Both radiating dykes and proximal cone sheets converge onto a positive aeromagnetic anomaly of an inferred carbonatitic centre, hidden beneath a retreating edge of the Frederikshåbs Isblink glacier. This convergence, together with sub-parallel incompatible element patterns by all intrusions, suggests a cogenetic relationship that warrants investigation into potential diversification processes. More primitive high- and low-Mg damtjernites, which for three dykes conform to more porphyritic dyke cores and aphyric margins, respectively, can be explained by high-Mg trends being controlled by the fractionation/accumulation of mainly augite and olivine (or other mafic phases), while discordant low-Mg trends require additional decoupled magnetite fractionation. It is proposed that each dyke intrusion tapped the differentiated top of a central magma chamber, occasionally followed by an unconsolidated mafic cumulate mush, excluding denser magnetites, with in situ flow segregation playing a subordinate additional role. Beyond the most differentiated damtjernite, more evolved phonolitic nephelinites to carbonaceous alnöites split into bulk rock geochemical T-trends that can only relate to late-stage segregations into magmas with varying proportions of interstitial igneous (not secondary) analcime and carbonate – collectively increasing in volume with differentiation. While the analcime component also appears to segregate more readily into veins and ocelli than carbonatite, it is speculated if such low viscosity, density and liquidus rest melts, inside igneous centres, more efficiently aggregated into voluminous, buoyant analcime caps above slightly denser carbonatites. Similar converging plumbing systems and diversification processes are proposed for other complexes, where kimberlitic parents were simply extracted from deeper mantle sources.

Ferrous or ferric Perchlorate, 0.01 M, was reacted with calcite in stirred aqueous suspensions which were bubbled vigorously with an oxidizing purge gas. Two and three equivalents of CaCO3 were dissolved per mole of Fe2+ and Fe3+ neutralized, respectively. With Fe(ClO4)2, the crystalline Fe oxide products partially coated the calcite surface. The dominant products were lepidocrocite and goethite when the purge gas was air or 20% CO2 (balance air), respectively. After reaction with Fe2+ the edges and corners of the calcite crystals were generally rounded and the faces were non-uniformly pitted; however, after reaction with Fe3+, a mosaic pattern with distinct ridges and channels was evident on the calcite. These ridges were somewhat pitted, but distinct stepped dislocations were present leading to a featureless and generally flat channel floor. When the calcite was separated from the Fe solution by a semi-permeable membrane, precipitation occurred predominantly on the calcite side and on the Fe side of the membrane in the Fe2+ and Fe3+ systems, respectively.

Fe oxyhydroxides precipitated from the Fe(ClO4)3 and Fe(ClO4)2 solutions by different mechanisms. In the Fe(ClO4)3 system, although the initial reaction may have been at the calcite surface, the bulk of the poorly crystalline ferrihydrite was formed by hydrolysis of Fe polymers in suspension. Neutralization occurred by the reaction with basic products of a surface-controlled dissolution of calcite, rather than by a direct reaction of acidic polymers with the calcite surface. In the Fe(ClO4)2 system, lepidocrocite or goethite formed by the partial hydrolysis of Fe2+ or Fe3+ by reaction with calcite or the basic products of calcite dissolution and subsequent precipitation of simple Fe species on existing FeOOH nuclei.

Iron salts react readily with calcite in oxidizing calcareous environments to produce solid phase Fe-oxides. These reactions represent important processes in aqueous, geologic, and pedogenic environments. In the present investigation, Fe-oxides were precipitated from Fe(ClO4)2 solutions on undisturbed calcite grains in aqueous suspension. In this way it was possible to investigate the sequence of events in the crystallization process. Following an initial precipitation on the calcite grains, a period of slow growth of lepidocrocite was noted wherein 4-μm euhedral platelets formed with uniform orientation perpendicular to the calcite surface. The slow growth and highly crystalline nature of the Fe-oxide product may be partially due to the diffusion barrier formed by the growing oxide crystal mass which influenced rate of movement of HCO3− to the dissolved Fe phase and Fe ions and H+ towards the calcite surface. Upon continued aging, the supernate became noticeably opaque. As the suspended nuclei settled, new surfaces for crystal growth were provided which resulted in somewhat less crystalline lepidocrocite and goethite.

