Impact of soil weathering degree on silicon isotopic fractionation during adsorption onto iron oxides in basaltic ash soils, Cameroon

The sequestration of silicon in soil clay-sized iron oxides may affect the terrestrial cycle of Si. Iron oxides indeed specifically adsorb aqueous monosilicic acid (H₄SiO₄⁰), thereby influencing Si concentration in soil solution. Here we study the impact of H₄SiO₄⁰ adsorption on the fractionation of Si isotopes in basaltic ash soils differing in weathering degree (from two weathering sequences, Cameroon), hence in clay and Fe-oxide contents, and evaluate the potential isotopic impact on dissolved Si in surrounding Cameroon rivers. Adsorption was measured in batch experiment series designed as function of time (0-72 h) and initial concentration (ic) of Si in solution (0.61-1.18 mM) at 20 °C, constant pH (5.5) and ionic strength (1 mM). After various soil-solution contact times, the δ³⁰Si vs. NBS28 compositions were determined in selected solutions by MC-ICP-MS (Nu Plasma) in medium resolution, operating in dry plasma with Mg doping with an average precision of ±0.15‰ (±2σ_SEM). The quantitative adsorption of H₄SiO₄⁰ by soil Fe-oxides left a solution depleted in light Si isotopes, which confirms previous study on synthetic Fe-oxides. Measured against its initial composition (δ³⁰Si = +0.02 ± 0.07‰ (±2σ_SD)), the solutions were systematically enriched in ³⁰Si reaching maximum δ³⁰Si values ranging between +0.16‰ and +0.95‰ after 72 h contact time. The enrichment of the solution in heavy isotopes increased with increasing values of three parameters: soil weathering degree, iron oxide content, and proportion of short-range ordered Fe-oxide. The Si-isotopic signature of the solution was partly influenced by Si release, possibly through mineral dissolution and Si desorption from oxide surfaces, depending on soil type, highlighting the complex pattern of natural soils. Surrounding Cameroon rivers displayed a mean Si-isotopic signature of +1.19‰. Our data imply that in natural environments, H₄SiO₄⁰ adsorption by soil clay-sized Fe-oxides at least partly impacts the Si-isotopic signature of the soil solution exported to water streams.     

Relationships between heavy metals and iron oxides,fulvic acids,particle size fractions in urban roadside soils

Urban roadside soils are the “recipients” of large amounts of heavy metals from a variety of sources including vehicle emissions, coal burning waste and other activities. The behavior of heavy metals in urban roadside soils depends on the occurrence as well as the total amount. Accordingly, knowledge of the interactions between heavy metals and other constituents in the soil is required to judge their environmental impact. In this study, correlations of heavy metal concentrations (Pb, Zn, Cu, Ag, Se, Ni, Cr and Ba) to iron extracted using dithionite–citrate–bicarbonate (DCB) buffer (Fe_DCB), fulvic acids and particle size fractions were examined from the Xuzhou urban roadside soils. Heavy metals except for Cr and fulvic acids had a positive significant correlation with Fe_DCB, indicating these metals and fulvic acids are principally associated with the surfaces of iron oxides of the soils. Significant positive correlations were also found between the contents of fulvic acids and heavy metals, showing these heavy metals (especially for Cu, Ni and Cr) form stable complexes with fulvic acids. Such finding is of importance with regard to the increased mobilization of heavy metals, e.g., into freshwater ecosystems. Ag, Se and Cr are independent of particle size fractions because of their low concentrations of Ag and Se in the studied soils. Pb, Zn, Cu, Ba and Ag are mainly enriched in the finer soil particles (especially <16 μm).     

Relationship between magnetic properties and heavy metals of urban soils with different soil types and environmental settings: implications for magnetic mapping

