Secondary carbonate precipitates on the surface of clasts have rarely been reported from Antarctica. Here, we infer the origin, age and palaeo-environmental significance of the calcite crusts in the Untersee Oasis, East Antarctica. The distribution of calcite crusts, which are up to 1 mm thick, is limited to locations with residual snow patches, and they have some of the highest δ18O (up to +17.4‰ Vienna Standard Mean Ocean Water (VSMOW)) and δ13C (up to +14.6‰ Vienna Pee Dee Belemnite (VPDB)) compositions of any carbonate deposits in terrestrial polar environments. Their δ18O and δ13C values are substantially enriched with respect to the isotopic values expected from equilibrium precipitation from the δ18O and δ13CDIC (DIC = dissolved inorganic carbon) of snow meltwater. The formation of the calcite crusts is ascribed to the evaporation of residual snow meltwater and the low relative humidity and strong winds, favouring a kinetic isotope effect. The 14C age distribution of the calcite crusts (1550 cal yr bp to modern) provides a minimum age for ice retreat and drainage of the palaeo-lake in Aurkjosen Cirque. However, in this polar desert environment in which surface melting is limited, the calcite crusts require sufficient snow accumulation and air temperatures warm enough to generate meltwater, and their age distribution corresponds to the late Holocene warm-wet climate period.

The reactions between montmorillonite and carbonates and hydroxides of Na, K and Li were studied at 550°C as a function of salt content and time. The reactions were found to be rapid with a half-time of 20–30 minutes. Good agreement was obtained between theoretical and experimental stoichiometric values for the clay-carbonate reaction. The 001 and 02,11 reflections of the products of the clay-salt reactions diminished in intensity and/or disappeared at and above the stoichiometric concentrations of the reactants.

Continuous wave and pulsed electron paramagnetic resonance spectroscopies combined with thermal and chemical methods were used to identify and characterize V(TV), Fe(III), Mn(II) and Cr(III) in a multimineral system that consists of vermiculite and impurities of carbonates. All of these transition metals were structure-bound in mineral phases. The V(IV) was located in octahedral layers of the vermiculite and became oxidized to V(V) during the transformation of the host mineral to enstatite at about 800 °C. The Fe(III) was associated with the vermiculite as well as the carbonate impurities. The Fe(III) identified in the vermiculite was transferred into the enstatite structure during the thermal conversion. An indirect proof of Fe(III) and Cr(III) in the impurities was found in the heated samples in which these cations occurred in Ca and/or Mg oxides that were formed by transformation of the carbonates. The Mn(II) in the untreated samples was associated with the impurities and was also detected in oxides formed from the samples heated at 600 °C.

The depositional history of the Bonneville Salt Flats, a perennial saline pan in Utah's Bonneville basin, has poor temporal constraints, and the climatic and geomorphic conditions that led to saline pan formation there are poorly understood. We explore the late Pleistocene to Holocene depositional record of Bonneville Salt Flats cores. Our data challenge the assumption that the saline pan formed from the desiccation of Lake Bonneville, the largest late Pleistocene lake in the Great Basin, which covered this area from 30 to 13 cal ka BP. We test two hypotheses: whether climatic transitions from (1) wet to arid or (2) arid to wet led to saline pan deposition. We describe the depositional record with radiocarbon dating, sedimentological structures, mineralogy, diatom, ostracode, and portable X-ray fluorescence spectrometer measurements. Gypsum and carbonate strontium isotope ratio measurements reflect changes in water sources. Three shallow saline lake to desiccation cycles occurred from >45 and >28 cal ka BP. Deflation removed Lake Bonneville sediments between 13 and 8.3 cal ka BP. Gypsum deposition spanned 8.3 to 5.4 cal ka BP, while the oldest halite interval formed from 5.4 to 3.5 cal ka BP during a wetter period. These findings offer valuable insights for sedimentologists, archaeologists, geomorphologists, and land managers.

