Temperature Dependence Of Fraction Research Articles

Experimental constraints on Mg isotope fractionation during the aragonite–calcite transition and implications for seawater δ26Mg reconstruction

The linkage between the variation of the seawater Mg budget and the long-term carbon cycle can be elucidated by seawater Mg isotope composition (δ26Mg). However, obtaining primary seawater δ26Mg signatures from marine archives is challenging due to the widespread alteration of diagenesis. Aragonite, a common primary marine carbonate, can effectively record seawater δ26Mg but is prone to alteration and transformation into calcite during early diagenesis. Therefore, a comprehensive understanding of Mg isotope behavior during the aragonite–calcite transition is essential to enhance the applicability of aragonite δ26Mg. In this study, we investigate the variation of aragonite δ26Mg during diagenesis with a limited supply of Mg by conducting a series of well-controlled aragonite–calcite transition experiments in a closed system. The experimental conditions encompass temperatures of 60 and 90 °C, the presence of Ca and Na in the solution, varying Na concentrations, as well as the presence of calcite seed. Results demonstrate that the significant decrease of bulk carbonate δ26Mg is accompanied by a substantial amount of Mg released into the solution during the aragonite–calcite transition, and the amount of released Mg is controlled by fluid chemistry via altering Mg partitioning in calcite. Furthermore, Mg isotope fractionation during calcite precipitation is influenced by temperature, ionic strength, and the presence of calcite seed, while kinetics played a negligible role in our experiments. Combined with previous experiments, the temperature-dependent Mg isotope fractionation during calcite precipitation in unseeded experiments is Δ26Mgcal-sol = (−0.13 ± 0.06) × 106/T2 – (0.47 ± 0.68). This fractionation is systematically higher than that of seeded experiments by 0.3–0.6 ‰ from 15 to 90 °C and can mainly be attributed to differences in surface free energy between homogeneous and heterogeneous calcite nucleation. These findings offer fundamental understandings of the Mg isotope behavior during the aragonite–calcite transformation, providing useful insights for interpreting the variation of δ26Mg in experimental and natural carbonates and facilitating ancient seawater δ26Mg reconstruction.

Aquatic moss δ18O as a proxy for seasonally resolved lake water δ18O, northwest Greenland

Reconstructing past climate seasonality is fundamental to understanding the nature of past climate changes. This is especially true in the Arctic, where climate is intensely seasonal and proxies that can distinguish climate conditions of multiple seasons in a single year are relatively rare. We propose that submerged aquatic mosses, which are abundant subfossils in some Arctic lake sediments and have distinctive seasonal growth morphologies, can be used to estimate past lake water oxygen isotope composition (δ18Olw) across multiple seasons. Aquatic mosses are abundant, well preserved, and grow continuously in Arctic lakes whenever light is available, with some species displaying unique seasonal morphologies influenced by water temperature. Although Greenland paleorecords suggest that aquatic moss oxygen isotope values (δ18Oom) reflect the δ18O values of lake water, no modern calibration between δ18Oom and δ18Olw exists in Greenland. We present a modern δ18Oom vs. δ18Olw calibration using multiple moss species or morphotypes from eight lakes and ponds near Pituffik (Thule), northwest Greenland. We find strong linear relationships (r2 = 0.76-0.85) between the δ18Oom and δ18Olw values of multiple species or morphotypes across the range of relatively low δ18Olw values at Pituffik, and our results indicate isotopic fractionations are similar to those found previously at lower latitudes. To assess the potential of mosses as archives of seasonal δ18Olw values, we analyzed δ18Oom in season-specific segments of moss strands, with seasons identified based upon growth morphology. Moss inferred lake water δ18O values (δ18Olwom) are higher in autumn than spring or summer, likely due to increasing contributions of 18O enriched precipitation and the cumulative effects of lake water evaporation throughout the ice-free season. For moss subsampled throughout summer, δ18Olwom values generally increased through the season in parallel with observed δ18Olw values. Potential temperature dependent fractionation effects during biosynthesis, however, remain unconstrained and should be further addressed with future research. Overall, these findings suggest that aquatic mosses from lake sediments could be used to directly resolve climate seasonality of the past.

