorphous substitutions in the clay structure. The montmorillonite was paramagnetic in both oxidized and reduced forms. Received: 23 March 1999 / Revised, accepted: 27 August 1999     

Chemical and isotopic investigations into the origin of clay minerals from the Galapagos hydrothermal mounds field

A dark green authigenic nontronite is the major component of the Galapagos hydrothermal mounds field sediments. Oxygen isotopic compositions of the chemically purified, <0.2-μm fraction of the nontronitic clays indicate formation temperatures of 25° to 47°C, in contrast with measured in situ mounds temperatures of up to 15°C. Assuming an authigenic origin, the Fe-rich montmorillonite that dominates in the noncarbonate clay fraction of the surrounding pelagic ooze has isotopic formation temperatures of 27° to 39°C, compared with measured in situ temperatures of ca. 3.5° to 6.5°C. The higher isotopic formation temperatures calculated for the hydrothermal nontronite suggest either complex patterns of fluid circulation and nontronite precipitation presently within the mounds or a higher thermal history associated with rapid and episodic periods of deposition during the Holocene-Pleistocene. The apparent high isotopic temperature of the Fe-rich montmorillonite may reflect: (1) formation under hydrothermal conditions at spreading centers with subsequent dispersal by bottom currents, (2) a detrital origin of the mineral, or (3) a mixture of authigenic Fe-montmorillonite and detrital Al-montmorillonite in this region.     

Composition,oxygen isotope geochemistry and origin of smectite in the metalliferous sediments of the Bauer Deep,southeast Pacific

The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite.Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite.Infra-red and Mossbauer spectroscopy and wet chemical analysis (LiBO₂ fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3°C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth.Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed.Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO₃ accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions).     

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.     

Occurrence of well-crystallized nontronite in the gas vesicles of a megaporphyritic basalt flow near Nighoj, Ahmednagar district, Maharashtra

Occurrence of well crystallized nontronite in a megaporphyritic basalt flow from Nighoj area, Maharashtra, India is reported. Thin section studies of the vesicles from periphery to the centre reveal the presence of greenish palagonite, probably indicating the stages of devitrification of glass and the weathering of palagonite to the formation of nontronite. The centre of the vesicles is marked by the presence of dark greenish-brown, radiating and fibrous sheets of nontronite. X-ray diffraction (XRD) analysis reveals the dominant presence of smectite (nontronite) as the major phase with traces of pyroxene. Scanning Electron Microscopy (SEM) shows well developed sheets of nontronite within the gas vesicles of the megaporphyritic basalt flows. In the present investigation, the nontronite within the gas vesicles of the megaporphyritic basalts at Nighoj was formed in-situ due to the devitrification of glass containing palagonite. Palagonite is an intermediate step in the alteration that may be accomplished by the steam generated in quenching of the lava. Weathering of palagonite under conditions of poor drainage is essential to the genesis of nontronite as has been suggested by Victor and Vernon (1946).     

Conditions and mechanism for the formation of iron-rich Montmorillonite in deep sea sediments (Costa Rica margin): Coupling high resolution mineralogical characterization and geochemical modeling

Iron-rich smectite is commonly described in the diagenetic fraction of deep-sea sediment, as millimeter to centimeter aggregates dispersed in the sediment, or as a coating on sedimentary particles or nodules. This study examines several factors to elucidate formation mechanisms of a particular iron-rich smectite and its potential transformation to glauconite. The study combines a detailed mineralogical investigation on natural samples and a chemical modeling approach to assess mineralogical reactions and pathways.Transmission electron microscopy (TEM) observations and analytical electron microscopy (TEM-AEM) analyses were conducted on microtomed samples of millimeter- to centimeter-long green grains. These grains are widespread in pelagic calcareous sediment from the Costa Rica margin. They are composed of pyrites that are partially dissolved and are surrounded by amorphous or very poorly crystallized iron-rich particles. Iron-rich montmorillonite grows from an amorphous precursor and its formation requires the input of Si, O, Mg, K, Na and Ca; our results suggest that these inputs are supported by the dissolution of sedimentary phases such as volcanic glasses, siliceous fossils and silicates.Thermodynamic modeling of fluid-sediment interactions was conducted with the geochemical computer code PhreeqC, using mineralogical and pore fluid compositions from sediment samples and calculated estimates for thermodynamic constants of smectites that are not maintained by the computer code. Simulations confirm the possibility that the green grains are the product of pyrite alteration by seawater under oxidizing conditions. The extent of smectite production is controlled by the kinetics of pyrite dissolution and fluid migration. The absence of aluminum in the Costa Rica margin system explains the formation of an iron-rich montmorillonite instead of glauconite, whereas the presence of calcite that buffers the system explains the formation of an iron-rich montmorillonite instead of iron oxides.     