Clays are used widely as facial masks to remove excess sebum, an oily substance released onto the skin. Smectite, illite, kaolinite, and in some cases, chlorite, are the dominant phyllosilicates in most commonly used clay facial masks. To date, the adsorption of human sebum has been proved only on smectite clays; in the present study the adsorption of two organic compounds found in human sebum by illitic, kaolinitic, and chloritic phyllosilicates was investigated. Illitic clays are often used in cosmetic clay masks, but usually contain some fine-grained non-clay minerals. The presence of carbonate, for example, can cause skin irritation because of its alkaline nature, and iron oxides and hydroxides reduce the adsorption properties of clays. The influence of the removal of these compounds on the adsorption properties of illitic clays was also investigated. The amounts of both compounds adsorbed were established by UV-VIS spectrophotometry. All samples were characterized by mineralogical composition, particlesize distribution, specific surface area, and cation exchange capacity (CEC). Oleic acid and squalene were adsorbed on all clay samples, but illitic and chloritic phyllosilicates showed the greatest adsorption capacity. After purification, the sizes of the particles decreased and the CEC values increased. Nevertheless, the dissolution of carbonates essentially had no influence on the adsorption properties, whereas the removal of iron oxides and hydroxides increased significantly the amounts adsorbed of both oleic acid and squalene.

Reliable radiocarbon (14C) ages of foraminifera are a prerequisite to generate robust high-resolution age-depth models or to obtain precise understanding of past carbon cycle dynamics. With the advance of small-scale 14C measurements, instrumental precision and levels of contamination (extraneous carbon introduced during sample pretreatment or analysis) became increasingly important to consider. To reduce the effect of carbon contamination, an attempt can be made to remove it by leaching the surface with weak acids. Alternatively, mathematical corrections (e.g., subtraction) based on processing blanks can be applied. We report on 14C analyses of monospecific foraminifera samples compared between different blank corrections (correction against 14C-free CO2, IAEA-C1 and foraminifera) and sample treatments (i) to examine whether chemical pretreatment and mathematical blank subtraction are comparable, and (ii) to determine limitations hindering reliable 14C dating with ever smaller sample sizes. The data show that chemical pretreatment of foraminifera corrected against IAEA-C1 does remove surface contamination and that the same effect can be achieved for untreated samples that were mathematically corrected for blank values determined from sample size-matched 14C-free foraminifera. Leaching only has a beneficial effect on 14C data for older samples, where the isotopic difference between untreated and chemically pretreated samples exceeds the analytical precision.

Understanding the distribution and geometry of faults and fractures is critical for predicting both subsurface permeability architecture and the integrity of geological fluid barriers, particularly in rocks with low primary porosity and permeability. While fracture patterns in relatively competent, weathering-resistant (therefore often well-exposed) rocks are generally well studied in outcrop, the role of mechanically weak layers in defining fracture patterns is frequently overlooked or under-represented. Here we show that rock composition, specifically clay and silicate minerals versus carbonate content, exerts a strong control on fault and fracture propagation and bed-containment within a mechanically layered, Cretaceous carbonate sequence at Canyon Lake Gorge, Texas. We find that relatively incompetent, clay-rich layers limit fault and fracture propagation, and cause bed-containment of fractures in more competent beds. In our results, no clear relationships exist between mechanical layer thickness and fracture abundance. These results are important for understanding the relative importance of composition versus bed thickness on fracture abundance in the subsurface, and for predicting fracture-controlled fluid flow pathways, seals and fracture connectivity across beds with variable compositions, thicknesses and competences.

In this work, we address the difficulty of reliably identifying traces of life on Mars. Several independent lines of evidence are required to build a compelling body of proof. In particular, we underline the importance of correctly interpreting the geological and mineralogical context of the sites to be explored for the presence of biosignatures. We use as examples to illustrate this, ALH84001 (where knowledge of the geological context was very limited) and other terrestrial deposits, for which this could be properly established. We also discuss promising locations and formations to be explored by ongoing and future rover missions, including Oxia Planum, which, dated at 4.0 Ga, is the most ancient Mars location targeted for investigation yet.

