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Geochemical analyses of carbonate minerals yield multiple parameters which can be used to estimate the temperature and water composition at which they formed. Analysis of fluid trapped in minerals is a potentially powerful tool to reconstruct paleotemperatures as well as diagenetic and hydrothermal processes, as these could represent the parent fluid. Internal fluids play important roles during the alteration of carbonate fossils, lowering energetic barriers associated with resetting of clumped isotopes, as well as mediating the transport of elements during diagenesis. Here, we explore the behavior of the ∆47–∆48 “dual‐clumped” isotope thermometer during fluid‐carbonate interaction and demonstrate that it is highly sensitive to the water/carbonate ratio, behaving as a linear system in “rock buffered” alteration, and as a decoupled system in water‐dominated systems due to non‐linear mixing effects in ∆48. Dry heating experiments show that the extrapolated “heated” end‐member is indistinguishable from the predicted ∆47 and ∆48 value expected for the experimental temperature. Furthermore, we evaluate two common laboratory sampling methods for their ability to thermally alter samples. We find that the temperature of the commonly used crushing cells used to vapourize water for fluid inclusion δ18O analyses is insufficient to cause fluid‐carbonate oxygen isotope exchange, demonstrating its suitability for analyses of fluid inclusions in carbonates. We also find that belemnites sampled with a hand‐drill yield significantly warmer paleotemperatures than those sampled with mortar and pestle. We conclude that thermally‐driven internal fluid‐carbonate exchange occurs indistinguishably from isotopic equilibrium, limited by the extent to which internal water and carbonate can react. Plain Language Summary Carbonate minerals contain multiple, independent, chemical and isotopic parameters which can be used to calculate the temperature at which the mineral formed. If these proxies agree with one another, it has been confidently assumed that the temperature is indeed genuine. Here, we investigate three such parameters and show how they record kinetic processes during mineral formation, as well as thermally‐driven processes which may alter a climate record. We find that this method could potentially be used to study the kinetic factors at play during biomineralization, even if the “true” temperature is unknown. We also find that some thermal processes result in all three parameters agreeing with one another. Because thermal alteration poses a potential dilemma for climate researchers, we investigate two common laboratory preparation techniques that involve heating a sample before analysis: drilling and heating sample for fluid inclusion analysis. We find that the heat of a drill is sufficient to facilitate these reactions, and potentially imparts a warm bias onto paleotemperatures, however the apparatus used for analyzing fluid inclusions does not appear to significantly alter the material. We conclude our approach using fluid inclusion analysis and dual‐clumped isotopes has the potential to resolve many ambiguities in interpreting climate records. Key Points We explore the behavior of dual‐clumped and fluid‐inclusion isotope paleothermometers during thermal alteration Different conditions during diagenesis may result in discrepant paleotemperature estimates, which may be used to identify altered records Hand‐drilling belemnites produces sufficient heat to reset paleotemperatures, but the heat during analysis of fluid inclusions does not

One of the five largest mass extinctions of the past 600 million years occurred at the boundary of the Triassic and Jurassic periods, 201.6 million years ago. The loss of marine biodiversity at the time has been linked to extreme greenhouse warming, triggered by the release of carbon dioxide from flood basalt volcanism in the central Atlantic Ocean. In contrast, the biotic turnover in terrestrial ecosystems is not well understood, and cannot be readily reconciled with the effects of massive volcanism. Here we present pollen, spore and geochemical analyses across the Triassic/Jurassic boundary from three drill cores from Germany and Sweden. We show that gymnosperm forests in northwest Europe were transiently replaced by fern and fern-associated vegetation, a pioneer assemblage commonly found in disturbed ecosystems. The Triassic/Jurassic boundary is also marked by an enrichment of polycyclic aromatic hydrocarbons, which, in the absence of charcoal peaks, we interpret as an indication of incomplete combustion of organic matter by ascending flood basalt lava. We conclude that the terrestrial vegetation shift is so severe and wide ranging that it is unlikely to have been triggered by greenhouse warming alone. Instead, we suggest that the release of pollutants such as sulphur dioxide and toxic compounds such as the polycyclic aromatic hydrocarbons may have contributed to the extinction. The extinction at the Triassic/Jurassic boundary is one of the five largest in Earth’s history. Microfossil and organic geochemical analyses link the vegetation turnover in Europe to the release of pollutants and toxic compounds from flood basalt volcanism in the central Atlantic Ocean.

