Metal corrosion and argillite transformation at the water-saturated,high-temperature iron–clay interface: A microscopic-scale study

In this study, microscopic and spectroscopic techniques (scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman microspectroscopy, micro X-ray fluorescence spectroscopy, micro X-ray fine structure adsorption spectroscopy, and micro laser-induced breakdown spectroscopy) were combined to decipher the chemical and mineralogical properties of a saturated Fe–clay interface reacted at 90 °C and 50 bar for 8 months. The results collectively confirm the presence of a corrosion layer and a clay transformation layer. The corrosion layer is made of a magnetite-containing internal sublayer and a Fe-phyllosilicate external sublayer enriched in Na, with traces of goethite presumably resulting from sample reaction with air. The clay transformation layer is made of predominantly Ca-rich siderite (FeCO₃). It is depleted in Al and K, suggesting dissolution of rock-forming minerals. The corroded thickness determined from the amount of Fe in corrosion and transformation layers and assuming zero porosity equals 19 ± 9 μm. These data indicate that the interfacial clay was transformed by dissolution of calcite and clay minerals and precipitation of siderite close to the original surface. Silica released upon clay dissolution diffused into the corrosion layer and coprecipitated with oxidized Fe to form Fe-phyllosilicate.     

Iron–bentonite interactions in the Kawasaki bentonite deposit,Zao area,Japan

Greenish veins occurring in brecciated bentonite were found in the Kawasaki bentonite deposit of the Zao region in Miyagi Prefecture, Japan. Their occurrence possibly indicates the interaction of bentonite with Fe-rich hydrothermal solutions. In order to prove the hypothesis and understand the long-term mineralogical and petrographic evolution of bentonite during such interactions, the greenish veins and the surrounding altered bentonite were analyzed using X-ray fluorescence (XRF), scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analysis (EPMA), scanning transmission electron microscopy with energy dispersed spectroscopy (STEM-EDS) and micro X-ray absorption near-edge structure (XANES). The greenish veins resulting from hydrothermal solution are composed of mixed-layer minerals consisting of smectite and glauconite (glaucony), pyrite and opal. The occurrences indicate that glaucony and pyrite formed almost simultaneously from hydrothermal solution prior to opal precipitation. The mineral assemblages of the greenish veins and their surroundings indicate that the hydrothermal activity had most likely taken place at a temperature of less than 100 °C and that the pH and Eh conditions of the reacted solution were neutral to alkaline pH and reducing. The unaltered bentonite is composed mainly of Al smectite and opal. These minerals coexist as a mixture within the resolution level of the microprobe analyses. On the other hand, the bentonite in contact with the greenish veins consists of discrete opal grains and dioctahedral Al smectite containing Fe and was altered mineralogically and petrographically by the hydrothermal activity. Both the clay minerals and the opal were formed by dissolution and subsequent precipitation from the interaction of the original bentonite with the hydrothermal solution.     

Investigating high zircon concentrations in the fine fraction of stream sediments draining the Pan-African Dahomeyan Terrane in Nigeria

Sixteen hundred stream sediments (<150 μm fraction) collected during regional geochemical surveys in central and SW Nigeria have high median and maximum concentrations of Zr that exceed corresponding Zr concentrations found in stream sediments collected from elsewhere in the World with similar bedrock geology. X-ray diffraction studies on a sub-set of the analysed stream sediments showed that Zr is predominantly found in detrital zircon grains. However, the main proximal source rocks (Pan-African ‘Older Granites’ of Nigeria and their Proterozoic migmatitic gneiss country rocks) are not enriched in zircon (or Zr). Nevertheless, U–Pb LA-ICP-MS dating with cathodoluminescence imaging on detrital zircons, both from stream sediment samples and underlying Pan-African ‘Older Granites’ confirms a local bedrock source for the stream sediment zircons. A combination of tropical/chemical weathering and continuous physical weathering, both by ‘wet season’ flash flooding and ‘dry season’ unidirectional winds are interpreted to have effectively broken down bedrock silicate minerals and removed much of the resultant clay phases, thereby increasing the Zr contents in stream sediments. The strong correlation between winnowing index (Th/Al) and Zr concentration across the study area support this interpretation. Therefore, ‘anomalous’ high values of Zr, as well as other elements concentrated in resistant ‘heavy’ minerals in Nigeria’s streams may not reflect proximal bedrock concentrations of these elements. This conclusion has important implications for using stream sediment chemistry as an exploration tool in Nigeria for primary metal deposits associated with heavy minerals.     