The nature, composition, and relative abundance of clay minerals in the sandstones of the Brent Group reservoir were studied between 3200–3300 m in a well of the Ellon Field (Alwyn area, North Sea). The sandstones have a heterogeneous calcite cement which occurred during early-diagenesis. Clay diagenesis of the cemented and uncemented sandstones was investigated using optical microscopy, scanning electron microscopy (SEM), X-ray diffraction analyses (XRD), and infrared spectroscopy (IR). The influence of cementation on clay neoformation is demonstrated in this study. Detrital illite and authigenic kaolinite are present in both the calcite-cemented and uncemented sandstones suggesting that kaolinite precipitated before calcite cementation. In the uncemented sandstones, blocky dickite replaces vermiform kaolinite with increasing depth. At 3205 m, authigenic illite begins to replace kaolinite and shows progressive morphological changes (fibrous to lath-shape transition). At 3260 m, all sandstones are not cemented by calcite. Illite is the only clay mineral and shows a platelet morphology.

In the cemented samples, vermiform kaolinite is preserved at all depths, suggesting that dickite transformation was inhibited by the presence of the calcite cement. This observation suggests that calcite cement would prevent fluid circulation and dissolution-precipitation reactions.

Calcite crystals exposed to clay volatiles react with some components of these volatiles, giving rise to a variety of surface morphologies. F, Cl, and S in different proportions were detected by electron microprobe analysis of the calcite surfaces. Under identical experimental conditions, volatiles from every clay mineral examined caused a specific morphology and chemical composition of the calcite surfaces, but these varied with temperature of the calcite. Changes in pH values and mass spectra of the volatiles after passage through calcite demonstrate that even on rapid heating some clay volatile-calcite reactions occur at temperatures as low as 150°C. Species other than those detectable by electron microprobe analysis also participate in the reactions in which CO2 is liberated.

For several decades, many efforts have been dedicated to enhancing the accuracy of mortar radiocarbon dating and evaluating the reliability of the results concerning the typology of the examined specimens. Several assumptions that are fundamental for the application of the method may be in many cases not fulfilled, such as (a) complete primary limestone dissociation during calcination, (b) efficient separation of geogenic carbon contained in calcareous aggregates, (c) short carbonation time, and (d) absence of secondary calcite. Many laboratories all over the world have proposed different methods to select suitable fractions of mortar.

The first intercomparison attempt, involving eight international laboratories, was organized in 2016 aiming at comparing and statistically treating the results obtained on the same materials by different laboratories with their own characterization and pre-treatment methods (Hajdas et al. 2017; Hayen et al. 2017). Following this first step, a new intercomparison experiment was proposed and set up in 2018 during the Mortar Dating International Meeting (Bordeaux, FR). A new set of three mortar samples was chosen, taking care of the selection of standardized materials (homogeneity, known mineralogical composition, absence of exogenous inclusions, known expected age).

This work describes the results of two research teams involved in the intercomparison. The samples were characterized, selected, and dated depending on each laboratory strategy. The results stress the importance of the characterization of the raw material is to better understand the mineralogical and petrographical composition of the samples. Such information can support the choice of the most appropriate strategy for the extraction of CO2 and then for data interpretation.

