Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.     

Origin of abundant moonmilk deposits in a subsurface granitic environment

Subsurface granitic environments are scarce and poorly investigated. A multi‐disciplinary approach was used to characterize the abundant moonmilk deposits and associated microbial communities coating the granite walls of the 16th Century Paranhos spring water tunnel in Porto city (north‐west Portugal). It is possible that this study is the first record of moonmilk in an urban subsurface granitic environment. The morphology and texture, mineralogical composition, stable isotope composition and microbial diversity of moonmilk deposits have been studied to infer the processes of moonmilk formation. These whitish secondary mineral deposits are composed of very fine needle‐fibre calcite crystals with different morphologies and density. Calcified filaments of fungal hyphae or bacteria were distinguished by field emission scanning electron microscopy. Stable isotope analysis revealed a meteoric origin of the needle‐fibre calcite, with an important contribution of atmospheric CO ₂, soil respiration and from weathering of Ca‐bearing minerals. The DNA ‐based analyses revealed the presence of micro‐organisms related to urban contamination, including Actinobacteria, mainly represented by Pseudonocardia hispaniensis , Thaumarchaeota and Ascomycota, dominated by Cladosporium . This microbial composition is consistent with groundwater pollution and contamination sources of the overlying urban area, including garages, petrol stations and wastewater pipeline leakage, showing that the Paranhos tunnel is greatly perturbed by anthropogenic activities. Whether the identified micro‐organisms are involved in the formation of the needle‐fibre calcite or not is difficult to demonstrate, but this study evidenced both abiotic and biogenic genesis for the calcite moonmilk in this subsurface granitic environment.     

海绵骨针特性及其仿生学研究

海绵是生长在海洋或淡水环境中的一种最简单的多细胞生物,3个主要海绵纲中有2个纲的海绵其主要骨架与支撑是玻璃纤维状的硅质骨针。近年来,人们发现了硅质海绵骨针独特的微结构及良好的光纤特性,特别是指出了这些特性给人类带来制造光纤的新思路,并很快引起了科学家对其结构、特性、生长机制与调控的生物学、生矿物学和仿生学的广泛研究兴趣。评述了海绵骨针内部结构和光学特性的发现、海绵骨针研究的热点领域及研究意义,并简要介绍了海绵骨针的国内外研究概况及主要工作。     

拓宽古生物研究领域

现代古生物学应加强横向联系,与其他有关学科相互渗透,扩大研究领域,拓宽研究内容、利用新技术,包括数学的、物理的、化学的以及现代生物学的理论和研究方法与沉积岩石学研究结合起来,提高古生物学的理论基础,给国家生产建设提供可靠的基础资料。     

蓝细菌聚金作用实验研究

蓝细菌聚金实验研究表明:①不同的生物由于生化组分的差异,其富金能力不同,低等蓝细菌生物比动物细胞富金能力强;②金在细胞中的分布与其各部分生化组成(也就是生物配体)密切相关;③金离子进入细胞不是一种简单的扩散作用,而是通过细胞膜界面两侧物质之间的交换而实现的,蓝细菌活体聚金机理主要是参与生命活动的吸收作用;④在较高温热水环境中微生物对成矿最显着。     

合浦珠母贝贝壳珍珠层EDTA可溶性基质蛋白对无定形碳酸钙稳定性的影响

通过红外光谱、扫描电镜、能谱等方法探讨了合浦珠母贝贝壳珍珠层EDTA可溶性基质蛋白(ESM)对无定形碳酸钙(ACC)晶型转化的影响。试验结果显示,合浦珠母贝贝壳珍珠层ESM在镁离子存在的条件下能够显著抑制ACC的转化,并减少最终诱导形成的方解石中的镁离子含量。同时,珍珠层ESM具有调节方解石晶体晶貌的作用。     

Silica biogeochemical cycle in temperate ecosystems of the Pampean Plain,Argentina