煤矸石淋滤液中污染物在GCL中的扩散性能

为验证土工合成黏土衬垫（Geosynthetic Clay Liners,GCL）作为煤矸石处置场衬垫层建设材料的可行性,采用垂直式双筒扩散装置进行室内扩散试验,研究了煤矸石淋滤液中典型污染物Zn2+、Mn2+和SO₄2-在人工钠化膨润土GCL中的扩散性能,使用有限层法模拟软件POLLUTE V7对污染物随时间变化的曲线进行拟合,确定3种污染物在人工钠化膨润土GCL中的扩散系数。研究结果表明,污染物在GCL中的扩散系数低于它们在传统压实黏土衬垫层中的扩散系数,从而能更有效地控制煤矸石淋滤液中污染物在GCL中的扩散迁移行为。      

Biodegradation of forest floor organic matter bound to minerals via different binding mechanisms

Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca²⁺ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5-130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca²⁺ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca²⁺ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ? phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca²⁺ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.     

广西红黏土矿物成分分析

黏土矿物成分对其工程力学性质具有显著的影响。目前,在黏土矿物种类鉴定方面已有一些成熟的方法技术,而对黏土的矿物成分定量分析尚没有成熟的方法。本文基于X射线衍射试验、全化学元素分析、Bogue法和K值法,对广西武鸣、桂林两地红黏土的矿物成分进行了定性鉴定和定量分析。研究结果表明:(1)桂林、武鸣两地红黏土的主要矿物均为高岭石、三水铝石、针铁矿,桂林红黏土还含有一定量的石英。(2)武鸣红黏土的矿物成分及其含量依次为:高岭石(74.0%)、三水铝石(12.53%)、针铁矿(2mm, 2.22%)、针铁矿(2mm, 8.37%)。(3)桂林红黏土的矿物成分及其含量依次为:高岭石(56.59%)、三水铝石(11.44%)、针铁矿(15.61%)、石英(12.45%)。     

3种典型富锰沉积物的形貌学与矿物学特征

本文采集了3种典型的富锰沉积物样品,即岩石漆、树枝晶与土壤铁锰胶膜,并制作了相应的纵切片。运用光学显微镜、原位微区拉曼光谱仪、扫描电镜、EDX能谱仪分别对其形貌学与矿物学特征进行了研究。结果表明岩石漆呈黑色致密层状、葡萄状,主要由水钠锰矿、赤铁矿、针铁矿、粘土矿物等组成,是一种高度混杂的沉积物。宏观上岩石漆与基岩有截然的接触面,发育有微层理结构,在微观上的表现即锰含量的周期性波动。树枝晶呈黑色分枝状,主要由锰钡矿组成,极端富锰而贫硅铝,与基质呈交织结构。土壤铁锰胶膜呈黑色粘稠层状,由水钠锰矿、赤铁矿、针铁矿、钛铁矿、粘土矿物等组成,可细分为外层黑褐色的富锰条带和内层黄棕色的富铁条带。这3种富锰沉积物的形貌学和元素分布特征与各自的成因机制密切相关。     

A new simple approach to evaluate pedogenic clay transformation in a Vertic Calcisol

The aim of this study is to characterize the pedogenic clay minerals by using simple approach: mixing mineralogical and geochemical findings.The fine clay fractions (< 0.1 μm) of a Vertic Cambisol profile were studied by means of X-ray diffraction (XRD), infrared spectroscopy (FTIR) and cation exchange capacity (CEC).Qualitative and quantitative mineralogical compositions of the clay mixture were determined.Moreover, chemical equilibria and thermodynamic stabilities of minerals (calcite, gypsum, kaolinite, smectites and illites) were studied using results of ionic activities obtained from total concentration of various aqueous species in water extracts from soil-saturated pastes.XRD analysis shows a good homogeneity in the mineralogical composition of the soil material, with depth of soil profiles. The identified clay minerals are mainly illite–smectite mixed layers (I/S) and kaolinite. The chemical analysis of saturated paste extracts with clay minerals shows a slight undersaturation of the illitic phase while smectites and also calcite and gypsum reach the thermodynamic equilibrium along the soil profile.     

