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Spring systems are efficient and fast precipitating non‐marine carbonate factories, but they are also prone to (early) diagenesis. Evidence of diagenesis in travertines remains controversial as the resulting textures have been considered primary in other deposits and the impact on geochemical/palaeo‐environmental signals is often poorly addressed. This study revisits the Y‐10 core, taken in 1967 at one of the upper terraces of Mammoth Hot Springs in Yellowstone National Park (USA). The travertine depositional facies in the upper 50 m of the core show a general distal to proximal facies trend upwards. To unravel the nature, impact and timing of early diagenesis, fabrics and geochemical signatures are also compared to modern hot spring carbonates. Secondary ion mass spectrometry and detailed microscopy proved powerful in determining the stable isotope signature of different cement generations, thereby detangling the fluid history. Diagenesis starts during spring activity, but these warm waters not only precipitate CaCO3 at the top, they also seem to have circulated through the porous spring fabrics below. It resulted in coarsening and homogenization of the primary textures through neomorphism of aragonite and calcite cementation, often resulting in new intracrystalline microporosity within the calcite crystals. Subsequent circulation of meteoric fluids led to dissolution and cementation, particularly near the top of the core. Careful interpretation of U/Th dates suggests that travertine deposition started at the beginning of the Holocene/end Pleistocene. Calculated depositional (precipitation) rates vary between 2 and 20 mm/year, assuming a constant rate between samples at different depths. Aragonite deposits are completely transformed to calcite below depths of 5–10 m, corresponding to a time span of 4,000 years. Core and petrography observations, together with dating, suggest that travertine strata below marine sandstones in the lower part of the core may relate to fault displacement after the onset of travertine deposition.

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 frommarine 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 amatrix 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 diagenesiswas 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 primarymicrobial 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., Swiss National Science Foundation (SNSF) 200021_163114, SNSF Ambizione 154810

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.

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 (< 1 mu m) - 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 (mu-CT), shows that NMR T-2 distributions systematically display a single group of micro-sized pore bodies, making up between 6 and 33% of the pore space (average NMR T-2 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.

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 ( δ 18 O 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 δ 18 O 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 δ 18 O 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 δ 18 O), 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.

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.

Nowadays most low-field NMR sensors, such as the single-sided Profile NMR-MOUSE®, still suffer from poor sensitivity, either resulting from low magnetic field strengths and correspondingly low NMR frequencies, or lack of sensitivity. Generally, micro-coils can improve sensitivity, but due to their small size, and thus small inductance, they are mainly used for high-field NMR. Their main application field is parallel imaging, where those coils are typically assembled to receive-only coil-arrays and increase the field-of-view. Prominent signal combination techniques such as GRAPPA and SENSE are used to combine the spatially independent NMR signals to images in order to increase acquisition speed. A decisive disadvantage of today's single-sided NMR probes is the limited accessibility for NMR imaging. Although it is possible to use flat gradient coils on top of the NMR-MOUSE® to apply imaging techniques, such images can only be recorded with very long acquisition times, excluding the NMR-MOUSE® for lateral imaging of time-dependent processes. In this study sensitivity improved micro-structured RF coils, optimized for low frequencies, and correspondingly arrays of these coils, were employed to improve sensitivity and gave access to lateral spatial resolution within the sensitive plane at several observation points at the same time. Recently developed three- and four-coil arrays were combined with a Profile NMR-MOUSE® and characterized in terms of coil coupling, noise correlation and signal combination. The three-coil array was used for lateral imaging of moisture transport in travertine rock samples and to study the one-dimensional drying of paint.

© 2016 Elsevier Ltd and INQUA 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. ispartof: Quaternary International vol:437 pages:129-146 status: published

Terra Nova, 23, 56–61, 2011 Abstract Authigenic carbonates at methane seeps provide valuable information on the evolution of seepage dynamics. In this study, we report on an unusual type of 13C-depleted [δ13C: −44.8‰ to −8.3‰V-PDB (Vienna PeeDee Belemnite)] calcite-cemented grapestone concretion composed of small spheroidal nodules

Up to 10 m in length and >1 m in diameter tubular, calcite-cemented sandstone concretions are hosted by the faulted Dikilitash unconsolidated sands and sandstones. These structures document shallow subsurface pathways of Early Eocene methane seepage in the Balkan Mountains foreland (NE Bulgaria). Their exceptional exposure allowed a unique study of the factors governing the morphology and spatial distribution of such fossilized fluid conduits. The large dimensions and subvertical, cylindrical shape of the most common tube type primarily reflects the buoyancy-driven, vertical path of an ascending gas-bearing fluid through permeable, mainly unconsolidated sandy host sediments. Tube morphology was also influenced by local stratigraphic anisotropies and might as well document differences in former seepage conditions. Mapping of >800 tubular concretions showed the NNW–NNE elongation and alignment of tube clusters and massive cemented sandstone structures. This suggests that Paleogene fault systems played a major role in directing the movement of fluids. However, within a single tube cluster, tubes are preferentially aligned, over distances up to 50 m along directions at an angle between 10° and 36° with respect to the inferred NNW–NNE, cluster parallel fault traces. In addition, cylindrical tubes of analogue dimensions are aligned over distances >100 m along N15° to N25°-oriented directions. It is hypothesized that this spatial geometry of tubular concretions reflects the complex geometry of deformations structures in fault damage zones along which fluids were preferentially channelled.

