What do we really know about early diagenesis of non-marine carbonates?

Non-marine carbonate rocks including cave, spring, stream, calcrete and lacustrine- palustrine sediments, are susceptible to early diagenetic processes. These can profoundly alter the carbonate fabric and affect paleoclimatic proxies. This review integrates recent insights into diagenesis of non-marine carbonates and in particular the variety of early diagenetic processes, and presents a conceptual framework to address them. With ability to study at smaller and smaller scales, down to nanometers, one can now observe diagenesis taking place the moment initial precipitates have formed, and continuing thereafter. Diagenesis may affect whole rocks, but it typically starts in nano- and micro-environments. The potential for diagenetic alteration depends on the reactivity of the initial precipitate, commonly being metastable phases like vaterite, Ca-oxalates, hydrous Mg‐carbonates and aragonite with regard to the ambient fluid. Furthermore, organic compounds commonly play a crucial role in hosting these early transformations. Processes like neomorphism (inversion and recrystallization), cementation and replacement generally result in an overall coarsening of the fabric and homogenization of the wide range of complex, primary microtextures. If early diagenetic modifications are completed in a short time span compared to the (annual to millennial) time scale of interest, then recorded paleoenvironmental signals and trends could still acceptably reflect original, depositional conditions. However, even compact, non-marine carbonate deposits may behave locally and temporarily as open systems to crystal- fluid exchange and overprinting of one or more geochemical proxies is not unexpected. Looking to the future, relatively few studies have examined the behaviour of promising geochemical records, such as clumped isotope thermometry and (non- conventional) stable isotopes, in well-constrained diagenetic settings. Ongoing and future in-vitro and in-situ experimental approaches will help to investigate and detangle sequences of intermediate, diagenetic products, processes and controls, and to quantify rates of early diagenesis, bridging a gap between nanoscale, molecular lab studies and the fossil field rock record of non-marine carbonates

Comparative study of the Pleistocene Cakmak quarry (Denizli Basin, Turkey) and modern Mammoth Hot Springs deposits (Yellowstone National Park, USA)

This study compares and contrasts the travertine depositional facies of two of the largest sites of travertine formation, located in very different geological contexts, i.e. the modern Mammoth Hot Spring (MHS) system in the active volcanic complex of Yellowstone National Park (USA) and the Pleistocene Cakmak quarry, a well-exposed example of the Ballık travertines in the extensional Denizli Basin (Turkey). New, 2D to 3D facies maps of both travertine systems, combined with microscopy, assist in proposing an integrated spring depositional model, based on the existing MHS facies model, understanding general controls on meter to kilometer scale travertine deposit architecture and its preservation, and provide quantitative estimates of facies spatial coverage and slope using GIS. The comparison resulted in the distinction of eight facies, grouped in five downstream facies zones from Vent to Distal Slope. Notwithstanding the different geological context of both travertine systems, observations show that several of the facies are strikingly comparable (draping Apron and Channel Facies, top-slope Pond Facies, crystalline Proximal Slope Facies and Distal Slope Facies), whereas other facies do not have a precise, exposed equivalent (Vent Facies, pavement Apron and Channel Facies, extended Pond facies and phyto Proximal Slope Facies). Combining observations of active springs at MHS with the Cakmak vertical travertine quarry exposures demonstrates that lateral and vertical facies transitions are a sensitive record of changes in the spring dynamics (flow intensity and paths) that become well-preserved in the geological record, and can be recognized as prograding, aggrading, retrograding trends or erosive surfaces, traceable over tens to hundreds of meters. Quantification of facies specific coverage at MHS shows that Proximal and Distal Slope Facies deposits cover as much as ∼90% of the total mapped surface area. In addition, only ∼7% of the surface is found to be marked by a waterfilm related to an active flowing spring. Slope statistics reveal that strong slope breaks can often be related to transgressive Apron and Channel Facies belts and that variable, but steep slopes (up to 40°) are dominated by Proximal Slope Facies, in agreement with the Cakmak exposures. Integrating travertine facies and architecture of deposits formed in distinct geological contexts can improve the prediction of general spring facies distributions and controls in other, modern and ancient, subsurface travertine systems