Mineralogy and geochemistry of alluvium contaminated by metal mining in the Rio Tinto area, southwest Spain

The Rio Tinto in SW Spain drains Cu and pyrite mines which have been in operation since at least the Bronze Age. Extensive metal mining, especially from 1873 to 1954, has resulted in contamination of the Rio Tinto alluvium with As, Cu, Pb, Ag and Zn. X-ray diffraction (XRD), wavelength-dispersive X-ray mapping, scanning electron microscope petrography and X-ray energy-dispersive (EDX) analysis has revealed that 4 major groups of contaminant metal and As-bearing minerals, including sulphides, Fe-As oxides, Fe oxides/hydroxides/oxyhydroxides, and Fe oxyhydroxysulphates, occur in the alluvium. Sulphide minerals, including pyrite, chalcopyrite, arsenopyrite and sphalerite, occur in alluvium near the mining areas. Iron hydroxides and oxyhydroxides such as goethite and possibly ferrihydrite occur in cements in both the mining areas and alluvium downstream, and carry minor amounts of As, Cu and Zn. Iron oxyhydroxysulphates, including jarosite, plumbojarosite and possibly schwertmannite, are the most common minerals in alluvium downstream of the mining areas, and are major hosts of Cu, Pb, Zn and of As, next to the Fe-As minerals. This work, and other field observations, suggest that (1) the extreme acidity and elevated metal concentrations of the river water will probably be maintained for some time due to oxidation of pyrite and other sulphides in the alluvium and mine-waste tips, and from formation of secondary oxide and oxyhydroxysulphates; (2) soluble Fe oxyhydroxysulphates such as copiapite, which form on the alluvium, are a temporary store of contaminant metals, but are dissolved during periods of high rainfall or flooding, releasing contaminants to the aqueous system; (3) relatively insoluble Fe oxyhydroxysulphates and hydroxides such as jarosite and goethite may be the major long-term store of alluvial contaminant metals; and (4) raising river pH will probably cause precipitation of Fe oxyhydroxides and oxides/hydroxides/oxyhydroxides and thus have a positive effect on water quality, but this action may destabilise some of these contaminant metal-bearing minerals, releasing metals back to the aqueous system.     

Sorption of selenite in a multi-component system using the “dialysis membrane” method

⁷⁹Se is a potentially mobile long-lived fission product, which may make a dominant contribution to the long-term radiation exposure resulting from deep geological disposal of radioactive waste. Its mobility is affected by sorption on minerals. Selenium sorption processes have been studied mainly by considering interaction with a single mineral surface. In the case of multi-component systems (e.g. soils), it is difficult to predict the radioelement behaviour only from the mineral constituents. This study contributes to the understanding of multi-component controls of Se concentrations towards predicting Se behaviour in soils after migration from a disposal site. This goal was approached by measuring selenite sorption on mono and multi-phase systems physically separated by dialysis membranes. To the best of the authors’ knowledge, very few studies have used dialysis membranes to study the sorption competition of selenite between several mineral phases. Other workers have used this method to study the sorption of pesticides on montmorillonite in the presence of dissolved organic matter. Indeed, this method allows measurement of individual K_d in a system composed of several mineral phases. Dialysis membranes allowed (i) determination of the competition of two mineral phases for selenite sorption (ii) and determination of the role of humic acids (HAs) on selenite sorption in oxidising conditions. Experimental results at pH 7.0 show an average Se(IV) sorption distribution coefficient (K_d) of approximately 125 and 9410 L kg⁻¹ for bentonite and goethite, respectively. The average K_d for goethite decreases to 613 L kg⁻¹ or 3215 L kg⁻¹ in the presence of bentonite or HA, respectively. For bentonite, the average K_d decreases slightly in the presence of goethite (60 L kg⁻¹) and remains unchanged in the presence of HA. The experimental data were successfully modelled with a surface complexation model using the PHREEQC geochemical code. The drastic decrease in Se(IV) sorption on goethite in a multi-phase system is attributed to competition with dissolved silica released by bentonite. As with Si the HA compete with Se for sorption sites on goethite.     

