Berthierine (formerly chamosite) occurs as concretions, lenses, and bands in carbonaceous, kaolinitic shale of freshwater coal-swamp deposits in Paleogene and Upper Triassic coal measures of Japan. Textural relations in thin sections of the Triassic berthierine rocks and a siderite-kaolinite-berthierine-quartz assemblage in Paleogene rocks indicate that the berthierine formed by reaction of siderite with kaolinite. The transformation of siderite and kaolinite to berthierine and quartz occurs progressively under reducing conditions between 65° and 150°C and at burial depths of 2–5 km. Utatsu berthierine is an aluminous, low-Mg variety as compared with berthierine pellets in modern marine and estuarine sediments and in ancient marine ironstones. Fe is the dominant octahedral cation with Fe2+ ≫ Fe3+. The composition of the berthierine varies between different morphological types. Utatsu berthierine transformed to ferrous chamosite when kaolinite in the host shale changed to pyrophyllite. These transformations are estimated to have occurred at ∼160°C and at a burial depth of ∼3 km.

Two distinct assemblages of authigenic phyllosilicates were distinguished in the Kremikovtsi sedimentary exhalative (SEDEX) siderite iron formation (SIF) and noted as important tracers of two styles of mineralization characteristic of this type of ore deposit. Hydrothermal-sedimentary layer silicates are represented by rare occurrences of relict microcrystalline Mg-rich berthierine with a relatively low degree of structural ordering, associated closely with framboidal pyrite as an intergranular matrix cementing sparry siderite grains; the larger silicates are also represented by the diagenetic transformation product of berthierine, chamosite. Berthierine precipitated under anoxic conditions during advanced early diagenesis after chert deposition. Hydrothermal-epigenetic phyllosilicates (berthierine, chamosite, illite-smectite (I-S), and kaolinite) from the barite-sulfide assemblage are characterized by: crystalline and undeformed habits; relatively larger particle size, low-temperature polytypes, low to no mixed layering, and a high degree of crystallinity; absence of impurities and dominant monomineralic aggregates; affiliation to initial open spaces and deposition mainly as vug fillings and linings. They formed under pronounced control by the vuggy porosity of the siderite host caused by the invasion of acid (pH = 3–5), hot (200–230°C) hydrothermal fluids probably at the stage of burial diagenesis of the SIF under relatively stable reducing conditions fluctuating near the sulfide/sulfate stability boundary $\left(\log {\text{P}}_{{\text{O}}_{\text{2}}}\cong -30\right)$. The greater Al concentration in hydrothermal solution than in seawater determines the affiliation of phyllosilicates in the Phanerozoic SEDEX SIFs to aluminous species (berthierine, chamosite) unlike low to non aluminous ones (greenalite, stilpnomelane) in the Precambrian IFs. The berthierine compositions, expressed by the Mg/Fe vs. Al/Si ratios, are a sensitive indicator of the geological conditions under which they formed (marine, non-marine, hydrothermal ore and pre-ore), thus allowing the genetic discrimination of this mineral from various localities.

Transgression by the Western Interior Sea during the Late Cretaceous in southwestern Minnesota caused swampy conditions to be imposed upon a laterite consisting of gibbsite, goethite and kaolinite. Reducing conditions overprinted upon the laterite reduced ferric Fe in goethite for incorporation of ferrous Fe into Fe-berthierine. Attendant oxidation of organic matter provided CO2 for siderite's formation. Thermodynamic calculations indicate that berthierine, gibbsite, goethite, kaolinite and siderite were in equilibrium with a solution whose pH was 5.2 and whose pCO2 was on the order of 0.3 atm. Formation of Fe-berthierine is favored by solutions having: 1) low silica concentration; 2) low [Mg2+]/[Fe2+] ratio; 3) high pCO2; 4) extremely low sulfate content before reduction takes place; and 5) moderate reducing conditions (Eh around −0.05 V).

Electron energy-loss spectroscopy (EELS), energy-filtered transmission electron microscopy (EFTEM), and high-resolution transmission electron microscopy (HRTEM) have been applied in mineralogy and materials research to determine the oxidation states of various metals at high spatial resolution. Such information is critical in understanding the kinetics and mechanisms of mineral–microbe interactions. To date, the aforementioned techniques have not been applied widely in the study of such interactions. In the present study, the three techniques above were employed to investigate mineral transformations associated with microbial Fe(III) reduction in magnetite. Shewanella putrefaciens strain CN32, a dissimilatory metal-reducing bacterium, was incubated with magnetite as the sole electron acceptor and lactate as the electron donor for 14 days under anoxic conditions in bicarbonate buffer. The extent of bioreduction was determined by wet chemistry and mineral solids were investigated by HRTEM, EFTEM, and EELS. Magnetite was partially reduced and biogenic siderite formed. The elemental maps of Fe, O, and C and red-green-blue (RGB) composite map for residual magnetite and newly formed siderite were contrasted by the EFTEM technique. The HRTEM revealed nm-sized magnetite crystals coating bacterial cells. The Fe oxidation state in residual magnetite and biogenic siderite was determined using the EELS technique (the integral ratio of L3 to L2). The integral ratio of L3 to L2 for magnetite (6.29) and siderite (2.71) corresponded to 71% of Fe(III) in magnetite, and 24% of Fe(III) in siderite, respectively. A chemical shift (~1.9 eV) in the Fe-L3 edge of magnetite and siderite indicated a difference in the oxidation state of Fe between these two minerals. Furthermore, the EELS images of magnetite (709 eV) and siderite (707 eV) were extracted from the electron energy-loss spectra collected, ranging from 675 to 755 eV, displaying different oxidation states of Fe in the magnetite and siderite phases. The results demonstrate that EELS is a powerful technique for studying the Fe oxidation-state change as a result of microbial interaction with Fe-containing minerals.