Two types of soil (fluvisols and anthrosols) were collected from different environmental settings (suburb and industrial area) in Wuhan, central China, aiming to examine the applicability of magnetic mapping for heavy metal pollution of urban soil in a large region. Magnetic measurements and chemical analysis indicated elevated magnetization and heavy metal concentrations of topsoils in the industrial area. Magnetic susceptibility (χ), anhysteretic remanent magnetization (ARM) and saturation isothermal remanent magnetization (SIRM) of fluvisols are much higher than those of anthrosols, but contrary for frequency-dependent susceptibility, indicating that soil magnetism strongly depends on the soil type/condition. Predominant magnetic carrier in topsoils in industrial area is pseudo-single-domain/multi-domain magnetite. Environmental scanning electron microscope/energy dispersive X-ray examination of the magnetic extracts from these topsoils revealed abundant spherical particles with diameters of 10–50 μm that are rich in iron-oxides, and could be attributed to the nearby industrial activities (e.g., steel work and power generation). Significant correlations were observed between magnetic concentration-related parameters (e.g., χ, ARM and SIRM) and concentrations of Cu, Pb, Zn, Hg and Tomlinson pollution load index. These results proposed that magnetic proxy mapping of soil pollution is an effective, fast and inexpensive tool for delineation of heavy metal pollution. However, interpretation of magnetic properties for such a purpose must be done on a site-specific basis, taking into account the possibilities of pedogenic enhancement/depletion under the specific soil conditions.     

Ichnoentomology: insect traces in soils,palaeosols and other substrates

Ichnology is the science that studies traces, mostly trace fossils, which are defined as morphologically recurrent structures (nests, burrows, trackways) resulting from the life activity of an individual organism modifying the substrate. Leonardo da Vinci was probably the first ichnologist. He mentioned the existence of traces of worms in rocks. Trace fossils reflect how extinct animals behaved. They are as parts of a time machine that allow us to almost see how extinct animals made their nests, fed, reproduced and walked. Moreover, they allow us to reconstruct palaeoenvironments and the evolutionary history of many taxa. Ichnology was originally developed by geologists; traces first caught our attention in rocks (palaeoichnology) and then in extant environments (neoichnology). For many years ichnology was only studied in marine or lacustrine environments, whereas terrestrial ichnology has been developed over the last few decades. Insect traces are the most common in terrestrial environments, such as palaeosols, but they are also common in plant remains, bones, and in some subaquatic substrates. Ichnoentomology deals with insect traces in soils, palaeosols and other substrates.     

河北阳原盆地井儿洼钻孔岩心氧化铁变化的古环境记录

系统分析了阳原盆地西部井儿洼钻孔剖面的Fe2O3、FeO、TFe(全铁)、Fe3 /Fe2 的变化特点,探讨了阳原古湖氧化铁地球化学特征及其所记录的气候变迁规律。结果表明,阳原盆地的沉积环境相对富集铁,气候总体较温和,垂向上的变化记录了气候的变化过程分为7个明显的阶段。0.2Ma以前以还原环境为主,以后以氧化环境为主。井儿洼岩心沉积物中全铁谱分析表明,0.78Ma之后,具有显著的21.7ka岁差周期,证明了天文因素对气候的影响,而100ka的周期不明显,这与黄土、深海沉积物的记录存在差别。另外还存在390ka、156ka、52ka、33.9ka及14.4ka等周期,表现了湖泊记录的古气候周期的复杂性。     

Retention of strontium,cesium, lead and uranium by bacterial iron oxides from a subterranean environment

Bacteriogenic Fe oxides (BIOS) and groundwater samples were collected 195 m underground at the Stråssa Mine in central Sweden. Ferrous iron oxidizing bacteria, including stalked Gallionella ferruginea and filamenous Leptothrix sp., were prominent in the BIOS samples. The BIOS samples were found to contain only poorly ordered (amorphous) hydrous ferric oxide, as determined by X-ray diffraction. Inductively coupled plasma mass spectroscopy revealed hydroxylamine-reducible Fe and Mn oxide contents that ranged from 55 to 85% on a dry weight basis. Concentrations of Sr, Cs, Pb and U in filtered groundwater ranged from 0.002 to 1.8 μM. Solid phase concentrations of these heavy metals in the BIOS spanned the 0.04–2.23 mmol/kg range. Distribution coefficients (K_d values), calculated as the ratio between BIOS and dissolved heavy metal concentrations, revealed solid phase enrichments that, depending on the heavy metal and Fe oxide content of the sample, extended from 10^3.0 to 10^4.7. At the same time, however, a strong inverse linear relationship was found between log K_d values and the corresponding mass fraction of reducible oxide in the samples, implying that metal uptake was strongly influenced by the relative proportion of bacterial organic matter in the composite solids. Based on the metal accumulation properties of the BIOS, an important role can be inferred for intermixed Fe oxides and bacterial organic matter in the transport and fate of dissolved metals in groundwater systems.     