Mineralogical and morphological constraints on the reduction of Fe(III) minerals by Geobacter sulfurreducens

The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p_3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.     

Distribution and speciation of gold in biogenic and abiogenic calcium carbonates - Implications for the formation of gold anomalous calcrete

Calcrete (pedogenic Ca carbonate) is an important sampling medium for geochemical gold (Au) exploration in semi-arid and arid regions of Australia, because it is widespread, easy to sample and calcium (Ca) shows a strong positive correlation with Au, but not with base metals, in calcrete overlying buried Au mineralization. In this study we show that the formation of Au-anomalous calcrete can be biomediated through the activity of resident microorganisms, and may not simply be the result of passive nucleation on inactive cells or evapotransporative processes. Calcified microfossils are highly abundant in calcrete from the Barns Au-prospect in South Australia. These microfossils are morphological analogues of calcified cells and biofilms formed in laboratory experiments conducted with active bacterial cultures enriched from Au-anomalous calcareous sand from the Barns prospect. Calcium carbonates precipitated by these cultures consisted mostly of calcite, which is the main carbonate mineral in calcrete. Synchrotron micro-X-ray fluorescence (S-μXRF) mapping was used to assess the distribution of Au, Zn, Ca and other metals in Ca carbonates precipitated by active bacterial cultures. On a μm-scale the distribution of Au was heterogeneous in these Ca carbonates and differed from base metal distribution, thus mimicking the spatial separation of these metals observed in calcrete. The speciation of Au in Ca carbonates precipitated by active bacteria was measured using micro-X-ray absorption near edge structure spectroscopy (μ-XANES) and resembled that observed in Au-anomalous calcrete closely. While metallic Au was observed in Au ‘hotpots’, ionic Au was detected in the halo surrounding the ‘hotspot’. In contrast, the precipitates produced in the presence of dead bacterial cells or by raising solution pH or pCO₂, i.e., hydroxylapatite, portlandite and vaterite, respectively, did not reflect the mineralogy of calcrete. Gold distribution and speciation in vaterite, formed by raising pCO₂, were homogenous and did not reproduce the variation observed in calcrete and Ca carbonates precipitated by active cells. Increasing the supersaturation with respect to Ca in solution by incremental drying of the medium produced only X-ray amorphous precipitates, or hydroxylapatite in the presence heat-killed cells. In conclusion, this study shows that active microbial processes that combine biogenic Ca carbonatogenesis with Au precipitation are likely to drive the formation of Au-anomalous calcrete.     

Mobilization and attenuation of heavy metals within a nickel mine tailings impoundment near Sudbury, Ontario, Canada

 The oxidation and the subsequent dissolution of sulfide minerals within the Copper Cliff tailings area have led to the release of heavy metals such as Fe, Ni, and Co to the tailings pore water. Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l Ni have been detected within the shallow pore water of the tailings, with increasing depth these concentrations decrease to or near analytical detection limits. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary phases are precipitating at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of goethite, jarosite, gypsum, native sulfur, and a vermiculite-type clay mineral. Goethite, jarosite, and native sulfur form alteration rims and pseudo-morphs of the sulfide minerals. Interstitial cements, composed of goethite, jarosite, and gypsum, locally bind the tailings particles, forming hardpan layers. Microprobe analyses of the goethite indicate that it contains up to 0.6 weight % Ni, suggesting that the goethite is a repository for Ni. Other sinks detected for heavy metals include jarosite and a vemiculite-type clay mineral which locally contains up to 1.6 weight % Ni. To estimate the mass and distribution of heavy metals associated with the secondary phases within the shallow tailings, a series of chemical extractions was completed. The experimental design permitted four fractions of the tailings to be evaluated independently. These four fractions consisted of a water-soluble, an acid-leachable, and a reducible fraction, as well as the whole-rock total. Twenty-five percent of the total mass of heavy metals was removed in the acid-leaching experiments, and 100% of the same components were removed in the reduction experiments. The data suggest that precipitation/coprecipitation reactions are providing an effective sink for most of the heavy metals released by sulfide mineral oxidation. In light of these results, potential decommissioning strategies should be evaluated with the recognition that changing the geochemical conditions may alter the stability of the secondary phases within the shallow tailings. Received: 9 April 1997 · Accepted: 21 July 1997     