Exploiting intermediate wetting on superhydrophobic surfaces for efficient icing prevention

HypothesisSuperhydrophobic surfaces can effectively prevent the freezing of supercooled droplets in technological systems. Droplets on superhydrophobic surfaces commonly not only wet the top asperities (Cassie State), but also partially penetrate into microstructure due to surface properties, environment, and droplet impact occurring in real-world applications. Implications on ice nucleation can be expected and are little explored. It remains elusive how anti-icing surfaces can be designed to exploit intermediate wetting phenomena. ExperimentsWe utilized engineered micro-/nanostructures, specifically micropillars, to modulate the wetting fraction in the microstructure. The behavior of intermediate wetting with supercooling and resulting implications on ice nucleation delay when potential nucleation sites are formed in the microcavities were investigated using experimental, theoretical, and simulation components. FindingsThe temperature-dependent wetting fraction in the microstructure increased at supercooled temperatures, partly activated by condensation in the microcavities. At −10/−20 °C, a critical wetting fraction led to maximum ice nucleation delays, with experimental results consistent with theoretical predictions. This critical wetting fraction minimized the effective contact area solid-to-liquid along the partially wetted microstructure. The study establishes physical relations between ice nucleation delays, geometrical surface parameters and wettability properties in the intermediate wetting regime, providing guidance for the design of ice resistant microstructured surfaces.

Temperature Dependence of the Number of Defect-Structures in Poly(vinylidene fluoride).

Poly(vinylidene fluoride) (PVDF) is predominantly characterized by alternating CH2 and CF2 units in a polymer backbone, originating from the head-to-tail addition of monomers or regular propagation. Due, to a small extent, to inverse monomer addition, so-called defect structures occur which influence the macroscopic properties of PVDF significantly. The amount of defect structures in the material is determined by the polymerization conditions. Here, the temperature dependence of the fraction of defect structures in PVDF obtained from polymerizations between 45 and 90 °C is reported. We utilized 19F-NMR spectroscopy to determine the fraction of defect structures as a function of temperature. To derive kinetic data, the polymerization of VDF is considered a quasi-copolymerization described by the Terminal Model involving four different propagation reactions. Based on the experimentally determined temperature-dependent fractions of defect structures, the known overall propagation rate coefficient, and taking into account the self-healing behavior of the macroradical, the Arrhenius parameters of the individual propagation rate coefficients were determined using the Monte Carlo methods.

Lithium isotope fractionation during submarine hydrothermal alteration processes

River water and submarine hydrothermal fluids are the two primary sources of lithium (Li) input to the ocean. However, compared to well-documented weathering processes, the behavior of Li isotopes during hydrothermal alteration processes remains obscure. In this research, we investigated the Li isotopic compositions (δ7Li) of hydrothermally altered sediments from two IODP drilling cores (C0013 and C0014) in the Iheya North Knoll of the middle Okinawa Trough. The sediments, primarily altered from volcanic clasts, exhibit a pristine δ7Li value (5.2 ± 0.7 ‰) similar to that of MORB (3.7 ± 1 ‰). Intense hydrothermal activity led to the complete conversion of primary feldspars into phyllosilicates, predominantly Mg-chlorite, at site C0013 and in the middle and deep parts of C0014. The altered samples showed a depletion of 7Li (ranging in δ7Li from −10.0 ‰ to 4.2 ‰) compared to background sediment, indicating the preferential incorporation of 6Li during the formation of secondary minerals. Furthermore, both drilling sites exhibited increasing trends in δ7Li values with depth, with the deepest samples approaching the pristine δ7Li values of unaltered volcanic rock. These trends were attributed to the significant thermal gradients present at both sites. The temperature-dependent fractionation factor of Li isotopes allowed us to estimate the alteration temperature, which yielded temperature values consistent with those obtained using the δ18O geothermometer. This finding underscores the potential of Li isotopes as a novel geothermometer tool, although further calibration work is required. Based on our research findings, we developed a dissolution-precipitation model (based on mass balance) that establishes a relationship between the δ7Li values of altered solids and hydrothermal fluids, with the aim of elucidating the relatively limited variation observed in global submarine hydrothermal fluids (ranging from 1.6 ‰ to 11.0 ‰, with an averaged value of 5.9 ± 3.0 ‰, mean ± SD). This model quantitatively depicted the strong restriction of the Li concentration in hydrothermal fluids on their isotopic compositions, as high concentrations of Li in the fluids necessitate a substantial release of Li from the solid phase, causing the fluids' δ7Li values to approach that of the bedrock. Additionally, limited fractionation factors at high temperatures further constrain the variations in the fluids' δ7Li values. Model predictions also suggest that the reported δ7Li values of hydrothermal fluids have encompassed the potential δ7Li variation, providing supporting evidence for the assumption that δ7Li values of submarine hydrothermal fluids have exhibited insignificant variations throughout Earth's history.