The residual stress state in cold spray coatings, which is typically compressive in nature, can be crucial for the coating integrity at high levels or for thick coatings. As an alternative, the analysis using the curvature measurement was applied in this study. The stress measurement during cold spray deposition was made by using an in situ coating property sensor (ICP sensor), which is relatively widely used in thermal spray and enables a fast comparison of several process parameters. The results were then compared to post-deposition curvature measurements. It could be revealed that the usage of a very slow robot traverse speed can lead to tensile residual stresses in cold-sprayed coatings. This finding was explained by the high local temperature during deposition and the formation of tensile stresses during cooling of the deposited material to the average substrate temperature. The increase in the powder feed rate can increase this effect. Preheating did not influence the final stress state. An analytical model is presented which can at least semi-quantitatively explain the observed findings. As an outcome of the research work, it is now possible to adjust the residual stress state in cold spray coatings from tensile to compressive and vice versa with the opportunity of a zero stress state.

In the cold gas spray process, deposition of particles takes place through intensive plastic deformation upon impact in a solid state at temperatures well below their melting point. The high particle impact velocities and corresponding peening effects can lead to high compressive residual stresses in cold spray coatings. This can be advantageous with regard to mechanical properties as fatigue life and hence, cold spray is an ideal process for repair applications. In this study, INCONEL 718 particles were cold sprayed by using nitrogen as propellant gas. The deposited coatings with different thicknesses were characterized using electron microscopy techniques to study grain refinement and precipitates in the coating. In addition, depth-resolved residual stress measurements have been performed by the incremental hole drilling method. The residual stress depth profiles in the coatings indicate compressive residual stresses of several hundred MPa which are hardly influenced by the coating thickness. In addition, large compressive stress levels are found in surface-near regions of the substrate due to the grit blasting process. Furthermore, a post-heat treatment analysis was performed to investigate its influence on residual stresses and bonding strength. These findings are used to develop a consistent explanation of the dependence of strength values on thickness.

The residual stresses induced by the various process conditions in engineering components can have a significant impact on their structural integrity and performance. It is essential to ensure reliable control of the mechanical properties of structural components during the repair process, as this directly affects their performance and longevity. Cold gas spray, a solid-state deposition technique, involves the high-velocity impact of fine powder particles onto a substrate, resulting in the formation of a dense, metallurgically bonded coating. The aim of this study is to investigate the suitability of cold gas spraying parameters for the repair of large cavities in components made of Inconel 718. Two sets of parameters, approaching the limits of the spraying facility, have been utilized and analyzed using particle diagnostics. Experimental methodologies involve the characterization of residual stress profiles using techniques such as in situ curvature measurement and the incremental hole drilling method after the cold gas spray repair. Additionally, the microstructure and topography of the as-sprayed repair coatings are demonstrated. The results demonstrate the ability of cold gas spray to successfully fill deep repair cavities and adjust the residual stress state of such repair coatings by varying the processing parameters. Lower residual compressive stresses in the layer were achieved by utilizing gas parameters, wherein the particles impact the substrate at an elevated temperature and at a comparatively reduced velocity. Both conditions exhibited coatings with consistent microstructure, good adhesion and uniform topography without major defects. This research demonstrates the potential of cold gas spray as a viable and efficient repair method for large repair geometries, offering a promising avenue for enhancing the reliability and lifespan of critical engineering structures.