Quantitative analysis of the clay minerals in the Shurijeh Reservoir Formation using combined X-ray analytical techniques

The Shurijeh Reservoir Formation of Neocomian age is represented by a sandstone sequence, occasionally interbedded with shale, in the Gonbadli gas field, Kopet-Dagh Basin, Northeastern Iran. In this study X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques were used together to characterize the Shuirjeh clay minerals in 76 core samples collected from two deep Gonbadli wells. The results of XRF analysis showed high percentages of silicon and moderate to low percentages of aluminum, sulfur, calcium, potassium, sodium, magnesium, and iron in both wells. The XRD analysis indicated that the above elements were concentrated in the form of quartz, anhydrite, dolomite, calcite, plagioclase, K-feldspar, hematite, and clay minerals. Further XRD examination of the clay fraction revealed that illite, chlorite, and kaolinite were the major types of clay minerals. Unlike, glauconite, smectite, and a mixed layer clays of both the illite–smectite and chlorite–smectite types were observed only in very few samples. The percentages of individual clay minerals were determined using external standard calibration curves and successfully validated by a system of simultaneous linear equations acquired from detailed elemental information based on the XRF analysis. The error reached ± 5% for the main mineral constituent and ± 15% for minor minerals. A local regression relationship was also derived, based on the XRF elemental information, which can be used to estimate the clay contents of other Shurijeh drilled wells with data of pulsed-neutron spectroscopy tools. According to the proposed quantitative approach, the amount of illite varied considerably, reaching 18.3%. In contrast, the amounts of kaolinite and chlorite were generally small, i.e., less than 8.4%. The amount of total clay minerals changed greatly from a minimum of 5% to a maximum of 32.5%. An increase in illite with increasing burial depth and temperature was an obvious indication of deep burial diagenesis in this formation.     

Climatic control on clay mineral formation: Evidence from weathering profiles developed on either side of the Western Ghats

Many physico-chemical variables like rock-type, climate, topography and exposure age affect weathering environments. In the present study, an attempt is made to understand how the nature of clay minerals formed due to weathering differs in tropical regions receiving high and low rainfall. Clay mineralogy of weathering profiles in west coast of India, which receives about 3 m rainfall through two monsoons and those from the inland rain-shadow zones (<200 cm rainfall) are studied using X-ray diffraction technique. In the west coast, 1:1 clays (kaolinite) and Fe—Al oxides (gibbsite/goethite) are dominant clay minerals in the weathering profiles while 2:1 clay minerals are absent or found only in trace amounts. Weathering profiles in the rain shadow region have more complex clay mineralogy and are dominated by 2:1 clays and kaolinite. Fe—Al oxides are either less or absent in clay fraction. The kaolinite—smectite interstratified mineral in Banasandra profiles are formed due to transformation of smectites to kaolinite, which is indicative of a humid paleoclimate. In tropical regions receiving high rainfall the clay mineral assemblage remains the same irrespective of the parent rock type. Rainfall and availability of water apart from temperature, are the most important factors that determine kinetics of chemical weathering. Mineral alteration reactions proceed through different pathways in water rich and water poor environments.     