La sédimentation argileuse depuis l'Eocène sur le plateau Vøring et à son voisinage, d'après le Leg 38 DSDP (Mer de Norvège)

The study of clays from sites 338 to 343 enables the main lines of the palaeogeographical evolution of the Vøring plateau, off Norway, to be determined. The following stages are proposed: (1) In early Eocene sediments, clays provide evidence of erosion of the Scandinavian shield; detrital primary minerals (illite, chlorite) derived from crystalline rocks are dominant. This erosion results from tectonic movements coeval with the opening of the Norwegian basin. The rejuvenation of marginal relief hinders pedogenesis, which is only indicated by the presence of minerals coming from the few soils which are developed. (2) From the Middle Eocene, primary minerals decrease while smectite becomes dominant. This trend increases through the late Eocene and at the beginning of the Middle Oligocene, where only smectite is present. During this period the basin margins are stabilized after the initial movements. In essentially pelagic marine sediments, the smectite seems to be derived from volcanic rocks. (3) During the Middle Oligocene and early to Middle Miocene, smectite is always dominant, but primary minerals reappear, with mixed-layers indicating a moderate continental alteration. This composition suggests a modification of the climate, mainly marked by an increase in humidity. (4) In Pliocene and Plio-Pleistocene sediments, primary minerals are dominant, while smectite decreases. The glacial climate is responsible for this mineralogy. Detrital minerals would come from the erosion of Scandinavian moraines and from rafting by icebergs.     

兰州盆地永登剖面晚古新世—早渐新世沉积物中粘土矿物的特征及其古气候指示意义

采用X射线衍射、扫描电镜分析方法,对兰州盆地永登剖面晚古新世—早渐新世沉积物中粘土矿物的相对含量、伊利石结晶度、显微形貌及其古气候意义进行深入研究。结果表明:晚古新世—早渐新世沉积物中粘土矿物主要为伊利石、蒙脱石、绿泥石和少量的坡缕石,其中伊利石的含量最高,而且从晚古新世到早渐新世,沉积物中伊利石的含量呈明显升高的趋势,蒙脱石则呈明显减少的趋势;在大约55 Ma处伊利石含量急剧减小,而蒙脱石含量急剧增大。此外,可见到毛发状的自生坡缕石沿蒙脱石晶片边缘交代生长,而碎屑成因的坡缕石则主要呈破碎的短棒状。粘土矿物分布特征表明,兰州盆地晚古新世—早渐新世的古气候以干旱为主导,并且经历了由相对温暖湿润到半干旱半湿润或干旱炎热的转变,这种气候转型主要受全球气候的影响,即受行星风系的控制;而在大约55 Ma处伊利石、蒙脱石的含量变化则记录了全球性的PETM事件。     

Variability of fluvial sediment supply to the Laptev Sea continental margin during Late Weichselian to Holocene times: implications from clay–mineral records

Three sediment cores from the Laptev Sea continental margin were investigated for their clay mineralogy by X-ray diffraction to study the fluvial sediment supply since the late Weichselian. In the study area, the clay-mineral composition of surface sediments is characterized by distinct regional variations. The source area for smectite in the eastern Eurasian Basin is the Putoran Plateau drained by the Khatanga and Yenisei rivers. Currents caused by river discharge and the inflow of Atlantic water masses along the Eurasian continental margin are responsible for sediment distribution. In the sediment cores, smectite and illite contents show an opposite trend which mainly results from variable smectite supply. During MIS 2 the amount of smectite on the Laptev Sea continental margin never exceeds 10 rel.%. Probably, reduced river discharge and the lowered sea level during MIS 2 caused a decreased sediment supply to the Laptev Sea. Additionally, the Putoran Plateau was covered by an ice sheet during the Late Weichselian preventing the erosion of smectite-rich soils. In contrast, maximum smectite contents (up to 30 rel.%) in Holocene sediments result from increased sediment input by the Khatanga River and from the Kara Sea through the Vilkitsky Strait and via St. Anna Trough into the western Laptev Sea.     