Impressive, several meters high tubular concretions in shallow marine calcareous sands and sandstones represent part of the well-exposed, subsurface plumbing network of an Early Eocene methane seep system in the Balkanides foreland (Pobiti Kamani area, Varna, NE Bulgaria). An integrated approach, including petrography, inorganic geochemistry and lipid biomarker analyses was used to reconstruct the evolution of pore fluids and cementation conditions during tube formation and particularly, the role of methane-related carbonate diagenesis. Host sediment lithification from marine pore waters was perturbed soon after deposition by oxidation of predominantly microbial methane causing pervasive cementation by a 13 C-poor, homogeneous calcite cement ( δ 13 C values as low as − 44.5‰ V-PDB). The importance of microbially mediated anaerobic oxidation of methane (AOM) is confirmed by extremely 13 C-depleted archaeal biomarkers ( δ 13 C values as low as − 123‰ V-PDB). A suite of macrocyclic dialkyl glycerol diethers (MDGD-0 to -2) and sn -3-hydroxyarchaeol comprises a characteristic trait of the Eocene tubular concretions and might represent molecular fossils of so far unknown methane-oxidizing archaea (ANME). Subsurface calcite cementation surrounding the ascending methane plume, resulted from the changing pore water chemistry in response to AOM and could have, on a local scale, been encouraged by the concurrent alteration of detrital feldspar. Fluctuating δ 13 C (up to − 8‰ V-PDB) and δ 18 O (− 0.5 to − 9‰ V-PDB) signatures within a single tubular sandstone concretion are at least partly the consequence of isotopic resetting during late meteoric water circulation.

The Mercator mud volcano, located in the Gulf of Cadiz off the coasts of Spain, Portugal, and Morocco (Figure 1), may provide an accessible field laboratory for studying local active venting and its possible internal and external controls. The recent discovery of the first active deep ocean ‘brown smoker’ chimney in this area can possibly be linked with the disintegration of a gas hydrate layer between the seafloor and a subsurface level that is dependent on pressure and temperature. For more than a decade, the international marine scientific community has deployed considerable efforts in exploring the Gulf of Cadiz. Since the discovery of the Gulf's first mud volcano in 1999, research cruises have steadily unveiled one mud volcano after another [Gardner, 2001; Pinheiro et al., 2003; Somoza et al., 2003]. These mud volcanoes are clustered in several fields on the Portuguese, Spanish, and Moroccan margins (Figure 1). Extensive geophysical evidence of shallow gas and subsurface fluid flow has been reported in the Gulf of Cadiz [Baraza and Ercilla 1996; Pinheiro et al., 2003].

In the last 10 years numerous research and commercial initiatives have been undertaken in Europe to develop abandoned coal mining fields into low-temperature resources. One of the most successful is the Minewater project of the municipality of Heerlen, the Netherlands, where a low-temperature district heating system was launched in operation in October 2008, under the European Interreg IIIB NWE programme and the 6th Framework Program project EC-REMINING-lowex. The Minewater project is now being upgraded from a straight forward pilot system to a full-scale hybrid sustainable energy structure called Minewater 2.0. A totally new concept which becomes an essential part of the Sustainable Energy Structure Plan of Heerlen and has the following landmarks: • Energy exchange instead of energy supply: cluster grids for energy exchange between buildings and the existing mine water grid for energy exchange between cluster grids. • Energy storage and regeneration in mine water reservoirs instead of depletion. • Addition of poly-generation: bio-CHP, solar energy, feed in of waste heat (data centres and industry), cooling towers for peak cold demands. • Enlargement hydraulic and thermal capacity mine water grid through improving well pumps, pressure boosting systems and reuse of the existing mine water return pipe for additional supply and disposal of hot mine water. • Fully automatic and demand-driven supply of hot and cold mine water through usage of pressurized buffer systems at the extraction wells and sophisticated injections valves at the injection wells. • All geographically dispersed mine water installations at buildings, clusters and wells are equipped with sophisticated process control units that communicate with a Central Monitoring System (CMS) through the internet. A very new application in the build environment. The first phase of the Minewater 2.0 project is in operation since June 2013. In November 2013 at the congress we will be able to share the first experiences.