The zeolites and coexisting minerals of the silicic vitric tuffs in the Alaçatı (Çeşme) area, west of İzmir (Turkey), were studied. Mordenite is the most abundant zeolite in tuffs of the Alaçatı area and usually coexists with clinoptilolite-heulandite, smectite and calcite. Opal-CT was identified by means of its crystal morphology and EDX spectrum. Scanning electron microscopy (SEM) revealed the relative age relationships between the zeolites and coexisting minerals, namely mordenite, clinoptilolite-heulandite, smectite, calcite, and, in addition, opal-CT. Smectite consistently crystallized earlier than any of the zeolites, and it occasionally coats the outer walls of some of the vitric material. The zeolites are commonly located on the smectite, although some mordenites were observed to be in direct contact with glass shards that lacked a smectite coating. Clinoptilolite-heulandite formed after smectite and before mordenite. Opal-CT is seen to postdate both smectite and needle-shaped mordenite. Calcite was probably the latest mineral to crystallize in the Alaçatı tuffs. The zeolites in the tuffs of the Alaçatı area formed by dissolution of silicic vitric tuffs by Na- and Ca-rich thermal waters which passed through the fracture zone. The appearance of zeolites together with smectite along this zone may be attributed to a semi-open system which subdivided into smaller closed systems. Small changes in the pH and chemical composition of the thermal waters during alteration produced the corrosion effects observed by SEM. Small amounts of clinoptilolite-heulandite were corroded prior to crystallization of coexisting mordenite. The different compositions of the thermal waters were probably inherited from water that resulted from mixing of thermal and groundwaters.

Liquid immiscibility has become the preferred mode of genesis for the carbonatite rocks, which commonly, but not exclusively, accompany silicate rocks in alkaline-rock complexes. This concept has been universally based on the presumption that nephelinitic and phonolitic magmas can evolve to a stage where two conjugate immiscible liquids separate. It is assumed that these two liquids separate quickly, or even instantaneously, into discrete bodies of magma capable of being intruded or extruded with subsequent independent crystallization. Supporting evidence generally given is: alleged consanguinity as discrete occurrence of the two rock types; similarity of radiogenic isotope ratios; trace element contents similar to those predicted from experimentally derived partition coefficients. We do not accept that a general case for liquid immiscibility has been demonstrated; although we do accept that silicate and carbonate liquids are inherently immiscible, we maintain that they are not conjugate in a petrogenetic context. We have reviewed and critically examined the experimental data purporting to establish liquid immiscibility and find that when applied to natural rocks, they are based on inappropriate experimental designs, which are not relevant to the genesis of calcite or dolomite carbonatites, although they might have some relevance to Oldoinyo Lengai nyerereite–gregoryite lavas. The design of these experiments guarantees immiscibility and ensures that the carbonate liquids formed will be calcitic or sodium-rich. We dispute the validity of comparing the trace element contents of natural rocks, which in many instances do not represent liquid compositions, to experimentally determine partition coefficients. We consider that experimental design inadequacies, principally assuming but not proving, that the liquids involved are conjugate, indicate that these coefficients are merely an expression of the preference of certain elements for particular liquids, regardless of how the liquids formed. Proof of consanguinity in alkaline complexes requires more accurate age determinations on the relevant rock types than has generally been the case, and in most complexes, consanguinity can be discounted. We dispute the contention that melt inclusions represent parental melts, although they might elucidate the character of magmas undergoing fractional crystallization from magmatic to carbothermal stages. Radiogenic isotope data are shown to be too widely variable to support a case for liquid immiscibility. We address the contention that calcite cannot crystallize from a dolomitic liquid formed by direct mantle melting, and must therefore have crystallized from a calcite carbonate liquid generated by liquid immiscibility, and demonstrate that it is an unsupported hypothesis as calcite can readily crystallize from dolomitic liquids. We observe that, because immiscible dolomite liquids have never been produced experimentally, the liquid immiscibility proposition could at best be applied only to calcite carbonatites, thus leaving unexplained the large number of dolomite carbonatites and those of either type, which are not accompanied by alkaline silicate rocks. The assumed bimodality of alkaline-rock carbonatite complexes is considered to be fallacious and no actual geological or petrographic evidence for immiscibility processes is evident in these complexes. Several examples of alkaline rock carbonatite complexes for which immiscibility has been proposed are evaluated critically and shown to fail in attempts to establish them as exemplifying immiscibility. We conclude that no actual geological or experimental data exist to establish liquid immiscibility being involved in the genesis of calcite or dolomite carbonatite-forming magmas.

