Description: The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Description: The assessment of diagenetic overprint on microstructural and geochemical data gained from fossil archives is of fundamental importance for understanding palaeoenvironments. The correct reconstruction of past environmental dynamics is only possible when pristine skeletons are unequivocally distinguished from altered skeletal elements. Our previous studies show (i) that replacement of biogenic carbonate by inorganic calcite occurs via an interface-coupled dissolution–reprecipitation mechanism. (ii) A comprehensive understanding of alteration of the biogenic skeleton is only given when structural changes are assessed on both, the micrometre as well as on the nanometre scale. In the present contribution we investigate experimental hydrothermal alteration of six different modern biogenic carbonate materials to (i) assess their potential for withstanding diagenetic overprint and to (ii) find characteristics for the preservation of their microstructure in the fossil record. Experiments were performed at 175°C with a 100 mM NaCl + 10 mM MgCl2 alteration solution and lasted for up to 35 days. For each type of microstructure we (i) examine the evolution of biogenic carbonate replacement by inorganic calcite, (ii) highlight different stages of inorganic carbonate formation, (iii) explore microstructural changes at different degrees of alteration, and (iv) perform a statistical evaluation of microstructural data to highlight changes in crystallite size between the pristine and the altered skeletons. We find that alteration from biogenic aragonite to inorganic calcite proceeds along pathways where the fluid enters the material. It is fastest in hard tissues with an existing primary porosity and a biopolymer fabric within the skeleton that consists of a network of fibrils. The slowest alteration kinetics occurs when biogenic nacreous aragonite is replaced by inorganic calcite, irrespective of the mode of assembly of nacre tablets. For all investigated biogenic carbonates we distinguish the following intermediate stages of alteration: (i) decomposition of biopolymers and the associated formation of secondary porosity, (ii) homoepitactic overgrowth with preservation of the original phase leading to amalgamation of neighbouring mineral units (i.e. recrystallization by grain growth eliminating grain boundaries), (iii) deletion of the original microstructure, however, at first, under retention of the original mineralogical phase, and (iv) replacement of both, the pristine microstructure and original phase with the newly formed abiogenic product. At the alteration front we find between newly formed calcite and reworked biogenic aragonite the formation of metastable Mg-rich carbonates with a calcite-type structure and compositions ranging from dolomitic to about 80mol % magnesite. This high-Mg calcite seam shifts with the alteration front when the latter is displaced within the unaltered biogenic aragonite. For all investigated biocarbonate hard tissues we observe the destruction of the microstructure first, and, in a second step, the replacement of the original with the newly formed phase.

Description: In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 − δ88/86Srfluid = −0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = −0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7–8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Description: The Pagassitikos Gulf in Greece is a semi-enclosed bay with a maximum depth of 102 m. According to the present-day bathymetric configuration and the sea level during the latest Pleistocene, the gulf would have been isolated from the open sea, forming a palaeolake since ~32 cal. ka b.p. Sediment core B-4 was recovered from the deepest sector of the gulf and revealed evidence of a totally different depositional environment in the lowest part of the core: this contained light grey-coloured sediments, contrasting strongly with overlying olive grey muds. Multi-proxy analyses showed the predominance of carbonate minerals (aragonite, dolomite and calcite) and gypsum in the lowest part of the core. Carbonate mineral deposition can be attributed to autochthonous precipitation that took place in a saline palaeolake with high evaporation rates during the last glacial–early deglacial period; the lowest core sample to be AMS 14C dated provided an age of 19.53 cal. ka b.p. The palaeolake was presumably reconnected to the open sea at ~13.2 cal. ka b.p. during the last sea-level rise, marking the commencement of marine sedimentation characterised by the predominance of terrigenous aluminosilicates and fairly constant depositional conditions lasting up to the present day.

Description: Magnesium calcites were synthesized from aqueous solutions supersaturated with respect to calcite at 25, 40, 60, and 80 °C in gas tight batch reactors for up to 35 days. Any amorphous material still present in the precipitates was removed using a partial dissolution treatment. Resulting purified Mg-calcite had Mg contents ranging from 6 to 32 mol% MgCO3. An isotopic steady-state was attained between the fluid and the precipitated solids within two weeks at 25 °C. δ18O values derived from the experiments at steady-state, depend on both temperature and the Mg content of the calcite in accord with: 1000lnαMg-calcite–H2O=18,030/T−32.42+(6×108/T3–5.47×106/T2+16,780/T−17.21)×CMg where αMg-calcite–H2O represents the calcite–water oxygen isotope fractionation factor, T refers to the temperature in °K and CMg denotes the mole percent of MgCO3 in the calcite. These results indicate that the addition of 5 mol% MgCO3 into the calcite increases 1000lnαMg-calcite–H2O by 0.88 as compared to that of pure calcite at 25 °C. This difference could lead to a 4.2 °C decrease in estimated formation temperature estimates. These results demonstrate that the accurate interpretation of oxygen isotope fractionation in magnesium calcites requires explicit provision for the effect of magnesium on oxygen isotope fractionation factors. Highlights ► The effect of Mg on calcite–aqueous fluid oxygen isotope fractionation was investigated. ► Mg incorporation is increasing the calcite–aqueous fluid oxygen isotope fractionation. ► This effect is reduced at higher temperatures. ► Obtained results are important for paleo-temperature estimation. Gadget timed out while loading

Description: Due to their thermodynamically stable low-Mg calcite mineralogy, the shells of brachiopods are often counted among the most reliable archives of the physicochemical conditions that occurred during the Phanerozoic in marine waters. Consequently, traditional and non-traditional isotope and elemental proxy data from brachiopod valves have been analyzed in numerous studies and results obtained have been placed in context with ancient seawater properties. This paper tests the sensitivity of brachiopod shell magnesium isotope (δ26Mg) data to diagenetic alteration. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data to naturally altered, ancient brachiopod shells. The degree of alteration of individual shells is assessed by a combination of fluorescence and cathodoluminescence microscopy. The absence of luminescence might indicate both well-preserved shell material, but also the secondary enrichment of quenching elements such as iron along diagenetic pathways. Complementary oxygen isotope data provide insight into the question of open versus closed system behavior of brachiopod shells. Brachiopod shell magnesium isotope values respond to differential fluid temperature, chemistry, and experiment durations. The patterns observed are complicated by the interplay of kinetic and thermodynamic patterns and the presence of variable amounts of water soluble and water insoluble organic matter within these biominerals. Generally, the range in bulk δ26Mg from experimentally altered (1.52‰) and that of bulk samples from ancient, diagenetically altered brachiopod valves (1.53‰) exceed the geochemical variability of δ26Mgbrachiopod bulk values of most recent specimens (1.26‰) in the lower and upper range. More 26Mg enriched (0.8‰) and more 26Mg depleted (0.7‰) values, respectively, are found in altered shells in comparison to unaltered ones. The data shown here are considered significant for those aiming to reconstruct palaeoenvironmental parameters based on brachiopod archives. Consequently, we propose tentative guidelines for magnesium isotope research applied to ancient carbonates.