The effect of a mixture of Lactobacillus strains on silage quality and nutritive value of grass harvested at four growth stages and ensiled for two periods

The effect of adding an inoculant containing Lactobacillus buchneri, L. plantarum and L. casei to wilted perennial ryegrass, harvested at four growth stages and ensiled for either 60 or 150 d on silage fermentation quality, chemical composition, rumen degradability of neutral detergent fibre (NDF) and organic matter (OM) and in vitro OM digestibility (OMd) was studied. Compared to the control silage, more sugars were fermented to lactic and acetic acid with the inoculant, resulting in a lower pH, less dry matter losses and protein degradation and a better aerobic stability. The effects of the additive on fermentation quality were more pronounced after 150 than after 60 d of ensiling, because the quality of the control silage was worse after the long ensiling period. The treatment lowered NDF content of grass harvested at the first two growth stages by degrading cell walls to complex sugars, but had no effect on NDF degradability of the silage. The inoculant had no effect on rumen OM degradability nor on OMd after the short ensiling period, but increased the rumen OM degradability for the first two growth stages and OMd for all growth stages after the long ensiling period

An analytical algorithm of porosity–permeability for porous and fractured media: extension to reactive transport conditions and fitting via flow-through experiments within limestone and dolomite

Accurate prediction of permeability evolution is essential for forecasting the long-term performance and lifetime of hydrothermal reservoirs, an important goal in the geothermal, ore, and petroleum industries. Erol et al. (Transp Porous Media 120(2):327–358, 2017. https://doi.org/10.1007/s11242-017-0923-z) introduced a general (non-empirical) analytical Kozeny–Carman type equation for predicting matrix and fracture permeability during single-phase, non-reactive flow. Here we incorporate the equation into an algorithm for addressing the influence on porous and fractured media permeability of the transient reactive processes of mineral dissolution and precipitation. Analytical algorithm predictions are identical to permeability values measured during fluid circulation through limestone and dolomite core samples from the Campine Basin deep geothermal system in Belgium. Benchmarking used identical values for initial hydraulic aperture dimension and porosity, measured during fluid circulation based on nondestructive micro-CT imaging. Analytical algorithm predictions of reactive surface area and fracture porosity are similar to results based on the TOUGHREACT reactive transport code. TOUGHREACT implements several well- established power-law models for predicting permeability, notably Civan (AIChE J 47(2):1167–1197, 2001. https://doi.org/10.1002/aic.690470206) and Verma and Pruess (J Geophys Res Solid Earth 93:1159–1173, 1988. https://doi.org/10.1029/jb093ib02p01159). However, these models rely on specification of empirical exponents, which are not straightforward to measure. Our results suggest that a more general, computationally inexpensive analytical method can lead to accurate permeability calculation

Vascular Responses following Light Therapy: A Pilot Study with Healthy Volunteers

(1) Background: Studies have reported the effectiveness of light therapy in various medical conditions. Our pilot study aimed to assess the effect of Maharishi light therapy (MLT) on physiological parameters, such as the heart rate (HR), HR variability (HRV), blood pressure (BP), BP variability (BPV), and the retinal microvasculature of healthy participants; (2) Methodology: Thirty (14 males and 16 females) healthy, non-smoking participants between 23 and 71 years old (46 ± 18 years) were included in this randomized crossover study. Each participant was tested with a placebo (using LED light) and gem lights, 24 h apart. Hemodynamic parameters were recorded during the session, and 24 h heart rate and BP levels were assessed via mobile devices. Retinal vascular responses were captured with fundus images and the subsequent analysis of retinal vessel widths. A linear model, using repeated measures ANOVA, was used to compare the responses across the sexes and to assess the effect of the MLT; (3) Results: Changes in the central retinal artery equivalent (CRAE) (p < 0.001) and central retinal vein equivalent (CRVE) (p = 0.002) parameters were observed. CRAE and CRVE decreased under MLT and increased under the placebo condition from before to after. However, the baseline values of the participants already differed significantly before the application of any therapy, and the variation in the retinal vessel diameters was already large in the baseline measurements. This suggests that the observed effect results may only reflect naturally occurring fluctuations in the microcirculation and not the effect of MLT. Furthermore, no significant effects were observed in any other investigated parameters; (4) Conclusion: Our study with healthy participants finds significant changes in retinal parameters, but the biological variation in the baseline measurements was large to begin with. This suggests that the observed effect results only reflect naturally occurring fluctuations in the microcirculation and not the effect of MLT. However, in the future, larger studies in which MLT is applied for longer periods and/or in patients with different diseases could discover the physiological impacts of this type of therapy.publishedVersio