Climate related phase transitions with moving boundaries by virtue of mushy zone investigation in Al–Cu: Experiment and phase‐field modeling

Studying Arctic ice formation stays in the focus of research groups over the past decades in the context of ice cover changes, thermal budget and climate agenda in general. Nevertheless, the phenomenon's underlying mechanisms are still not completely understood and described. The main reason for the lack in understanding is the limited experimental access to the field data when it comes to the processes that occur below the ice floe. Thus, there is a need to build competent analogies between the natural (ocean water–ice) and laboratory (here: binary alloy) conditions of the experiment as a step of data preparation for the verification of the mathematical model. In the current paper, the existing qualitative models describing the process of melting and crystallization were expanded and the experimental method was developed copying the layering of the natural ocean water–ice mixture. The experimental set‐up for studying the solidification within the intermediate zone was designed for Al–Cu alloys being the system with appropriate solidus line for creating a sufficient concentration gradient and by that temperature dependent phase fraction under isothermal conditions. The gained experimental data were used for validating a binary phase‐field model for solidification considering moving boundaries. The model includes the description of the free energy of both phases and their respective diffusion coefficients. It allows modeling a binary system at a mesoscopic spatial level by including the concentration‐driven phase transition and resolidification in the two‐phase region. The novel results will help the quantitative understanding of solidification phenomena and are highly‐evaluated from interdisciplinary point of view, including glaciology and geosciences, being ultimately significant for the understanding the global climate change landscape.

Fractionation of iron and titanium isotopes by ilmenite and the isotopic compositions of lunar magma ocean cumulates

Basaltic volcanism on the Moon produced low- and high-Ti mare basalt suites that are also distinct with respect to their iron, titanium, and magnesium isotopic compositions. Here, the equilibrium fractionation of Fe and Ti isotopes between ilmenite and melt was experimentally investigated in order to evaluate the role of ilmenite in generating the isotopic compositional variability among the lunar mare basalts. Ilmenite crystallization experiments were conducted using two bulk compositions: an ilmenite-saturated basaltic andesite and an ilmenite-saturated Apollo 14 black glass, and the Fe and Ti isotopic compositions of the experimental ilmenites and glass (quenched melt) were analyzed using solution MC-ICPMS after hand-picking. Additionally, Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements on synthetic ilmenite were conducted and compared to previous NRIXS measurements on synthetic lunar glasses in order to derive temperature-dependent equilibrium ilmenite-melt Fe isotopic fractionations. Experimentally determined ilmenite-melt fractionations were then incorporated into a lunar magma ocean crystallization model that tracks the major element and isotopic compositional evolution of lunar magma ocean cumulates and residual liquid. There is good agreement between the Fe equilibrium isotopic fractionation measured by NRIXS and the laboratory equilibration experiments, and we find that the isotopic fractionation is sensitive to ilmenite compositional differences (0 vs. 10% Fe3+). Further, the light Ti isotopic composition of ilmenite relative to the melt (Δ49Ti=ilmenite-melt−0.09±0.03‰ at 1100∘C) is consistent with the higher coordination of Ti in ilmenite relative to melts and results of previous studies. The modeled Ti isotopic compositions for lunar magma ocean cumulates display Ti isotopic variability sufficient to explain the low- and high-Ti mare basalt sources. However, the difference in Fe isotopic composition between the low- and high-Ti mare basalts cannot be attributed solely to ilmenite fractionation. Instead, Fe isotopic fractionation by additional products of lunar magma ocean crystallization, such as clinopyroxene, is required to generate the inferred Fe and Mg isotopic variability in the lunar mantle. Alternatively, the Fe and Mg isotopic compositions of the lunar mare basalts may indicate Fe-Mg interdiffusion has occurred in the Ti-rich component of the mare basalt source regions via reaction between ilmenite cumulates and the olivine- and pyroxene-rich lunar mantle.