Silicophytoliths were produced in the plant communities of the Pampean Plain during the Quaternary. The biogeochemistry of silicon is scarcely known in continental environments of Argentina. The aim of this work is to present a synthesis of: the plant production and the presence of silicophytoliths in soils with grasses, and its relationship with silica content in soil solution, soil matrix and groundwaters in temperate ecosystems of the Pampean Plain, Argentina. We quantified the content of silicophytoliths in representative grasses and soils of the area. Mineralochemical determinations of the soils' matrix were made. The concentration of silica was determined in soil solution and groundwaters. The silicophytoliths assemblages in plants let to differenciate subfamilies within Poaceae. In soils, silicophytoliths represent 40–5% of the total components, conforming a stock of 59–72 × 10³ kg/ha in A horizons. The concentration of SiO₂ in soil solution increases with depth (453–1243 μmol/L) in relation with plant communities, their nutritional requirements and root development. The average concentration of silica in groundwaters is 840 umol/L. In the studied soils, inorganic minerals and volcanic shards show no features of weathering. About 10–40% of silicophytoliths were taxonomically unidentified because of their weathering degrees. The matrix of the aggregates is made up by microaggregates composed of carbon and silicon. The weathering of silicophytoliths is a process that contributes to the formation of amorphous silica-rich matrix of the aggregates. So, silicophytoliths could play an important role in the silica cycle being a sink and source of Si in soils and enriching soil solutions and groundwaters.     

The biogenic origin of needle fibre calcite

Needle fibre calcite is one of the most ubiquitous habits of calcite in vadose environments (caves deposits, soil pores, etc.). Its origin, either through inorganic, indirect or direct biological processes, has long been debated. In this study, investigations at 11 sites in Europe, Africa and Central America support arguments for its biogenic origin. The wide range of needle morphologies is the result of a gradual evolution of the simplest type, a rod. This rod is the elementary brick which, by aggregation and welding, builds more complex needles. The absence of cross‐welded needles implies that they are welded in a mould, or under a longitudinal and unidirectional constraint, before being released inside the soil pores. The difference between the lengthening of the needles and the c axis can be explained by the existence of needles observed under a scanning electron microscope in organic sleeves, which can act as a mould during rod growth. Complex morphologies with epitaxial outgrowths on straight rods cannot have grown entirely inside organic microtubes; they must result from soil diagenesis after the release of straight rods in a soil‐free medium. Whisker crystals are interpreted as the result of growth and coalescence of euhedral crystals on a rod. Rhomb chains are considered to be the consequence of successive epitaxial growth steps on a needle during variations in growth conditions. Isotopic signatures for needle fibre calcite vary from ?16·63‰ to +1·10‰ and from ?8·63‰ to ?2·25‰ for δ¹³C and δ¹⁸O, respectively. The absence of high δ¹⁸O values for needle fibre calcite precludes a purely physicochemical origin (evaporative) for this particular habit of calcite. As epitaxial growth cannot precipitate in the same conditions as initial needles, needle fibre calcite stable isotopic signatures should be used with caution as a proxy for palaeoenvironmental reconstructions. In addition, it is suggested that the term needle fibre calcite should be kept for the original biogenic form. The other habit should be referred to as epitaxial forms of needle fibre calcite.     

碳酸盐生物沉积作用的研究现状与展望

碳酸盐矿物是地球上最丰富的矿物之一,碳酸盐沉积在许多地质过程中起着非常重要的作用.生物沉积碳酸盐的现象在自然界普遍存在,其中又以生物沉积碳酸钙(CaCO3)为主.生物从周围环境中选择性地吸取元素,在严格的生物控制下,组装成功能化的碳酸盐结构;生物也可以通过改变周围的环境诱导碳酸盐的沉积或自身参与碳酸盐的沉积.不同生物对碳酸盐沉积的作用扣机理不同,综述了海洋动植物、藻类生物、菌类生物对碳酸盐的沉积作用及其机理以及实验室模拟调控CaCO3生物矿化方面的一些研究成果和研究现状,提出未来亟待解决的一些重要问题,并指出生物沉积碳酸盐研究所具有的巨大应用前景.     

上扬子区早寒武世黑色页岩磷结核特征及生化淀磷机制

通过野外观察、室内化学分析、矿物学分析、硫同位素分析、光学显微镜和扫描电镜观察,发现磷结核内所观察到的许多现象均与微生物的活动有关,微生物是使磷淀积的重要营力,这为磷结核的生物成矿作用提供了有力的证据.沉积物孔隙水物理化学条件的变化直接影响着磷结核的生长过程.