Bioreduction of Fe-bearing clay minerals and their reactivity toward pertechnetate (Tc-99)

⁹⁹Technetium (⁹⁹Tc) is a fission product of uranium-235 and plutonium-239 and poses a high environmental hazard due to its long half-life (t_1/2 = 2.13 × 10⁵ y), abundance in nuclear wastes, and environmental mobility under oxidizing conditions [i.e., Tc(VII)]. Under reducing conditions, Tc(VII) can be reduced to insoluble Tc(IV). Ferrous iron, either in aqueous form (Fe²⁺) or in mineral form [Fe(II)], has been used to reduce Tc(VII) to Tc(IV). However, the reactivity of Fe(II) from clay minerals, other than nontronite, toward immobilization of Tc(VII) and its role in retention of reduced Tc(IV) has not been investigated. In this study the reactivity of a suite of clay minerals toward Tc(VII) reduction and immobilization was evaluated. The clay minerals chosen for this study included five members in the smectite-illite (S-I) series, (montmorillonite, nontronite, rectorite, mixed layered I-S, and illite), chlorite, and palygorskite. Surface Fe-oxides were removed from these minerals with a modified dithionite-citrate-bicarbonate (DCB) procedure. The total structural Fe content of these clay minerals, after surface Fe-oxide removal, ranged from 0.7% to 30.4% by weight, and the structural Fe(III)/Fe(total) ratio ranged from 45% to 98%. X-ray diffraction (XRD) and Mössbauer spectroscopy results showed that after Fe oxide removal the clay minerals were free of Fe-oxides. Scanning electron microscopy (SEM) revealed that little dissolution occurred during the DCB treatment. Bioreduction experiments were performed in bicarbonate buffer (pH-7) with structural Fe(III) in the clay minerals as the sole electron acceptor, lactate as the sole electron donor, and Shewanella putrefaciens CN32 cells as a mediator. In select tubes, anthraquinone-2,6-disulfate (AQDS) was added as electron shuttle to facilitate electron transfer. In the S-I series, smectite (montmorillonite) was the most reducible (18% and 41% without and with AQDS, respectively) and illite the least (1% for both without and with AQDS). The extent and initial rate of bioreduction were positively correlated with the percent smectite in the S-I series (i.e., layer expandability). Fe(II) in the bioreduced clay minerals subsequently was used to reduce Tc(VII) to Tc(IV) in PIPES buffer. Similar to the trend of bioreduction, in the S-I series, reduced NAu-2 showed the highest reactivity toward Tc(VII), and reduced illite exhibited the least. The initial rate of Tc(VII) reduction, after normalization to clay and Fe(II) concentrations, was positively correlated with the percent smectite in the S-I series. Fe(II) in chlorite and palygorskite was also reactive toward Tc(VII) reduction. These data demonstrate that crystal chemical parameters (layer expandability, Fe and Fe(II) contents, and surface area, etc.) play important roles in controlling the extent and rate of bioreduction and the reactivity toward Tc(VII) reduction. Reduced Tc(IV) resides within clay mineral matrix, and this association could minimize any potential of reoxidation over long term.     

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.     

Clay mineralogy of the late pleistocene red sediments of the Visakhapatnam region,east coast of India

The fine-fraction mineralogy of the red sediments and of the upland soils along the Visakhapatnam—Bhimunipatnam coastal region has been studied by X-ray analysis. Dominant kaolinite with subordinate illite is the general clay-mineral assemblage in both the red sediments and the soils. The similar clay-mineral composition indicates that the upland soils are the source for the clay material in the red sediments. Montmorillonite is present in some samples and shows greater abundance in the red sediments than in the soils. The additional montmorillonite is considered to have been formed by post-depositional diagenesis in the red sediments at the expense of illite. Differences in the intensity of the weathering process controlled by the gradient in the source area have been suggested as being responsible for the variation in type and abundance of the clay minerals in the red sediments. It is inferred that humid and tropical to subtropical climatic conditions prevailed and persisted throughout the Late Pleistocene and Holocene in the Visakhapatnam region.     