Pleistocene aragonite crust diagenesis mimics microbialite fabrics (Danakil Depression, Ethiopia)

Fibrous aragonite crusts occur in two consecutive Pleistocene successions in the Danakil Depression (Afar, Ethiopia). Lateral transitions between pristine and altered fibrous aragonite crusts document changes in texture associated with diagenesis. Crusts formed as essentially abiotic seafloor precipitates at the transition from marine to evaporitic conditions. Diagenesis started with the dissolution of aragonite fans at the interface between single fans in non-laminated crusts and along lamination planes in isopachous, irregular, or crudely laminated crusts. Incomplete dissolution resulted in the development of secondary porosity within a matrix of undissolved aragonite fibers. Subsequently, the porosity was filled with calcite that systematically encased remaining aragonite crystals. This was followed by the dissolution of remnant aragonite fibers, producing a network of elongated inter- and intracrystalline pores that were eventually filled with low-Mg calcite. The stepwise substitution of fibrous aragonite by low-Mg calcite resulted in sparry, sparry-cloudy, sparry-micritic (including clotted micrite), and peloidal textures, which obscure the fibrous nature of the original deposits. Stable C- and O-isotope compositions suggest that early diagenesis was driven by meteoric and evaporative fluids. These observations unequivocally demonstrate destructive diagenesis, resulting in secondary textures, which mimic micritic and grumous (peloidal and clotted) textures associated with sparry microfabrics. This suggests that these textures, classically interpreted as primary microbial precipitates and used as evidence of biogenicity in ancient microbialites, might be diagenetic products in some cases, even though at some stage, microbial processes and/or degradation of organic matter could have been involved in the diagenetic process

Multiscale approach to (micro)porosity quantification in continental spring carbonate facies: Case study from the Cakmak quarry (Denizli, Turkey)

Carbonate spring deposits gained renewed interest as potential contributors to subsurface reservoirs and as continental archives of environmental changes. In contrast to their fabrics, petrophysical characteristics – and especially the importance of microporosity (< 1µm) – are less understood. This study presents the combination of advanced petrophysical and imaging techniques to investigate the pore network characteristics of three, common and widespread spring carbonate facies, as exposed in the Pleistocene Cakmak quarry (Denizli, Turkey): the extended Pond, the dipping crystalline Proximal Slope Facies and the draping Apron and Channel Facies deposits formed by encrustation of biological substrate. Integrating mercury injection capillary pressure, bulk and diffusion Nuclear Magnetic Resonance (NMR), NMR profiling and Brunauer–Emmett–Teller (BET) measurements with microscopy and micro-computer tomography (µ-CT), shows that NMR T2 distributions systematically display a single group of micro-sized pore bodies, making up between 6 and 33% of the pore space (average NMR T2 cut-off value: 62 ms). Micropore bodies are systematically located within cloudy crystal cores of granular and dendritic crystal textures in all facies. The investigated properties therefore do not reveal differences in micropore size or shape with respect to more or less biology-associated facies. The pore network of the travertine facies is distinctive in terms of (i) the percentage of microporosity, (ii) the connectivity of micropores with meso- to macropores, and (ii) the degree of heterogeneity at micro- and macroscale. Results show that an approach involving different NMR experiments provided the most complete view on the 3-D pore network especially when microporosity and connectivity are of interest

Multiscale approach to (micro)porosity quantification in continental spring carbonate facies: Case study from the Cakmak quarry (Denizli, Turkey)