13C-depleted methane pyrolyzed from contaminated Gale Crater sediment cores, Mars

This work re-interprets published SAM-EGA (Sample Analysis at Mars-Evolved Gas Analysis) geochemical data for twenty-four sediment cores sampled by the Curiosity rover. The samples were pyrolyzed at 35 °C/min in the range ∼ 100-850 °C. The amount of methane generated from carbonaceous matter in the cores and its stable carbon isotope ratio (δ13C-CH4) in selected cuts within the full temperature range were determined by tunable laser spectrometry (TLS cut). Chemometric analysis of five independent variables for eighteen of the cores identifies four genetic families in which three endmembers explain most data variance. One endmember is contamination by silylating agent (MTBSTFA) introduced unintentionally from wet-chemistry cups during flight and/or after landing of the rover. Five subsamples from the Cumberland (CB) core show a linear relationship between δ13C-CH4 and mean pyrolysis temperature (R2 = 0.77) within TLS cuts in the range 99-786 °C, which conforms with temperature-dependent kinetic theory. Based on dates of pyrolysis for the five CB samples, BSW (bisylylated water, a marker of MTBSTFA contamination) peaked on sol 281 and progressively decreased to sol 382. Linear regression of δ13C-CH4 versus BSW concentration (R2 = 0.98) yields δ13C-CH4 ∼ -70‰ for carbonaceous matter in uncontaminated CB core. Higher BSW yields systematically more negative δ13C-CH4 to the most negative value of −133‰ for CB1, which equates to an apparent fractionation of ∼98‰ from bulk MTBSTFA (δ13C = −35‰) to CB1 methane. Previous workers suggested that δ13C-CH4 from MTBSTFA could not be more than ∼5‰ depleted compared to bulk MTBSTFA. However, their SAM-like laboratory pyrolysis experiments for analogs of MTBSTFA yield δ13C-CH4 values that correspond only to gas trapped within the analyzed pyrolysis temperature cut (455-755 °C). Lower temperature TLS cuts for CB1 and CB2 (220-349 °C and 99-349 °C) trapped more 13C-depleted methane as reflected in their anomalous δ13C-CH4 of −133 and − 115‰, respectively. In addition, pyrolysis of MTBFTSA byproducts, residual solvent, and internal standards with Martian minerals, perchlorates, and sorption or desorption on clays may contribute to more negative δ13C-CH4 than expected from laboratory experiments that lack these components. It is not possible to determine bulk δ13C or δ13C-CH4 for the remaining two carbonaceous endmembers because of the effects of three factors: (1) Chemometric results by alternating least squares regression (ALS) define the relative contributions of endmembers based on five independent variables, not just δ13C-CH4. (2) Samples from distinct locations and stratigraphic ages are subject to variations in δ13C of deposited carbonaceous matter. (3) δ13C-CH4 values for samples from different TLS cuts differ due to temperature-dependent kinetic fractionation.