Light lithophile elements in pyroxenes of Northwest Africa (NWA) 817 and other Martian meteorites: Implications for water in Martian magmas

Zoning patterns of light lithophile elements (the LLE: Li, Be, and B) in pyroxenes of some Martian basaltic meteorites have been used to suggest that the parent basalts were saturated in water and exsolved an aqueous fluid phase. Here, we examine LLE zoning in the augites of a quickly cooled Martian basalt that was not water-saturated—the Northwest Africa (NWA) 817 nakhlite. Analyses for LLE were by secondary ion mass spectrometry (SIMS), supported by EMP analyses of major and minor elements. In NWA 817, zoning of Be and B is consistent with igneous fractionations while Li abundances are effectively constant across wide ranges in abundance of other incompatible elements (Be, B, Ti, and Fe*). The lack of strong zoning in Li can be ascribed to intracrystalline diffusion, despite the rapid cooling of NWA 817. Most other nakhlites, notably Nakhla and Lafayette, cooled more slowly than did NWA 817 [Treiman, A.H., 2005. The nakhlite Martian meteorites: augite-rich igneous rock from Mars. Chem. Erde65, 203-270]. In them Li abundances are constant across augite, as are abundances of other elements. In Nakhla pyroxenes, all the LLE have effectively constant abundances across significant ranges in Fe* and Ti abundance. Lafayette is more equilibrated still, and shows constant abundances of LLE and nearly constant Fe*. A pyroxene in the NWA480 shergottite has constant Li abundances, and was interpreted to represent mineral fractionation coupled with exsolution of aqueous fluid. A simple quantitative model of this process requires that the partitioning of Li between basalt and aqueous fluid, ^LiD_aq/bas, be 15 times larger than its experimentally determined value. Thus, its seems unlikely that the Li zoning pattern in NWA480 augite represents exsolution of aqueous fluid. Late igneous or sub-solidus diffusion seems more likely as is suggested by Li isotopic studies [Beck, P., Chaussidon, M., Barrat, J.-A., Gillet, Ph., Bohn, M., 2005. An ion-microprobe study of lithium isotopes behavior in nakhlites. Meteorit. Planet. Sci.40, Abstract #5118; Beck, P., Chaussidon, M., Barrat, J.-A., Gillet, Ph., Bohn, M., 2006. Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: the case of pyroxene phenocrysts from nakhlite meteorites. Geochim. Cosmochim. Acta70, in press]. Pyroxenes of the Shergotty and Zagami meteorites have nearly constant abundances of B, and Li that decreases core-to-rim. Applying the quantitative model to the constant B in these pyroxenes requires that ^BD_aq/bas be 25 times larger than experimentally constrained values. Li abundances in pigeonite can be fit by the model of crystal fractionation and fluid loss, but only if ^LiD_aq/bas is 30 times the experimentally constrained value. The Li abundance pattern in augite cannot be modeled by simple fractionation, suggesting some strong crystal-composition effects. Thus, Li and B distributions in Shergotty and Zagami pyroxenes cannot be explained by igneous fractionation and exsolution of aqueous vapor. Intracrystalline diffusion, complete for B and incomplete for Li, seems more consistent with the observed zoning patterns.     

Minor and trace-element data of iron oxides from iron-formations of the Iron Quadrangle,Minas Gerais,Brazil

Summary Chemical investigations of 192 hand-picked iron-oxide concentrates from banded iron-formation of the Iron Quadrangle, Brazil, did not yield any significant difference in minor and trace-element contents between itabirite and iron-ore samples (Fe >63%). Mean values (171–177 samples) are: Ca 82 ± 12 ppm; Co 120 ± 8; Cr 77 ± 8; Cu 40 ± 2; Mg 40±5; Mn 170±L28; Ni 167±7; P 905±23; Ti 114±13; V 138±8; Al 1068 ± 174 ppm (52 samples) and Au 33 ± 8 ppb (50 samples). Microprobe results indicate different trends of Fe-substitution by minor elements depending on the different lattice types of magnetite and hematite. Mg and Mn are much more concentrated in magnetite than in hematite whereas hematite is distinctly enriched in titanium due to the isostructural nature of the hematite and ilmenite lattices.