Carbonate spring deposits gained renewed interest as potential contributors to subsurface reservoirs and as continental archives of environmental changes. In contrast to their fabrics, petrophysical characteristics – and especially the importance of microporosity (< 1µm) – are less understood. This study presents the combination of advanced petrophysical and imaging techniques to investigate the pore network characteristics of three, common and widespread spring carbonate facies, as exposed in the Pleistocene Cakmak quarry (Denizli, Turkey): the extended Pond, the dipping crystalline Proximal Slope Facies and the draping Apron and Channel Facies deposits formed by encrustation of biological substrate. Integrating mercury injection capillary pressure, bulk and diffusion Nuclear Magnetic Resonance (NMR), NMR profiling and Brunauer–Emmett–Teller (BET) measurements with microscopy and micro-computer tomography (µ-CT), shows that NMR T2 distributions systematically display a single group of micro-sized pore bodies, making up between 6 and 33% of the pore space (average NMR T2 cut-off value: 62 ms). Micropore bodies are systematically located within cloudy crystal cores of granular and dendritic crystal textures in all facies. The investigated properties therefore do not reveal differences in micropore size or shape with respect to more or less biology-associated facies. The pore network of the travertine facies is distinctive in terms of (i) the percentage of microporosity, (ii) the connectivity of micropores with meso- to macropores, and (ii) the degree of heterogeneity at micro- and macroscale. Results show that an approach involving different NMR experiments provided the most complete view on the 3-D pore network especially when microporosity and connectivity are of interest

Assessing the impact of diagenesis on foraminiferal geochemistry from a low latitude, shallow-water drift deposit

Due to their large heat and moisture storage capabilities, the tropics are fundamental in modulating both regional and global climate. Furthermore, their thermal response during past extreme warming periods, such as super interglacials, is not fully resolved. In this regard, we present high-resolution (analytical) foraminiferal geochemical (δ18O and Mg/Ca) records for the last 1800 kyr from the shallow (487 m) Inner Sea drift deposits of the Maldives archipelago in the equatorial Indian Ocean. Considering the diagenetic susceptibility of these proxies, in carbonate-rich environments, we assess the integrity of a suite of commonly used planktonic and benthic foraminifera geochemical datasets (Globigerinoides ruber (white), Globigerinita glutinata (with bulla), Pulleniatina obliquiloculata (with cortex) and Cibicides mabahethi) and their use for future paleoceanographic reconstructions. Using a combination of spot Secondary Ion Mass Spectrometer, Electron Probe Micro-Analyzer and Scanning Electron Microscope image data, it is evident that authigenic overgrowths are present on both the external and internal test (shell) surfaces, yet the degree down-core as well as the associated bias is shown to be variable across the investigated species and proxies. Given the elevated authigenic overgrowth Mg/Ca (∼12–22 mmol/mol) and δ18O values (closer to the benthic isotopic compositions) the whole-test planktonic G. ruber (w) geochemical records are notably impacted beyond ∼627.4 ka (24.7 mcd). Yet, considering the setting (i.e. bottom water location) for overgrowth formation, the benthic foraminifera δ18O record is markedly less impacted with only minor diagenetic bias beyond ∼790.0 ka (28.7 mcd). Even though only the top of the G. ruber (w) and C. mabahethi records (whole-test data) would be suitable for paleo-reconstructions of absolute values (i.e. sea surface temperature, salinity, seawater δ18O), the long-term cycles, while dampened, appear to be preserved. Furthermore, planktonic species with thicker-tests (i.e. P. obliquiloculata (w/c)) might be better suited, in comparison to thinner-test counter-parts (i.e. G. glutinata (w/b), G. ruber (w)), for traditional whole- test geochemical studies in shallow, carbonate-rich environments. A thicker test equates to a smaller overall bias from the authigenic overgrowth. Overall, if the diagenetic impact is constrained, as done in this study, these types of diagenetically altered geochemical records can still significantly contribute to studies relating to past tropical seawater temperatures, latitudinal scale ocean current shifts and South Asian Monsoon dynamics