The formation of siderite and magnetite by Fe(III)-reducing bacteria may play an important role in C and Fe geochemistry in subsurface and ocean sediments. The objective of this study was to identify environmental factors that control the formation of siderite (FeCO3) and magnetite (Fe3O4) by Fe(III)-reducing bacteria. Psychrotolerant (<20°C), mesophilic (20–35°C) and thermophilic (>45°C) Fe(III)-reducing bacteria were used to examine the reduction of a poorly crystalline iron oxide, akaganeite (β-FeOOH), without a soluble electron shuttle, anthraquinone disulfuonate (AQDS), in the presence of N2, N2-CO2(80:20, V:V), H2 and H2-CO2 (80:20, V:V) headspace gases as well as in -buffered medium (30–210 mM) under a N2 atmosphere. Iron biomineralization was also examined under different growth conditions such as salinity, pH, incubation time, incubation temperature and electron donors. Magnetite formation was dominant under a N2 and a H2 atmosphere. Siderite formation was dominant under a H2-CO2 atmosphere. A mixture of magnetite and siderite was formed in the presence of a N2-CO2 headspace. Akaganeite was reduced and transformed to siderite and magnetite in a -buffered medium (>120 mM) with lactate as an electron donor in the presence of a N2 atmosphere. Biogeochemical and environmental factors controlling the phases of the secondary mineral suite include medium pH, salinity, electron donors, atmospheric composition and incubation time. These results indicate that microbial Fe(III) reduction may play an important role in Fe and C biogeochemistry as well as C sequestration in natural environments.

This paper addresses the application of thermal analytical methods (DTA/DSC/TG/ MS) in soil investigations, especially the interrelation of exothermic effects and analytical or preparative parameters. For the superimposed decomposition/ oxidation reactions of siderites, FeCO3, the heating rate is shown to have a decisive influence because low heating rates tend to suppress the endothermic effect. In mixtures of small amounts of organic matter (glucose and starch) with talc, the phyllosilicate acts as a catalyst by influencing the intensity of combustion of the organic matter.

A three-fold zonation can be imaged within authigenic siderite from sandstones of the Brent Group using back-scatter SEM techniques. We interpret this zonation in terms of the biogeochemical zonation of shallow buried sediment. The innermost siderite crystal zone is very Fe rich (95.0±0.5 mol.% FeCO3), with high Mn levels relative to Ca and Mg. This is interpreted as forming within the Fe reduction zone, with Mn from the closely associated Mn reduction zone. The second siderite crystal zone is frequently represented either by an episode of dissolution, or is impure (80±1 mol.% FeCO3), and this corresponds to the sulphate reduction zone. The outer crystal zone is intermediate in composition, and is equated with the zone of methanogenesis (88±1 mol.% FeCO3). Isotopic values cannot be assigned to individual crystal zones. Bulk δ18O values (−2.7 to −13.0‰ V-PDB) are not consistent with precipitation from seawater at low temperatures, but suggest meteoric pore-waters. δ13C data (−4.3 to −15.7‰ V-PDB) are consistent with microbially-mediated precipitation.

Pyrite and siderite are usually mutually exclusive within a single sample. Sedimentary conditions which favour the development of a strong sulphate reduction zone, and hence the formation of pyrite, do not favour the formation of a strong sub-oxic zone, where siderite is preferentially precipitated, and vice versa. There is a strong facies control upon siderite formation, with ripple cross-laminated sands being most strongly siderite cemented.

Carbonates of the magnesite-siderite series have been found and analysed in carbonatites from the Lueshe, Newania, Kangankunde, and Chipman Lake complexes. This series has been represented until now only by a few X-ray identifications of magnesite and three published analyses of siderite and breunnerite (magnesian siderite). Most of the siderite identified in carbonatites in the past has proved to be ankerite, but the new data define the complete solid-solution series from magnesite to siderite. They occur together with dolomite and ankerite and in one rock with calcite. The magnesites, ferroan magnesites and some magnesian siderites may be metasomatic/hydrothermal in origin but magnesian siderite from Chipman Lake appears to have crystallized in the two-phase calcite + siderite field in the subsolidus CaCO3-MgCO3-FeCO3 system. Textural evidence in Newania carbonatites indicates that ferroan magnesite, which co-exists with ankerite, is a primary liquidus phase and it is proposed that the Newania carbonatite evolved directly from a Ca-poor, Mg-rich carbonatitic liquid generated by partial melting of phlogopite-carbonate peridotite in the mantle at pressures >32 kbar.