Four unconformity-bound sequences can be identified in the Purana successions in southern India, of which the third sequence (Sequence III) has the widest distribution. Sequence III contains deep-water carbonate units with consistent sedimentological characteristics across the subcontinent. The current extent of field relationships and existing ages has not allowed the correlation and chronology of these carbonates to be established conclusively. Palaeomagnetism may help resolve this essential question for the Purana sedimentation. Here, we report new palaeomagnetic results (HIG+/– pole: 21.7° N, 81.1° E, radius of cone of 95% confidence A95 = 15.9°) from Sequence III carbonates in the Kaladgi (Badami Group) and Bhima (Bhima Group) basins. The HIG+/– magnetization, revealed after the removal of secondary magnetizations that include a present-day field and an Ediacaran–Cambrian overprint, is interpreted to be primary based on its dissimilarity to known younger magnetizations, the presence of distinctly different magnetic components in sites and a positive reversal test. Our HIG+/– pole differs from the c. 1.4 Ga pole and various c. 1.1 Ga and younger poles. Instead, it overlaps with the Harohalli dyke pole that was long considered to be c. 823 Ma in age, but has recently been suggested to be much older with an age of c. 1192 Ma. We therefore consider the uppermost carbonate beds of Badami and Bhima groups to have been deposited during late Mesoproterozoic times. A critical evaluation of parameters from which an earlier Neoproterozoic age for these carbonates was established indicates that the available 40Ar/39Ar, Rb–Sr and U–Pb ages in the Kaladgi and Bhima basins could reflect the timing of post-depositional alteration events.

Laser ablation (LA) accelerator mass spectrometry (AMS) is a novel method for rapid online radiocarbon (14C) analysis of carbonates. The quasi-continuous 14C profiles obtained with this technique demand a customized data evaluation protocol to relate the acquired 14C data to the analyzed sample. We take into account the mixing effects due to the minimal counting (integration) time of the AMS, the finite width of the laser beam and the gas washout of the ablation volume. Thereby we mathematically describe our LA setup with a system function that acts on the produced CO/CO2 (COX) from the sample resulting in a mixing of the 14C profiles obtained by AMS analysis. Furthermore, we analyze the long-term target memory effect in the gas ion source and establish a routine for correction. The correction routine is tested with a stalagmite comprising a growth stop that is analyzed at different scanning velocities indicating that only the slow scanning velocity can provide the necessary resolution to determine the width of the growth stop of 365 μm.

Late to post-Variscan sedimentary basins of Sardinia were influenced during Pennsylvanian to Permian times by two main tectono-sedimentary cycles: a Pennsylvanian to Cisuralian cycle represented mainly by dark limnic deposits, overlain by a Guadalupian to a possibly Lopingian cycle, mostly characterized by red-bed deposits. Lacustrine waterbodies developed in some sedimentary basins that were filled with siliciclastic to frequently early silicified carbonate deposits, depending on the climate and environmental conditions, landscape morphology and tectonic regime. The limnic successions of the lower tectono-sedimentary cycle were deposited in permanent, tens of metres deep lakes in deep, narrow tectonic strike-slip basins under a temperate to warm-humid climate. They started as lakes with terrigenous sedimentary input and developed minor carbonate deposits mainly at the end of their story. Conversely, the red-bed successions of the upper cycle were deposited in ephemeral, shallow playa lakes related to wider basins in an extensive alluvial plain under a hot and arid climate. Here, the siliciclastic sediments are intercalated with thin carbonate beds that are typical of a high evaporation rate. The evolution of the lake type could be related not only to a major climatic shift, but also to the changing morphotectonic conditions of the Variscan chain influencing the local microclimate. Comparisons with coeval successions in the Provence Basin, the Massif Central Aumance basin (France) and the Saar–Nahe Basin (Germany) show both similarities and differences between the basins.

Lead white is a man-made white pigment commonly used in works of art. In this study, the possibility of radiocarbon dating lead white pigments alone and in oil paints was explored using well-dated lead white pigments and paints. Resulting 14C ages on lead white pigments produced following the traditional stack process, where carbonate groups results from the incorporation of CO2 originating from fermentation, matched the production years, while radiocarbon dating of lead white made using other industrial processes indicate that 14C depleted CO2 was used in their production. The method was applied to two case studies, where lead carbonate samples were dated in two oil paintings, one Baroque and one from the 20th century. We hereby show that the lead white pigment can be dated by 14C and used as proxy for the time of creation of an artwork. Additionally, a two-step method was developed to allow 14C analysis of both the lead white pigment and oil binder from the same sample. A single lead white paint sample can yield two distinct radiocarbon ages, one from the carbonate and one from the natural organic binder. This study thus proposes new strategies for 14C dating of artworks.