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Zusammenfassung Chemische Analysen von 192, unter dem Binokular ausgelesener Eisenoxidkonzentrate von Proben aus den Eisenerzlagerstätten des Eisernen Vierecks in Brasilien, ergaben keinerlei Unterschiede in den Neben- und Spurenelementgehalten zwischen den Itabiriten und den Reicherzen (Fe >63%). Die Mittelwerte von jeweils 171–177 Elementbestimmungen ind folgende: Ca 82± 12 ppm; Co 120± 8; Cr 77± 8; Cu 40± 2; g 40±5; Mn 170±28; Ni 167±7, P 905±23; Ti 114:L13; V 138±8, Al 1068 ± 174 ppm (52 Proben) und Au 33 ± 8 ppb (50 Proben).Aus Mikrosondenuntersuchungen ergeben sich in Abhängigkeit von den unterschiedlichen Kristallgittertypen des Magnetits und Hämatits verschiedene Substitutionsraten des Eisens durch Nebenelemente. So zeigen Mg und Mn in Magnetiten um eine Vielfaches höhere Werte als in Hämatiten, während Ti im Hämatit wegen der Isotypie des Hämatit-Ilmenit-Gitters deutlich angereichert ist.

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With 1 Figures     

吉林西部土壤铁形态分布及其与土壤性质的关系研究

对吉林西部三个主要农牧区(洮南市、通榆县和乾安县)50个表层土样进行测试,探究其土壤铁形态分布及其与土壤性质的关系。研究结果表明,其土壤铁形态的含量分布为:残渣态铁(A)铁锰结合态铁(B)腐植酸结合态铁(C)碳酸盐态铁(D)强有机结合态铁(E)水溶态铁(F)离子交换态铁(G),主要以A形式存在,且全铁平均含量均低于中国铁元素背景值。A与阳离子交换量(CEC)呈极显著正相关,B与p H值呈极显著正相关,C、E与有机质呈极显著正相关。A与土壤矿质元素的关系最为密切,C、D、G次之。各形态铁之间,B、C、D两两呈极显著正相关,其他形态铁彼此间关系不大。     

Biomineralization and magnetic and thermal properties of the iron concretion from the laterite bauxite deposit of Bao Lok,South Vietnam

Doklady Earth Sciences -     

Phosphate removal from water by naturally occurring shale,sandstone, and laterite: The role of iron oxides and of soluble species

Aqueous phosphate removal by three geomaterials from Ivory Coast was evaluated to determine their potential application as low-cost phosphate adsorbents in wastewater treatment. Batch experiments showed that phosphate uptake strongly depended on pH. Laterite and sandstone dissolution was less pronounced compared to shale. A correlation between concentrations of aqueous cation species released from shale and phosphate uptake was observed. The kinetics were well described using the pseudo-second-order model. Isotherms displayed a saturation level on shale, while phosphate uptake continuously increased for laterite and sandstone. The removal efficiency decreased in the following ranking order: laterite > sandstone > shale. Laterite was also the most efficient adsorbent in column experiments. The high phosphate removal efficiency of laterite (8.3 mg PO₄ g^?1) was attributed to the presence of superparamagnetic low grain sizes of goethite. Laterite is a particularly promising material for further investigation in wastewater treatment technology such as constructed wetlands.     

Response of soil enzyme activities to synergistic effects of biosolids and plants in iron ore mine soils

Past mining activities in Swaziland have left a legacy of abandoned mine sites (iron ore, asbestos, diamond and coal mine dumps), all of which have not been reclaimed. These sites were recently (2013) considered by the country’s wastewater treatment authorities as suitable places where biosolids can be applied, firstly as a biosolids disposal alternative and, secondly, as a strategy to accelerate mine soil remediation through phytostabilization. In order to understand the effects that this might have on mine soil conditions and microbiota, two (2) plant growth trials were conducted in biosolid-treated iron mine soils and one (1) trial on undisturbed soil, under greenhouse conditions, for twelve (12) weeks. According to the results obtained, the combination of biosolids and plants led to significant improvements (p < 0.05) in parameters related to soil fertility. Significant increases (p < 0.05) in alkaline phosphatase, β-glucosidase and urease soil enzyme activities were also observed. Copper and zinc were significantly (p < 0.05) increased (Cu from 17.00–50.13 mg kg^?1; Zn from 7.59–96.03 mg kg^?1); however, these sludge-derived metals did not affect enzyme activities. Improvements in soil physicochemical conditions, organic matter–metal complexes, effects of plants on metals and the essentiality of Cu and Zn to soil enzymes were thought to have masked the effects of metals. Increases in soil enzyme activities were considered to be indicative of improvements in the quality, fertility health and self-purification capacity of iron mine soils due to synergistic effects of biosolids and plants.     

Texture development during progressive deformation of hematite aggregates: Constraints from VPSC models and naturally deformed iron oxides from Minas Gerais,Brazil

We show that naturally-deformed hematite from the Quadrilátero Ferrífero Province, Minas Gerais, Brazil, develops CPOs by dislocation creep, strongly influenced by basal plane parallel glide, even when this is not the favored slip system. Characterization of microstructure and texture, particularly intragranular misorientations, of naturally deformed hematite aggregates by EBSD allowed us to determine the importance of different slip systems, and confirm dislocation creep as the dominant deformation mechanism. Viscoplastic self-consistent (VPSC) models were constructed to constrain the slip systems required to operate for the observed CPO to develop, and its rheological implications. Changes in the CRSS ratio of hematite prism and basal slip systems and deformation regime lead to the development of distinct patterns of hematite crystallographic orientations. The basal slip-dominated simple shear model is the only one that can develop quasi-single-crystal CPO of the kind observed in highly deformed rocks from Quadrilátero Ferrífero. Comparison between naturally deformed hematite aggregates and VPSC models shows that CPO development of hematite is strongly influenced by a highly viscoplastic anisotropy through dislocation creep on hematite basal plane. Nonetheless, our results demonstrate that even the unfavorable slip systems should be regarded when the bulk rheology of mineral aggregates is evaluated.     

Mineral magnetic properties of Holocene lake sediments and soils from the Kårsa valley,Lappland, Sweden,and their relevance to palaeoenvironmental reconstruction

A mineral magnetic study of lacustrine sediments and soils from the Kårsa valley in Lappland, Sweden was undertaken to estimate the potential of mineral magnetic techniques in elucidating the variability of climate, recorded by glacier fluctuations and soil development. Sediment cores from two lake basins receiving sediment input from a glacial outflow stream, and their respective catchments, show a mineral magnetic record that can be interpreted in terms of glacial activity and soil development. Dissolution of magnetite is indicated during periods of climatic amelioration and causes a high S-ratio. During periods of glacial advance (and colder, wetter climate) the minerogenic sediment supply is increased and magnetite is preserved in the sediment, resulting in a low S-ratio. Variations in the S-ratio can then be used as a proxy-climate indicator.     

The tetrahedral framework in glasses and melts — inferences from molecular orbital calculations and implications for structure,thermodynamics, and physical properties

Results of ab initio molecular orbital (MO) calculations provide a basis for the interpretation of structural and thermodynamic properties of crystals, glasses, and melts containing tetrahedrally coordinated Si, Al, and B. Calculated and experimental tetrahedral atom-oxygen (TO) bond lengths are in good agreement and the observed average SiO and AlO bond lengths remain relatively constant in crystalline, glassy, and molten materials. The TOT framework geometry, which determines the major structural features, is governed largely by the local constraints of the strong TO bonds and its major features are modeled well by ab initio calculations on small clusters. Observed bond lengths for non-framework cations are not always in agreement with calculated values, and reasons for this are discussed in the text. The flexibility of SiOSi, SiOAl, and AlOAl angles is in accord with easy glass formation in silicates and aluminosilicates. The stronger constraints on tetrahedral BOB and BOSi angles, as evidenced by much deeper and steeper calculated potential energy versus angle curves, suggest much greater difficulty in substituting tetrahedral B than Al for Si. This is supported by the pattern of immiscibility in borosilicate glasses, although the occurrence of boron in trigonal coordination is an added complication. The limitations on glass formation in oxysulfide and oxynitride systems may be related to the angular requirements of SiSSi and Si(NH)Si groups. Although the SiO and AlO bonds are the strongest ones in silicates and aluminosilicates, they are perturbed by other cations. Increasing perturbation and weakening of the framework occurs with increasing ability of the other atom to compete with Si or Al for bonding to oxygen, that is, with increasing cation field strength. The perturbation of TOT groups, as evidenced by TO bond lengthening predicted by MO calculations and observed in ordered crystalline aluminosilicates, increases in the series Ca, Mg and K, Na, Li. This perturbation correlates strongly with thermochemical mixing properties of glasses in the systems SiO₂-M ₁ ^n/n+ AlO₂ and SiO₂-M ⁿ⁺O _n/2 (M=Li, Na, K, Rb, Cs, and Mg, Ca, Sr, Ba, Pb), with tendencies toward immiscibility in these systems, and with systematics in vibrational spectra. Trends in physical properties, including viscosity at atmospheric and high pressure, can also be correlated.     

Correlation of magnetic and lithologic features of soils and Quaternary sediments from the Undulating Pampa,Argentina

A lithological and mineral magnetic study of three soil and underlying sedimentary sections located at different topographic positions in the Undulating Pampa was performed. On the basis of grain size analyses, clay, silt and sand mineralogy, and total Ti/Zr relationship three different sedimentary units were recognised in the profiles under study suggesting that the area has been influenced by three different sources of sediments. Magnetic susceptibility (MS) appears to be related to lithology, allowing the identification of some material and lithologic discontinuities. In the studied cases the maximum values of MS appear in both the B horizons of the present zonal soils as well as in the primary or reworked loess levels. In contrast, minimum values are associated with calcrete, paleosol, and hydromorphic horizons. Although magnetic susceptibility appears to be an effective means for identifying different materials and pedological features in this area, due to the superposition of effects on the magnetic signal a thorough interpretation of MS requires that a composite analysis should be made.     

Magnetic properties of microcrystalline iron (III) oxides and related materials as reflected in their Mössbauer spectra

Iron (III) oxides are common constituents of geologic materials, they are products and by-products of many industrial processes, they are involved in biological processes, and they are the outcome of iron and steel corrosion. In many of these examples the iron oxides are — fortuitously or intentionally — of small particle size, and as a consequence difficult, if not impossible, to characterize by standard physicochemical techniques. ⁵⁷Fe Mössbauer spectroscopy is suitable for this purpose because it can serve as a probe of the electric and magnetic conditions in the vicinity of iron nuclei in solid samples, no matter how the iron may be bound. Deviations of the magnetic properties of iron oxides of small particle size from those of their bulk counterparts lead to radical changes in the appearance of their Mössbauer spectra. Diverse models that have been put forward to account for such changes are discussed in this paper, including superparamagnetism, collective magnetic excitations, anomalous recoil-free fractions, superferromagnetism, spin canting and speromagnetism, reduced hyperfine field supertransfer, and Néel temperature reductions and distributions. Specific examples of microcrystalline iron (III) oxides and related minerals originating from different natural environments, resulting from technical processes, and being studied as planetary analogs are presented and discussed in the light of present-day knowledge on the properties of such materials.     

Citywide distribution of lead and other element in soils and indoor dusts in Syracuse,NY

Associations between Pb, Zn, Fe and Mn in soils and indoor dusts in urban Syracuse, NY have been investigated at different levels of spatial aggregation. The concentrations of these elements of interest (EOI) in 3566 soil samples were mapped across the city to investigate variations in concentration potentially associated with specific city locations. Indoor floor dust loadings for the EOI determined at 433 residences were mapped in a similar fashion. Pearson product correlation coefficients at different levels of soil sample aggregation (individual sampling points, block group averages, and census tract (CT) averages), consistently demonstrated a strong correlation between soil Pb and Zn concentrations. Correlations between Pb and both Fe and Mn soil concentrations were also significant. However, the correlation between the Fe and Mn floor dust loadings was much stronger than that for soil, as were the correlations between the Pb and both the Fe and Mn dust loadings. The correlation between the Fe and Zn floor dust loadings was far less significant. Surprisingly, most of the correlations between the paired EOI in the dusts and soils at the individual homes were mostly not statistically significant. The two correlations of any significance, and these were between the Pb in soil and the Pb in the dust, and between Pb in dust and Zn in soil.     

Authigenic iron and titanium oxides in triassic red beds: (St. Bees Sandstone), Cumbria,Northern England

Authigenic iron and titanium oxides occur in three main textural varieties in the St. Bees Sandstone, a Triassic red bed succession in Cumbria. These are: (a) overgrowths of haematite, titaniferous haematite, anatase, and rutile which generally occur on detrital host grains of similar compositions. The overgrowths may occur as syntaxial rim cements or rhombohedral and prismatic projections and are always in optical continuity, (b) discrete crystals of anatase (including octahedrite) and haematite 10-40 μm in size occur in pore spaces, and (c) fine grained ( < 1 μm) pigmentary haematite occurs as grain coatings around detrital grains and in the interstitial matrix. The euhedral nature and pore-filling habit clearly indicate the authigenic origin of these iron- and titanium oxides. All three textural varieties are believed to have been precipitated from ground waters containing dissolved ferrous and titanium ions. These ions were derived from the intrastratal solution of detrital iron and titanium bearing grains including ferromagnesian silicates and iron-titanium oxides. The precipitation of iron oxides from migrating ground waters in the manner described here goes some way to explaining how thick, uniformly red successions can be formed.