土壤/沉积物中石油烃微生物降解研究综述

结合目前国内外研究进展,综述了土壤和沉积物中石油烃污染物的来源、危害和生物降解的菌种及降解途径,分析了微生物性质和包括氧、营养物、温度、土壤/沉积物理化性质等环境因素对石油烃降解的影响,指出这些研究往往局限于某种特殊污染物、特殊污染降解菌种和单一条件下辅助降解方面,引入了人为因素的影响,造成与实际不符的降解假象。因此,自然条件下石油烃生物降解将成为重要的研究课题。     

东太平洋水合物海岭沉积物中黏土矿物与水合物饱和度相关性研究

为了探讨水合物储层中不同黏土矿物与水合物饱和度的关系,选取位于东太平洋水合物海岭国际大洋钻探计划204航次中的3个钻孔(1245B孔、1244C孔和1251B),开展储层沉积物黏土矿物的测试和综合分析。结果表明,蒙脱石、伊利石、绿泥石为主要黏土矿物(平均含量分别为40.3%、33.4%、21.4%);高岭石为次要黏土矿物(平均4.9%)。伊利石、绿泥石、高岭石三种矿物含量的垂向变化规律相似,但它们与蒙脱石的垂向变化趋势相反。该区水合物饱和度与蒙脱石含量呈正相关,且正相关程度在“细粒岩性”层段较高(R=0.55~0.97);水合物饱和度与伊利石、绿泥石、高岭石则显示负相关。3个钻孔中水合物储层厚度、水合物饱和度在各钻孔中分布的差异性表明水合物饱和度的受控因素复杂,首先是气源和流体迁移与供给,其次为沉积物岩性;而“细粒岩性”层段较高含量蒙脱石与水合物饱和度正相关关系可能代表了更次一级的沉积影响因素。为检验其它海区是否也存在黏土矿物对水合物饱和度的影响,将上述3个钻孔与印度外海Krishna-Godavari盆地17-07P钻孔记录进行对比。结果显示,17-07P孔的砂含量高,在粗砂层蒙脱石含量与水合物饱和度呈正相关,反映两个海域岩性对水合物饱和度控制机理不同。上述“细粒岩性”层段蒙脱石含量和伊利石、绿泥石、高岭石3种黏土矿物含量与水合物饱和度之间相关性的差异,可能因为蒙脱石具有特殊层状结构和表面化学性质(层间表面带负电荷、具有可交换的层间水合阳离子等),有利于促进水合物的形成和富集,因而表现为正相关;而伊利石、绿泥石、高岭石自身属性与蒙脱石不同(吸水膨胀能力、对甲烷的吸附能力较蒙脱石弱),不利于水合物的聚集,表现为负相关。     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

Modelling Zn(II) sorption onto clayey sediments using a multi-site ion-exchange model

In environmental studies, it is necessary to be able to predict the behaviour of contaminants in more or less complex physico-chemical contexts. The improvement of this prediction partly depends on establishing thermodynamic models that can describe the behaviour of these contaminants and, in particular, the sorption reactions on mineral surfaces. In this way, based on the mass action law, it is possible to use surface complexation models and ion exchange models. Therefore, the aim of this study is (i) to develop an ion-exchange model able to describe the sorption of transition metal onto pure clay minerals and (ii) to test the ability of this approach to predict the sorption of these elements onto natural materials containing clay minerals (i.e. soils/sediments) under various chemical conditions. This study is focused on the behaviour of Zn(II) in the presence of clayey sediments. Considering that clay minerals are cation exchangers containing multiple sorption sites, it is possible to interpret the sorption of Zn(II), as well as competitor cations, by ion-exchange equilibria with the clay minerals. This approach is applied with success to interpret the experimental data obtained previously in the Zn(II)–H⁺–Na⁺–montmorillonite system. The authors’ research team has already studied the behaviour of Na⁺, K⁺, Ca²⁺ and Mg²⁺ versus pH in terms of ion exchange onto pure montmorillonite, leading to the development of a thermodynamic database including the exchange site concentrations associated with montmorillonite and the selectivity coefficients of Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺ versus H⁺.