Retention of arsenic and phosphorus in iron-rich concretions of Tagus salt marshes

Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O₂ takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O₂ and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g⁻¹ and 3.1 μmol g⁻¹, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g⁻¹), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g⁻¹ and 1.6 mmol g⁻¹, respectively) and of cracks (5.1 μmol g⁻¹ and 0.47 mmol g⁻¹). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.     

Mineralogical changes during thermal demagnetization of natural continental sandstones

We study the mineralogical changes suffered by specimens of natural miocene red and green continental sandstones (from Pozuelos Formation and Tiomayo Formation) cropping out in the Argentine Puna that increase their bulk magnetic susceptibility and change color when thermally treated. We hypothesize that on heating siderite, which is present in small quantities as cement in the studied sandstones, would oxidize and decompose into maghemite and/or magnetite. Subsequent heating to higher temperatures sometimes would bring about the conversion of maghemite and/or magnetite to hematite. Mössbauer spectroscopy proved to be a very valuable tool for the determination of the presence of siderite in small amounts in the studied samples. The present results show that further work is needed in order to fully understand the mineralogical changes suffered by continental sandstones during heating. The characterization of such changes occurred during laboratory routines is relevant, since they can help to better understand natural processes.     

扬子板块北缘下志留统龙马溪组重晶石结核特征及其成因机制分析

在扬子板块北缘城口明中剖面及巫溪徐家坝剖面下志留统龙马溪组底部的硅质岩、泥岩中发现椭球状重晶石结核。其矿物组成主要为重晶石颗粒与作为"基质"的黄铁矿、粘土矿物和石英。通过重晶石岩石学、矿物学及锶同位素分析表明,重晶石结核形成于早期成岩阶段松软沉积物的孔隙水中。上升洋流带来丰富的营养及富钡物质,表层海水的高初始生产力促使生物繁盛,海水中的钡通过生物作用富集形成生物钡,生物钡(bio-barite)在埋藏过程中的硫酸盐耗竭区(sulfate depleted zones)通过硫酸盐细菌作用(BSR)溶解被激活提供了钡的来源。围岩岩性(黑色泥岩和硅质泥岩)表明重晶石结核形成于缺氧的环境中。上述研究对深入理解早志留世时期扬子板块北缘古海洋环境有一定的启示作用。     

高压下天然菱铁矿的压缩性和电子结构研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对天然菱铁矿的压缩性和电子结构进行了原位X射线衍射(XRD)和X射线吸收近边结构谱(XANES)测试研究。在室温下随着压力逐渐升高至50.2 GPa,菱铁矿保持方解石型结构不变,但是逐渐向Na Cl型结构转变;刚性[CO3]2-基团平行于ab-平面定向排列使c轴的压缩性大于a轴。菱铁矿在44.6~47.1 GPa之间发生电子由高自旋态(HS)向低自旋态(LS)的转变,表现为体积塌陷8%。HS菱铁矿的等温状态方程参数为K0=112(5)GPa和K'0=4.6(3)。首次采用XANES技术对菱铁矿中Fe2+的电子结构进行了研究,结果表明:随着压力升高至37.3 GPa,Fe2+的配位和局域对称并未发生明显变化;此后电子结构开始转变,Fe2+的3d轨道分裂能降低,电子跃迁概率增大,呈现LS特性。     

Root‐related rhodochrosite and concretionary siderite formation in oxygen‐deficient conditions induced by a ground‐water table rise

Sedimentological, mineralogical, stable carbon and oxygen isotope determinations and biomarker analyses were performed on siderite concretions occurring in terrestrial silts to understand their formation and to characterize the sedimentary and diagenetic conditions favouring their growth. High δ¹³C values (6·4‰ on average) indicate that siderite precipitated in an anoxic environment where bacterial methanogenesis operated. The development of anoxic conditions during shallow burial was induced by a change in sedimentary environment from flood plain to swamp, related to a rise of the ground‐water table. Large amounts of decaying plant debris led to efficient oxygen consumption within the pore‐water in the peat. Oxygen depletion, in combination with a decrease in sedimentation rate, promoted anoxic diagenetic conditions under the swamp and favoured abundant siderite precipitation. This shows how a change in sedimentary conditions can have a profound impact on the early‐diagenetic environment and carbonate authigenesis. The concretions contain numerous rhizoliths; they are cemented with calcium‐rhodochrosite, a feature which has not been reported before. The rhodochrosite cement has negative δ¹³C values (?16·5‰ on average) and precipitated in suboxic conditions due to microbial degradation of roots coupled to manganese reduction. The exceptional preservation of the epidermis/exodermis and xylem vessels of former root tissues indicates that the rhodochrosite formed shortly after the death of a root in water‐logged sediments. Rhodochrosite precipitated during the initial stages of concretionary growth in suboxic microenvironments within roots, while siderite cementation occurred simultaneously around them in anoxic conditions. These suboxic microenvironments developed because oxygen was transported from the overlying oxygenated soil into sediments saturated with anoxic water via roots acting as permeable conduits. This model explains how separate generations of carbonate cements having different mineralogy and isotopic compositions, which would conventionally be regarded as cements precipitated sequentially in different diagenetic zones during gradual burial, can form simultaneously in shallow burial settings where strong redox gradients exist around vertically oriented permeable root structures.     

川北地区寒武系筇竹寺组钙质结核裂缝充填物特征及指示意义

川北地区寒武系筇竹寺组钙质结核泥页岩中早成岩期钙质结核较发育,结核裂缝中见多期次矿物充填。为揭示钙质结核裂缝形成机理,本次结合岩石学特征及地球化学特征等开展系统研究。川北筇竹寺组钙质结核裂缝中见三~四期矿物充填。第一期微晶方解石表面较脏,阴极发光暗淡,δ13C_(PDB)、δ18O_(PDB)平均值分别为-4.26‰及-7.69‰;第二期为细—中晶粒状方解石充填,阴极发光为橘黄色,流体包裹体均一温度为平均值为86.4℃,δ13C_(PDB)、δ18O_(PDB)平均值分别为-3.15‰及-7.41‰;第三期为粗晶方解石充填阴极发光暗淡,流体包裹体均一温度平均值为96.6℃,δ~(13)C_(_(PDB))、δ~(18)O_(_(PDB))平均值分别为-1.73‰及-10.28‰;第四期为重晶石充填。结合区域构造史—热演化史分析表明,钙质结核裂缝中四期充填物分别指示早期脱水、烃源岩早成熟期生烃、加里东构造运动抬升释压及深埋藏期硫酸盐热还原作用事件。     

Methane-derived authigenic carbonates from active hydrocarbon seeps of the St. Lawrence Estuary,Canada

Nearly 2000 pockmarks with diameters ranging from a few tens of meters up to 700 m are present on the seafloor of the St. Lawrence Estuary in eastern Canada. Coring of some pockmarks resulted in the recovery of various-sized and shaped carbonate concretions in a predominantly silty mud matrix. Petrographic and geochemical data on four authigenic carbonate concretions are reported as well as data from shell material in the unconsolidated sediment. Video observations and echo-sounder images indicate that the sampled pockmarks are actively gas venting. The video images show significant look-alike microbial mats in areas where gas is venting. The carbonate concretions are primarily made up of carbonate cements with varying percentage of shell fragments, micrite particles and fine-grained clastics. Orthorhombic crystal morphology and diagenetic fabrics including isopachous layers and botryoids characterize the aragonite cement. Oxygen isotopes ratios for the cement crusts do not record any thermal anomaly at the site of precipitation with δ¹⁸O_VPDB ratios (+3‰) in equilibrium with cold (5 °C) deep marine waters, whereas significant negative δ¹³C_VPDB ratios (−9.9 to −33.5‰) for cement and shell material within concretions indicate that the carbonates largely derive from the microbial oxidation of methane. The δ¹³C_VPDB ratios of aragonite shells (−2.7 to −5.6‰) taken from unconsolidated sediments at some distance from the concretions/vents show variable dilution of HCO₃⁻ with negative δ¹³C_VPDB ratios derived from microbial oxidation of methane with isotopically normal (0‰) marine bicarbonate. These results are in agreement with other lines of evidence suggesting that pockmarks formed through the recent and still active release of gas from a reservoir within the Paleozoic sedimentary succession.     

Nature and origin of arsenic carriers in shallow aquifer sediments of Bengal Delta,India

Sediments from shallow aquifers in Bengal Delta, India have been found to contain arsenic. Rivers of Ganga-Brahmaputra system, responsible for depositing these sediments in the delta, have created a store of arsenic. Geomorphological domains with different depositional styles regulate the pattern of distribution of zones with widely different content of groundwater arsenic. The high arsenic zones occur as narrow sinuous strips confined to channel deposits. A few iron-bearing clastic minerals and two post-depositional secondary products are arsenic carriers. Secondary siderite concretions have grown on the surface of the clastic carriers in variable intensity. The quantity of arsenic in all clastic carriers is in excess of what is generally expected. Excess arsenic is contributed by the element adsorbed on the concretion grown on the surface of the carriers, which adds up to the arsenic in the structure of the minerals. Variable abundance of concretions is responsible for the variable quantity of arsenic in the carriers and the sediment samples. Fe²⁺ for the growth of siderite concretions is obtained from the iron-bearing clastic carriers. The reaction involves reduction of trivalent iron to bivalent and the required electron is obtained by transformation of As³⁺ to As⁵⁺. It is suggested that oxidation of As³⁺ to As⁵⁺ is microbially mediated. In the Safe zone arsenic is retained in the carriers and groundwater arsenic is maintained below 0.05 mg/l. In the Unsafe zone sorbed arsenic is released from the carriers in the water through desorption and dissolution of concretion, thereby elevating the groundwater arsenic level to above 0.05 mg/l.     