Mineralogical attenuation for metallic remediation in a passive system for mine water treatment

Passive systems with constructed wetlands have been consistently used to treat mine water from abandoned mines. Long-term and cost-effective remediation is a crucial expectation for these water treatment facilities. To achieve that, a complex chain of physical, chemical, biological, and mineralogical mechanisms for pollutants removal must be designed to simulate natural attenuation processes. This paper aims to present geochemical and mineralogical data obtained in a recently constructed passive system (from an abandoned mine, Jales, Northern Portugal). It shows the role of different solid materials in the retention of metals and arsenic, observed during the start-up period of the treatment plant. The mineralogical study focused on two types of materials: (1) the ochre-precipitates, formed as waste products from the neutralization process, and (2) the fine-grained minerals contained in the soil of the wetlands. The ochre-precipitates demonstrated to be poorly ordered iron-rich material, which gave rise to hematite upon artificial heating. The heating experiments also provided mineralogical evidence for the presence of an associated amorphous arsenic-rich compound. Chemical analysis on the freshly ochre-precipitates revealed high concentrations of arsenic (51,867 ppm) and metals, such as zinc (1,213 ppm) and manganese (821 ppm), indicating strong enrichment factors relative to the water from which they precipitate. Mineralogical data obtained in the soil of the wetlands indicate that chlorite, illite, chlorite–vermiculite and mica–vermiculite mixed-layers, vermiculite, kaolinite and goethite are concentrated in the fine-grained fractions (<20 and <2 μm). The chemical analyses show that high levels of arsenic (up to 3%) and metals are also retained in these fractions, which may be enhanced by the low degree of order of the clay minerals as suggested by an XRD study. The obtained results suggest that, although the treatment plant has been receiving water only since 2006, future performance will be strongly dependent on these identified mineralogical pollutant hosts.     

Iron and manganese diagenesis in deep sea volcanogenic sediments and the origins of pore water colloids

Volcanogenic sediments are typically rich in Fe and Mn-bearing minerals that undergo substantial alteration during early marine diagenesis, however their impact on the global biogeochemical cycling of Fe and Mn has not been widely addressed. This study compares the near surface (0-20 cm below sea floor [cmbsf]) aqueous (<0.02 μm) and aqueous + colloidal here in after ‘dissolved’ (<0.2 μm) pore water Fe and Mn distributions, and ancillary O_2(aq), and solid-phase reactive Fe distributions, between two volcanogenic sediment settings: [1] a deep sea tephra-rich deposit neighbouring the volcanically active island of Montserrat and [2] mixed biosiliceous-volcanogenic sediments from abyssal depths near the volcanically inactive Crozet Islands archipelago. Shallow penetration of O_2(aq) into Montserrat sediments was observed (<1 cmbsf), and inferred to partially reflect oxidation of fine grained Fe(II) minerals, whereas penetration of O_2(aq) into abyssal Crozet sediments was >5 cmbsf and largely controlled by the oxidation of organic matter. Dissolved Fe and Mn distributions in Montserrat pore waters were lowest in the surface oxic-layer (0.3 μM Fe; 32 μM Mn), with maxima (20 μM Fe; 200 μM Mn) in the upper 1-15 cmbsf. Unlike Montserrat, Fe and Mn in Crozet pore waters were ubiquitously partitioned between 0.2 μm and 0.02 μm filtrations, indicating that the pore water distributions of Fe and Mn in the (traditionally termed) ‘dissolved’ size fraction are dominated by colloids, with respective mean abundances of 80% and 61%. Plausible mechanisms for the origin and composition of pore water colloids are discussed, and include prolonged exposure of Crozet surface sediments to early diagenesis compared to Montserrat, favouring nano-particulate goethite formation, and the elevated dissolved Si concentrations, which are shown to encourage fine-grained smectite formation. In addition, organic matter may stabilise authigenic Fe and Mn in the Crozet pore waters. We conclude that volcanogenic sediment diagenesis leads to a flux of colloidal material to the overlying bottom water, which may impact significantly on deep ocean biogeochemistry. Diffusive flux estimates from Montserrat suggest that diagenesis within tephra deposits of active island volcanism may also be an important source of dissolved Mn to the bottom waters, and therefore a source for the widespread hydrogenous MnO_x deposits found in the Caribbean region.     