Tubular carbonate concretions of up to 1 m in length and perpendicular to bedding, occur abundantly in the Upper Pliensbachian (upper Amaltheus margaritatus Zone, Gibbosus Subzone) in outcrops (Fontaneilles section) in the vicinity of Rivière-sûr-Tarn, southern France. Stable isotope analyses of these concretions show negative δ13C values that decrease from the rim to the center from −18.8‰ to −25.7‰ (V-PDB), but normal marine δ18O values (−1.8‰). Carbon isotope analyses of Late Pliensbachian bulk carbonate (matrix) samples from the Fontaneilles section show clearly decreasing C-isotope values across the A. margaritatus Zone, from +1‰ to −3‰ (V-PDB). Isotope analyses of coeval belemnite rostra do not document such a negative C-isotope trend with values remaining stable around +2‰ (V-PDB). Computer tomographic (CT) scanning of the tubular concretions show multiple canals that are lined or filled entirely with pyrite. Previously, the formation of these concretions with one, two, or more central tubes, has been ascribed to the activity of an enigmatic organism, possibly with annelid or arthropod affinities, known asTisoa siphonalis. Our results suggest tisoan structures are abiogenic. Based on our geochemical analyses and sedimentological observations we suggest that these concretions formed as a combination of the anaerobic oxidation of methane (AOM) and sulfate reduction within the sediment. Fluids rich in methane and/or hydrocarbons likely altered local bulk rock carbon isotope records, but did not affect the global carbon cycle. Interestingly, Tisoa siphonalis has been described from many locations in the Grands Causses Basin in southern France, and from northern France and Luxemburg, always occurring at the same stratigraphic level. Upper Pliensbachian authigenic carbonates thus possibly cover an area of many thousand square kilometers. Greatly reduced sedimentation rates are needed to explain the stabilization of the sulfate-methane transition zone in the sedimentary column in order for the tubular concretions to form. Late Pliensbachian cooling, reducing run-off, and/or the influx of colder water and more vigorous circulation could be responsible for a halt in sedimentation. At the same time (thermogenic) methane may have destabilized during a major phase of Late Pliensbachian sea level fall. As such Tisoa siphonalis is more than a geological curiosity, and its further study could prove pivotal in understanding Early Jurassic paleoenvironmental change.

Most models of osteoporotic bone fractures are performed unilaterally (UL). We investigated healing of tibia osteotomy performed either UL or bilaterally (BL) in ovariectomized rats. Behavior of animals and muscle structure were assessed. Three-month-old female Sprague-Dawley rats were ovariectomized (n = 32). After 10 weeks, half the rats underwent UL osteotomy of tibia metaphysis (right limb) with plate osteosynthesis. The other rats were osteotomized BL. Half of the rats in each group received either standard pain treatment with carprofen (5 mg/kg body weight (BW), 1x/day for 2 days) or carprofen and buprenorphine (5 mg/kg BW, 1x/day and 0.03 mg/kg BW, 2x/day for 5 days) after osteotomy. The UL rats started to load the injured limb from day 27 ± 9; BL rats did this from day 4 ± 4 onward. The UL rats more frequently loaded only one hind limb; BL rats more often loaded both hind limbs. Osteotomy was not bridged in 20% of UL rats and in 4% of BL rats. Callus volume and bone volume fraction were lower in UL group. Weight and fiber size of UL-intact limb muscles were enhanced, compared to the osteotomized limb and those in BL group. Most of the other parameters which assess physiology, activity, body posture, head, or coat were not different. The effect of two pain therapies was not significant on any variable studied. Welfare of the animals was acceptable in all rats. In UL rats, bone healing was delayed. The more advanced healing in BL rats suggested a positive effect of earlier loading. In studies on bone healing, it is advisable to perform BL osteotomy.