The diffusive exchange of dissolved material between fluid flowing in a fracture and the enclosing wallrocks (rock matrix diffusion) has been proposed as a mechanism by which radionuclides derived from a radioactive waste repository may be removed from groundwater and incorporated into the geosphere. To test the effectiveness of diffusive exchange in igneous and metamorphic rocks, we have carried out an investigation of veins formed at low temperatures (<100°C), comparing the oxygen isotopic composition of vein calcite with that of secondary calcite in the wallrocks. Two examples of veins from the Borrowdale Volcanic Group, Cumbria, and one from the Mountsorrel Granodiorite, Leicestershire, UK, have remarkably similar vein calcite compositions, ca. +20‰(SMOW) or greater, substantially heavier than the probable compositions of the host rocks, and these vein calcite compositions are inferred to reflect the infiltrating fluid and the temperature of vein formation. Calcites from the wallrocks are similar to those in veins, with little evidence for exchange with the wallrocks. The results support existing models for this type of vein which suggest low-temperature growth from formation brines originally linked to Permian or Triassic evaporites. The results are consistent with flow through fractures being attenuated through a damage zone adjacent to the fracture and provide no evidence of diffusional exchange with pore waters from wallrocks.

In many locations around the world, shell radiocarbon dates underpin archaeological research. The dating of shell brings the chronological relationship between the sample and target event (e.g., hunting and food preparation) into congruence, while shells are valuable geochemical proxies for understanding past climate dynamics and environments. However, this information can be lost as the shell, composites of biopolymers and carbonate minerals (mostly calcite and or aragonite), undergo diagenetic alteration. While studies into Pleistocene-age carbonates are common in the radiocarbon literature, there has been little research into the impact of alteration on Holocene-age shells used to interpret recent societal developments. The limits of our understanding of these diagenetic changes became evident when dating Placuna placenta (naturally calcitic) and Tegillarca granosa (naturally aragonitic) shells from the site of Thach Lac in Vietnam. These shells returned ages significantly younger than associated charcoal and terrestrial bone at the site, but standard tests for secondary recrystallization (XRD and staining techniques) did not indicate any alteration. Further investigation revealed that cryptic recrystallization (i.e., of the same crystal structure) had occurred in both the calcite and aragonite shells. This finding suggests recrystallization may have an undetected impact on some shell radiocarbon dates.

The production of pottery in the traditional manner using local raw materials can provide insights into the provenance of ancient artefacts. This study uses mineralogical analysis to evaluate the raw clays and tempers used for pottery production in Zlakusa (western Serbia). Particle-size distribution, plasticity, X-ray fluorescence spectroscopy, X-ray powder diffraction, scanning electron microscopy/energy-dispersive X-ray spectrometry and differential thermal analysis techniques were applied. The mineral phases identified in the raw clay sample are kaolinite/halloysite, mica/illite, smectite, quartz, paragonite, feldspar, calcite and hematite. The clay body sample is a mixture of raw clay and crushed calcite in a ~50:50 ratio, which was confirmed using various techniques. We have also considered and investigated the technological potential of the sampled materials, taking into consideration their actual and potential applications. It was confirmed that the clay body may be used in the manufacture of bricks and pottery, but its industrial application is limited by the paste recipe.

Electron paramagnetic resonance (EPR) spectroscopy is a well-established method of dating based on trapped charges, applied to various crystalline materials, including carbonates, bones, and teeth. It provides a detailed insight into the structure of radiation defects—paramagnetic centers generated by irradiation, without the need of a painstaking sample preparation, often challenging in other methods. Using EPR we studied the effect of γ radiation on lime mortars and plasters from ancient settlement Hippos in Israel, in order to analyze the process of defect generation. Analysis of the complex spectra revealed the presence of radiation-induced species, including CO2–, NO32– and organic radical. Using an artificial UV source, we generated relatively strong signals of paramagnetic centers, analogous to those created by γ irradiation, reaching their maximum intensity after 5–6 hr of UV exposure. Our results confirm the previous reports that radiation defects can also be generated, instead of bleached, in calcite by UV radiation, which is crucial for identifying the issues related to light exposition, affecting the accuracy of age determinations in trapped-charge dating methods.