Phase and thermodynamics-informed predictive model for laser beam additive manufacturing of a multi-principal element alloy

The complex solidification cycles experienced by multi-principal element alloys (MPEAs) during laser-based additive manufacturing (LBAM) often lead to structural defects that affect the build quality. The underlying thermal processes and phase transformations are a function of the process parameters employed. With a moving Gaussian heat source to mimic LBAM and leveraging material thermodynamics guidelines from CALculation of PHAse Diagrams (CALPHAD), we estimate the temperature-dependent thermal properties, phase fractions, and melt pool geometry using an experimentally validated computational fluid dynamics model. The results substantiate that the peak temperatures are inversely correlated to the scan speeds, and the melt pool dimensions can assist in the predictive selection of process parameters such as hatch distance and layer thickness. A relatively low cooling rate recorded during the process is ascribed to the preheating of the substrate to ensure printability of the alloy.

Superconducting vortices carrying a temperature-dependent fraction of the flux quantum.

Magnetic field penetrates type-II bulk superconductors by forming quantum vortices that enclose a magnetic flux equal to the magnetic flux quantum. The flux quantum is a universal quantity that depends only on fundamental constants. In this study, we investigated isolated vortices in the hole-overdoped Ba1-xKxFe2As2 (x = 0.77) by using scanning superconducting quantum interference device (SQUID) magnetometry. In many locations, we observed objects that carried only part of a flux quantum, with a magnitude that varied continuously with temperature. We demonstrated mobility and manipulability of these objects and interpreted them as quantum vortices with nonuniversally quantized (fractional) magnetic flux whose magnitude is determined by the temperature-dependent parameters of a multicomponent superconductor.

Effect of Intercritical Annealing on the Properties of Dual Phase Steel via Finite Element Method

Dual phase (DP) steels are rapidly becoming more and more popular for automotive applications. They offer a weight reduction with a combination of energy absorption for crash zones. Rails, reinforcements, back panels, cross members, and pillars can be given as application examples. DP steels microstructure consists of a soft ferrite matrix with hard martensite islands. The hard martensite islands provide strength while the ductile ferrite provides formability. The strength level of DP steel is related to the amount of martensite in the microstructure, and the martensite amount can be arranged via intercritical annealing. In this work, thermodynamic analysis of St52 steel was carried out with Thermo-Calc software. A1 and A3 temperatures were determined by calculating the temperature-dependent phase fractions. Intercritical annealing temperatures were determined according to the calculated critical temperatures (A1 and A3). The intercritical annealing process was modelled by using Simheat NxT software. In this modelling and simulation work, the effect of intercritical annealing temperature on the final microstructure and hardness of DP steel was investigated.

Interactions in Ammonia and Hydrogen Oxidation Examined in a Flow Reactor and a Shock Tube

Ammonia (NH3) is a promising fuel, because it is carbon-free and easier to store and transport than hydrogen (H2). However, an ignition enhancer such as H2 might be needed for technical applications, because of the rather poor ignition properties of NH3. The combustion of pure NH3 and H2 has been explored widely. However, for mixtures of both gases, mostly only global parameters such as ignition delay times or flame speeds were reported. Studies with extensive experimental species profiles are scarce. Therefore, we experimentally investigated the interactions in the oxidation of different NH3/H2 mixtures in the temperature range of 750-1173 K at 0.97 bar in a plug-flow reactor (PFR), as well as in the temperature range of 1615-2358 K with an average pressure of 3.16 bar in a shock tube. In the PFR, temperature-dependent mole fraction profiles of the main species were obtained via electron ionization molecular-beam mass spectrometry (EI-MBMS). Additionally, for the first time, tunable diode laser absorption spectroscopy (TDLAS) with a scanned-wavelength method was adapted to the PFR for the quantification of nitric oxide (NO). In the shock tube, time-resolved NO profiles were also measured by TDLAS using a fixed-wavelength approach. The experimental results both in PFR and shock tube reveal the reactivity enhancement by H2 on ammonia oxidation. The extensive sets of results were compared with predictions by four NH3-related reaction mechanisms. None of the mechanisms can well predict all experimental results, but the Stagni et al. [React. Chem. Eng. 2020, 5, 696-711] and Zhu et al. [Combust. Flame 2022, 246, 115389] mechanisms perform best for the PFR and shock tube conditions, respectively. Exploratory kinetic analysis was conducted to identify the effect of H2 addition on ammonia oxidation and NO formation, as well as sensitive reactions in different temperature regimes. The results presented in this study can provide valuable information for further model development and highlight relevant properties of H2-assisted NH3 combustion.