Shells of the extremely long-lived bivalve mollusk Arctica islandica (Linnaeus 1767) provide century-long, multi-proxy records of inter-annual environmental variability in middle- to high-latitude marine settings. Reliable interpretation of these climate archives, however, requires exact knowledge of the length and timing of the growing season and which environmental parameters control shell growth rate during the year. Here, intra-annual growth microstructures, δ18O-derived ambient water temperatures, and δ13C from A. islandica shells collected from the southern and central North Sea are studied. Such data were analyzed in conjunction with observational sea-surface temperature and primary productivity data. Arctica islandica produces circadian growth increments in its shell (on average 31.5 μm per day during age four, measured along the outer shell surface), which allow assignment of calendar dates to each shell portion. The growing season of A. islandica in the upper mixed layer of the ocean (here 25 m water depth) is not continuous over an eight-month period as previously suggested. Rather, it is interrupted during spawning between early September and mid-November. In addition, shell production ceases or is strongly retarded due to food scarcity between mid-December and mid-February. Water temperatures derived from oxygen-isotope ratios are in good accord with observed sea-surface temperatures. In specimens at 25 m water depth, abrupt changes in shell δ18O-derived temperature (Tδ18O) were interpreted to represent vertical displacements of the seasonal thermocline. Daily shell growth is controlled by temperature and food availability. Up to 58% of the variation in daily growth rate is explained by these environmental parameters. This study demonstrates that A. islandica can provide seasonal to subseasonal, precisely dated proxies of environmental variables. Such data are of increasing importance for climate models.

Corals are important marine archives for high-resolution reconstructions of low-latitude climate variability in preinstrumental and historical periods. Herein, we present monthly-resolved records of δ18O and Sr/Ca for the 20th century (1917–2007) from a Porites lutea colony from the Maldives (northwestern Indian Ocean). Previous studies of annual mean extension rates of this coral revealed a distinct dependency of coral growth on variations of sea surface temperature (SST) and hydraulic energy, driven by El Niño-Southern Oscillation (ENSO) and southwestern Indian monsoon forcing. This enables the investigation of coral δ18O and Sr/Ca ratios from the Maldives as archives of historical ENSO and Indian monsoon variability. Unlike other locations in the Indian Ocean, correlation of δ18O and SST is weak (r  =  −0.42; p < 0.001), suggesting interferences of SST and seawater δ18O at the location. These interferences probably caused significantly weaker interannual ENSO signatures in δ18O as evident in the extension rates of our coral and in geochemical proxies measured at other sites in the northwestern Indian Ocean. Sr/Ca ratios show bias by nontemperature effects, and were not used to estimate seawater δ18O and salinity. Strong decadal variability (10–14 years) in δ18O, indicative of a Pacific ENSO signal, is not found in instrumental SST, and could be explained by variations in salinity. Interannual and decadal monsoon variability (6–7 yrs and 18–19 yrs), found in the extension rates, was not found in δ18O, suggesting, in agreement with other studies, that geochemical coral proxy records from the northwestern Indian Ocean do not capture temporal variations of the Indian monsoon strength.

During the Middle Miocene, the Earth shifted from a warm state, the Miocene Climatic Optimum (MCO; 16.9–14.7 Ma), to a colder state associated with the formation of extensive and permanent ice sheets on Antarctica. This climatic shift, the Middle Miocene Climatic Transition (MMCT; 14.7–13.8 Ma) strongly affected the composition and structure of major biomes, ocean circulation, and precipitation patterns. Although Middle Miocene climate dynamics are well documented in marine records, our knowledge of terrestrial climate change is not well constrained. Here we present a long-term (23–13 Ma) stable (δ13C, δ18O) and clumped (Δ47) isotope record of soil carbonates from a northern Mediterranean Alpine foreland basin: the Digne–Valensole basin (DVB), France. Δ47-derived soil carbonate formation temperatures indicate a highly dynamic dry season temperature pattern that is consistent with multiple periods of reorganization of atmospheric circulation during the MCO. We propose that changes in atmospheric circulation patterns modified the seasonality of precipitation and, ultimately, the timing of pedogenic carbonate formation. Consequently, Δ47 soil carbonate temperature data record the combined effects of long-term regional temperature and carbonate formation seasonality change. The data are consistent with the existence of a proto-Mediterranean climate already during certain MCO time intervals. Following the MMCT, the stable and clumped isotope record displays pronounced cooling after 13.8 Ma accompanied by a rather large (−5.0 %) decrease in soil water δ18O values. Our northern Mediterranean foreland basin climate record shares strong similarities with time-equivalent records from the terrestrial European mid-latitudes and the global oceans and enhances our understanding of the circum-Alpine Middle Miocene terrestrial climate dynamics.