Characteristics,modification and environmental application of Yemen’s natural bentonite

The bentonite deposit of Lahij Province, Yemen, has very promising commercial applications due to its mineralogy and physical and chemical properties. It was examined to determine its mineralogical composition, chemical and physical properties of the bentonite deposit, purity and sodium-exchanged bentonite. Modified bentonite was synthesized by exchanging cetyltrimethylammonium cations for inorganic ions on the bentonite and its adsorption properties for ammonium were characterized in batch experiments. Analytical methods were carried out to study the bentonite comprising X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy, chemical analysis and kinetic and isotherm models were also tested. The results have shown that the purification of bentonite resulted in a bentonite fractions of the total sample composed of montmorillonite and <5 % quartz. The XRD data showed that the interlayer spacing (d ₀₀₁) of bentonite decreased from 15.3 to 12.5 Å and then increased to 19.7 Å. Moreover, high cation exchange capacity, good water absorption and high swelling capacity were also obtained. The results have shown that the modified bentonite was more effective than the natural bentonite for ammonium removal. In addition to that, pseudo-second-order kinetic model, Freundlich and the Langmuir models described the adsorption kinetics and isotherm well. It was concluded that Yemen (Alaslef) bentonite can be potential adsorbents for ammonium removal.     

Glass-iron-clay interactions in a radioactive waste geological disposal: An integrated laboratory-scale experiment

Glass-iron-clay setups were reacted at 90 °C for 6-18 months to investigate the coupled interactions between glass alteration, Fe corrosion and clay transformation. The reacted interfaces were probed at the microscopic level using complementary characterization methods (scanning electron microscopy coupled with energy-dispersive X-ray analysis, micro-Raman spectroscopy, micro X-ray diffraction, micro X-ray fluorescence spectroscopy, and micro X-ray absorption near-edge structure spectroscopy). The 10-μm thick Fe foil was fully corroded within 10 months, exposing glass to the pore solution. Iron corrosion led to the formation of a layer containing mostly magnetite, siderite and Fe-rich phyllosilicates with one tetrahedral and one octahedral sheet (TO) or two tetrahedral and one octahedral (TOT) sheet per layer. The clay in contact with this corrosion layer was enriched in siderite (FeCO₃). Glass alteration resulted in the formation of a gel layer whose thickness increased with reaction time (from 20 μm after 6 months to 80 μm after 18 months) and a thin layer of secondary precipitates that concentrated lanthanides, P, and Mo. Assuming conservative behavior of Zr, the Si molar concentration in the gel is about 57% that in the glass. Glass dissolution remained at a rate close to the initial dissolution rate r₀. The data are consistent with glass dissolution sustained by the uptake of dissolved Si and charge-compensating cations on secondary (corrosion) products, thus maintaining the gel porosity open and facilitating the leaching of easily soluble elements.     

江西赣南风化淋滤型稀土矿床中的粘土矿物研究

对江西赣南6个地区风化淋滤型稀土矿中全风化层的粘土矿物进行了研究,为进一步了解粘土矿物对该类型稀土矿中稀土元素分异的影响奠定了基础。X射线衍射自然定向片、甲酰胺片、饱和乙二醇片和加热片、红外光谱及扫描电镜观察结果表明该区粘土矿物以片状高岭石和针管状7埃洛石为主,其中坳背塘、长坑屋、上堡、杨村样品主体为高岭石,足洞样品中发育大量埃洛石,而石排样品中高岭石与埃洛石比例相当。电感耦合等离子体质谱分析表明稀土元素在粘土矿物中大量富集,其稀土元素配分不仅受到原岩的影响,而且受到粘土矿物本身性质的影响。Ce元素在足洞和石排样品的粘土矿物中表现出正异常,而在其他样品粘土矿物中表现为负异常,可能与其中发育的埃洛石密切相关。Ce元素可能以方铈矿胶膜的形式包裹在针状埃洛石中,和/或以离子形式被选择性吸附于埃洛石表面。