Radiocarbon (14C) dating of anthropogenic carbonates (CaCO3) such as ash, lime plaster and lime mortar, has proven a difficult task due to the occurrence of a number of contaminants embedded within the CaCO3 pyrogenic binder. These include 14C-free geologic components and/or secondary phases bearing an unknown amount of 14C, and thus the alteration of the original pyrogenic isotopic signature of the material results in major age offsets when carbon recovery is performed through acid hydrolysis. Here we present a characterization/quantification approach to anthropogenic carbonates that includes Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, thin section petrography, thermogravimetric analysis and scanning electron microscopy coupled with high-resolution cathodoluminescence, with which we identified the pyrogenic CaCO3 fraction in an aerial lime plaster and two hydraulic mortars. The preserved pyrogenic component was then isolated by density separation and its purity checked again using FTIR. Carbon was recovered through thermal decomposition in vacuum. The resulting 14C age matches the expected age of the lime plaster, whereas hydraulic mortars are slightly offset due to the carbonation of calcium hydroxide lumps. This approach highlights the importance of a dedicated characterization strategy prior to dating and may be applied to aerial lime plasters to obtain accurate ages.

The mineralogical characteristics of authigenic palygorskite occurring with chlorite and illite in Miocene sediments in Linxia basin were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). The XRD results suggest that the mineral composition of the sediments includes mainly quartz, chlorite, illite, calcite, plagioclase, orthoclase, minor palygorskite and small amounts of gypsum and ankerite. Two kinds of palygorskite were observed in the sediments, relatively straight fibrous particles found in matted, felted masses associated with platy chlorite and silky aggregates found in the void spaces. The former probably replaces chlorite grains, growing from the edges or the fissures of chlorite particles. Chlorite grains exhibit bay-shaped or rounded edges, with ambiguous felted boundaries between chlorite particles, indicative of an intensive dissolution process and the growth of palygorskite at the expense of chlorite. Palygorskite is also observed as inclusions within calcite, sprouting from or coating calcite surfaces, suggesting that palygorskite crystallized from solution. The textural relations of palygorskite and the occurrence of ankerite and the characteristically Fe-bearing palygorskite in the sediments suggest the destruction and hydrolysis of chlorite. The ankerite seems to be preferentially present in the void spaces, closely associated with chlorite and illite; fibrous palygorskite crystallizes at the edges of these clay mineral particles and the platy clay mineral particles are gradually replaced by fibrous palygorskite crystals, suggesting that alteration of chlorite to palygorskite involves an interaction with water during the diagenetic process.

The influence of grinding on colour and particle-size properties of talc and smectite from a white bentonite were studied and compared with a fine-grained calcite from a chalk. Grinding decreased the grain size of all three minerals. The crystallite size and structure of smectite was not affected but the crystallite size of talc decreased. The Si–O–Mg and Mg–O bonds of talc were disrupted and cation exchange capacity increased with increasing grinding. Delamination of talc crystallites was observed in the initial stages of grinding, whereas with more intense treatment, amorphous material was formed. Comminution improved the colour properties of all three minerals, namely brightness, L* (lightness) and ΔE*ab (deviation from perfect white diffuser). Grinding time exerts greater influence on the reflectance from calcite surfaces than from clay minerals. This difference is attributed to continuous formation of progressively smaller diffuse reflection units forming a smoother calcite surface. Decrease of grain size does not form considerably smaller diffuse reflection units in clay minerals unless delamination takes place. With prolonged grinding, amorphization forms additional diffuse reflection units and a smoother surface due to comminution.