Green rusts, GRs, can act as both sorbents and reductants towards selected pollutants. Organo-GRs are expected to combine these properties with a high affinity for hydrophobic substances. A novel organo-GR, GRLAS, was synthesized by incorporating a mixture of linear alkylbenzenesulphonates (LAS) into the interlayer space of synthetic sulphate green rust, GRSO4 . Mössbauer analysis of GRLAS indicates that the structure of the organo-GR is very similar to that of the initial GRSO4 with regard to the FeII/FeIII ratio and local coordination of Fe atoms. X-ray diffraction demonstrates that the GRLAS formed was well ordered, although a mixture of surfactant was used for intercalation. The basal spacings of the GRLAS and the kinetics of the ion-exchange process were dependent on the initial surfactant loading; basal spacings of ~2.85 nm were obtained at LAS solution concentrations >10 mM. The ratio LASadsorbed/SO42–desorbed significantly exceeded the stoichiometric ratio of 2 during the initial part of the ion-exchange process (t = 5 h). However, this ratio was reached progressively with time. GRSO4 preferentially sorbed LAS homologues with long alkyl chains over short ones. Carbon tetrachloride was successfully adsorbed into GRLAS. The adsorption isotherm was linear with a distribution coefficient, Kd, of 505±19 litre kg–1.

Diagenetic palaeotemperatures determined from aqueous fluid inclusions can be affected by re-equilibration during burial heating. Calculations based on the observed behaviour of inclusions in fluorite under external confining pressure allows prediction of the temperatures and depths of burial necessary to initiate re-equilibration of aqueous inclusions in the common size range 40 to 4 µm. Heating of 20° to 60°C over the initial trapping temperature may cause errors of 10° to 20°C in the homogenization temperature. This suggests re-equilibration may cause aqueous inclusions in carbonates to yield a poor record of their low-temperature history, but a useful record of the maximum temperature experienced by the host rock. Previous work suggests inclusions containing petroleum fluids will be less susceptible to re-equilibration.

Cathodoluminescence emission spectra and luminescence excitation spectra of Mn2+ in calcites, dolomites, magnesites, a manganocalcite and a rhodochrosite have been measured at both room temperature and 77 K. Ligand-field parameters have been calculated from the excitation spectra which reflect the size of the metal cation site in which the Mn2+ ion resides. The technique of luminescence excitation spectra has enabled the absorption profile of Mn2+ in Mg and Ca sites in dolomite to be separately determined. The variation of the distribution of Mn2+ between Mg and Ca sites in dolomites is demonstrated and discussed in terms of a simple model. It is concluded that the distribution of Mn2+ in dolomites may well provide information about its conditions of formation and/or subsequent alteration.

Crystallographic studies of micro-inclusions in diamond coat, carried out by analytical electron microscopic techniques, show that structures possessing rhombohedral symmetry form a significant fraction of the population of well-crystaUised particles. They are, however, less frequent than apatite or biotite, which were identified earlier by the same investigative methods. Thin-foil specimens of diamond coat were prepared by mechanical fine-polishing, and subsequently ion-beam milling, sawn and polished plates of coated diamonds oriented parallel to (100) or (110). The majority of crystalline inclusions analysed were ≤0.2 p,m in diameter. Data obtained on 15 individual inclusions, including composition analysis by energy-dispersive X-ray spectroscopy, are reported and discussed. The a-axis of the hexagonal unit cell, and the c/a ratio, were determined for all specimens, and are believed to be accurate to ≈1% in most cases. In 12 out of 15 specimens, the cations with Z ≥ 11 identified comprised substantially only Mg, Fe and Ca. Values of a in these specimens ranged from 4.81 to 4.92 Å; and for three of them the space group R, corresponding to the dolomite structure, was positively identified. These crystals are classed as ankerites. Representative Mg:Fe:Ca ratios in the ankerites are 28 : 18 : 54, with cell dimensions a = 4.87 Å, c/a = 3.37. The ankerites contained small amounts of Ba, typically 1-3%, and smaller amounts of Sr, typically 0.2-2%. Three out of the 15 specimens contained >10% Ba. In two of these, Ba and Ca concentrations were roughly equal, and in one of the two, which had cell parameters a = 5.11 Å, c/a = 3.50, the space group symmetry Rc, corresponding to the calcite structure, was verified.