Recent TEM observations of two-phase microstructures and associated crystal defects in selected, rare dolomites have been extended to calcite-structured (R3̄c) carbonates and to other natural and synthetic carbonates that crystallize with the dolomite (R3̄) structure. The samples included siderites (FeCO3), smithsonites (ZnCO3), ankerites (Ca[Mg,Fe](CO3)2), and kutnahorites (Ca[Mn,Fe](CO3)2).

TEM methods show that the forms of second phases which result from the presence of common, divalent, metallic impurities are morphologically similar in R3̄c and R3̄ carbonates and occur more widely than hitherto realized. The most common form consists of thin ribbons of second phase which are coherent with and have the same crystallographic orientation as the host carbonate. Another form of microstructure, manifest as modulations in diffraction contrast, appears to be associated with incipient breakdown of single-phase carbonate. The results of extensive TEM/EDS microanalyses show that in siderite and ankerite the formation of ribbons is promoted by Ca impurity or Ca excess (with respect to R3̄c stoichiometry). In smithsonite, Cu and Ca impurities can play similar roles in relation to modulated microstructures. In kutnahorites, the perfection of grains and the absence of second-phase effects is strongly dependent on the ratio of Fe to Mn but is also affected by Ca in excess of the stoichiometric requirement. Electron diffraction results from several of the minerals show c-type spots, which can be interpreted as indicating ordering within basal layers of cations.

The results show that, by correlating analytical TEM data with the study of second phases and incipient two-phase microstructures, it should be possible to determine the limits of solid solubility in carbonate systems.

The Rhenohercynian thrust- and fold-belt of Central Europe hosts a syn- to post-kinematic Variscan vein mineralisation, which is restricted to the Rhenish Massif, Germany. It is formed during four major stages and siderite is the principal ore mineral of the 'main stage'. The latter can be traced throughout the massif, but is mainly developed in the Siegerland district as synkinematic lodes which are hosted by low-grade metamorphic pelites of Lower Devonian age.

Fluid inclusion studies prove large-scale homogeneous ore forming fluids of low salinity (≤5 wt.% NaCI equiv.) and Na(-K > -Fe ≫ Mg)-C1 composition, which are CO2 undersaturated (XCO2 = 0.003-0.1). Siderite precipitation at 220−≤320°C and 0.7-1.4 kbar can be deduced by microthermometry, chlorite themometry, REE fractionation and experimental data. Thereby the maximum formation temperature comes close to or even exceeds the peak metamorphic temperature. From Mn contents and δ13C-δ18O variation of siderite a trend is apparent in which formation temperatures gradually decrease from S.E. to N.W. across the belt. This trend correlates with decreasing degree of host-rock deformation and decreasing metamorphic grade. Fluid composition as well as stable isotopes and REE fractionation of siderite point to ore-forming solutions, which were generated and equilibrated at depth during prograde metamorphism.

Structural characteristics of the lodes, age determinations, and P-T estimations prove fluid ascent and siderite precipitation during and/or immediately after peak metamorphism predating the postkinematic magmatism of the Rhenohercynian belt. Main(-siderite)-stage mineralisation of the Rhenish Massif is classified as metamorphogeneous.

The chemical and mineralogical composition of rattlestones found near the main Dutch rivers has been studied by Mössbauer spectroscopy, INAA and XRD. Rattlestones are concretions of iron, formed in an environment of lateral iron accumulation, under the influence of periodical oxidation, around a fine core of ferruginous sediments, mainly clay and sand. The core has shrunk and detached itself from the mantle around it. 57Fe Mössbauer spectroscopy was applied to identify the iron oxides, among which goethite is predominant. The goethite crystallinity was investigated by measuring its magnetic properties and its crystallinity, which is poorest at the outer side of the stone. The latter is confirmed by the broadening of the different X-ray reflections. In addition, illite and vermiculite were identified by XRD; these clay minerals were found mainly in the core.

The elemental composition was determined by INAA. The iron content in the mantle is about 50% by weight and gradually decreases outwards, while the core contains 2–15% Fe by weight. Differences between rattlestones from the Middle Pleistocene East of the Meuse river and those from the Late Pleistocene North of it are the absence of lepidocrocite and a richer mineralogy in the former.

It is concluded that the rattlestones are formed around a fine clayey core. Groundwater supplied the iron and other (trace) elements for the genesis. It is unlikely that rattlestones are the result of oxidation of siderite.