陕西大西沟喷流沉积型菱铁矿矿床地质特征及矿床成因

陕西大西沟铁矿床位于秦岭造山带山-柞盆地西北部,与银洞子大型银铅矿床毗邻。矿体主要赋存在泥盆系青石垭组中上段,容矿岩石为一套海相复理石碎屑岩和碳酸盐岩建造。矿床的金属矿物主要有菱铁矿、磁铁矿、黄铁矿,其次为黄铜矿、磁黄铁矿等;非金属矿物主要是重晶石、石英、铁白云石,其次为方解石、绢云母、绿泥石、黑云母、斜长石、钠长石、堇青石等,局部地段由于表生氧化和次生富集作用而形成针铁矿、赤铁矿、蓝辉铜矿等。与矿化有关的围岩蚀变较弱,主要有硅化、绢云母化、绿泥石化和碳酸盐化。基于野外地质观察、矿物共生组合和矿石结构构造的系统研究,将大西沟铁矿床的形成划分为3期6阶段,分别是:①喷流沉积期:硅质岩-黄铁矿-菱铁矿阶段(Ⅰ)、重晶石-磁铁矿阶段(Ⅱ);②热液改造期:堇青石-黄铁矿-磁铁矿阶段(Ⅲ)、石英-碳酸盐阶段(Ⅳ)、碳酸盐-硫化物-磁铁矿阶段(Ⅴ);③表生氧化期(Ⅵ)。流体包裹体显微测温结果表明,喷流沉积期Ⅰ阶段菱铁矿完全均一温度和盐度w(NaCl_(eq))峰值区间分别为230～270℃和13%～14.5%,Ⅱ阶段重晶石中流体包裹体的完全均一温度和盐度w(NaCl_(eq))峰值区间分别为220～290℃和9%～13%;热液改造期Ⅳ阶段菱铁矿和石英中气液两相包裹体均一温度峰值区间为240～300℃,盐度w(NaCl_(eq))为2.6%～15.7%;热液改造期Ⅴ阶段菱铁矿与石英中流体包裹体,除大量气液两相包裹体外,还发育有含子矿物多相包裹体,其中,气液两相包裹体均一温度峰值区间为290～340℃,盐度w(NaCl_(eq))为5.1%～13.4%,含子矿物多相包裹体均一温度峰值区间为380～440℃,盐度w(NaCl_(eq))为40.6%～59.7%。含子晶流体包裹体可能是流体不混溶或/和高盐度流体加入的反映。矿区内不同产状碳酸盐矿物的C、O同位素组成比较均一,δ~(13)C_(PDB)值集中在-3.58‰～-1.15‰之间,δ~(18)O_(SMOW)值为21.22‰～21.82‰,均表现出海相碳酸盐或海底喷流热液溶解海相碳酸盐的特征。大西沟矿床的地质、矿化和流体特征与海底热液喷流沉积型矿床一致,可能属于典型的喷流沉积型菱铁矿床,但后期受到秦岭造山作用的影响及热液叠加改造并形成磁铁矿和少量硫化物。大西沟菱铁矿矿床与邻近的银洞子铅锌矿组成一个较完整的喷流沉积成矿系统,两者可能分别代表了喷流沉积的边缘相和中心相。     

Anatomically preserved plants in siderite concretions in the shale split of the Foord Seam: mineralogy, geochemistry, genesis (Upper Carboniferous, Canada)

A shale split in the well-studied Foord Seam (Upper Carboniferous), Stellarton Basin, Nova Scotia, provides a rare opportunity to study little known siderite concretions with anatomically preserved plants from a limnic basin. Siderite concretions occur throughout the split, commonly as sheet-like, inter-connected lepidodendrid logs, or less frequently as spherical masses; they are typically vuggy. A sample of 14 stratigraphically oriented concretions in the split shows that primary siderite varies from 45% to 80% (wt.%) due to selective replacement by 5% to 40% ferroan dolomite or ankerite in plant tissues. These two minerals show large Mg/Fe and Mg/Ca variability and are Fezoned. Clay content ranges from trace to 20%, and quartz from 5% to 10%. Partial cell-wall destruction by erosion and changeable oxic/anoxic conditions, prior to siderite permineralization, resulted in preservation mainly of the more resistant plant tissues. On average, carbon from siderite is isotopically heavier (+4.8±1.9 0/00) than that from ‘dolomite' (−7.2±1.1 0/00). The distribution of and the positive correlation between δ¹³C and δ¹⁸O probably reflects the two fractionation processes associated with methanogenesis and ‘dolomitization', respectively, in the genetic history of the siderite concretions in the split. Siderite concretions formed diagenetically early from bicarbonate under reducing conditions in a slightly alkaline freshwater environment that precluded calcite deposition.