Data for "Observation of superconducting vortices carrying a temperature-dependent fraction of the flux quantum"

Data for "Observation of superconducting vortices carrying a temperature-dependent fraction of the flux quantum"

Influence of thermochemical sulfate reduction on oxygen isotopic composition of calcite cements in carbonates of the Triassic Feixianguan and Permian Changxing formations in the Sichuan Basin, China

Calcite cement is a common diagenetic mineral in carbonate rocks and plays an important role on rock quality as hydrocarbon reservoirs. Traditionally, oxygen isotopic compositions (δ18O) of the diagenetic calcites tend to decrease with increasing depths due to temperature-dependent isotope fractionation. In this study, the stable isotope compositions of the calcite cements in the Changxing and Feixianguan formations from the Puguang, Yuanba, Jiannan and Fuling carbonate fields in the Sichuan Basin were analyzed. The results show that some calcite cements have δ18O values similar to those of their host carbonates, despite the fact that these calcites formed at elevated temperatures (>∼100°C). Based on petrographic and geochemical analyses, the 18O-enriched calcites commonly occur with solid bitumens and have lower δ13C values compared with host rocks, suggesting thermochemical sulfate reduction (TSR) provided organic carbon for these calcite precipitation. During TSR, thermal oxidation of hydrocarbons generated the light carbon, and simultaneously the reduced sulfate ions provided the oxygen. Comparison of our study with the TSR calcites worldwide, a model for oxygen isotope behavior during TSR was established. Oxygen isotope compositions of TSR-related calcites are a function of isotope compositions and amounts of the initial anhydrite and pore waters. TSR shows two opposing effects on the δ18O values of calcites, depending on the δ18O ratios of the initial anhydrite. The reduction of anhydrite with relatively low δ18O values causes the calcite δ18O lower than theoretical values of calcites directly precipitated from pore waters. The heavy δ18O ratios of calcites formed during TSR are not only attributed to the 18O-enriched pore water resulting from extensive water-rock interaction, but also probably due to the involvement of anhydrite with high δ18O values.

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part I: branched pentanol isomers.

Theoretical investigations on the kinetics of decomposition and isomerization reactions for five types of branched pentanol radicals are carried out in this work. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all reactants, transition states, and products, while the hindrance potentials for the lower frequency modes in all of the species were obtained through a relaxed scan with an increment of 10° at the M06-2X/6-31G level of theory. Single-point energies of all species were determined at the QCISD(T)/cc-pVDZ, TZ level of theories with basis set corrections from MP2/cc-pVDZ, TZ, QZ methods. The RRKM/master equation was solved to calculate the pressure- and temperature-dependent rate coefficients for all channels in the pressure range of 0.01-100 atm over 250-2000 K. Pressure and temperature-dependent branching fractions of key species produced from pentanol radicals show that most of the pentanol radical isomers tend to isomerize to alkoxy radicals via a six-membered-ring or five-membered-ring transition state at low temperatures, producing ketones or aldehydes. At higher temperatures, the β-scission reactions are the main reaction channels for the consumption of pentanol radicals. A weak pressure dependence has been found for all isomerization reactions, and it becomes more and more important as pressure increases. The pressure dependence trends are different for the β-scission reactions of different branched pentanol radicals. In part I, the results for branched pentanol radical isomers are presented in detail, while in part II the results for linear pentanol radical isomers will be discussed.

Narrowing provenance for ancient Greek silver coins using Ag isotopes and Sb contents of potential ores

Variations of 109Ag/107Ag in silver coins and ores are particularly useful in assessing the provenance of silver bullion. Silver isotope variability results from the temperature-dependent thermodynamic fractionation of Ag isotopes among the solutions and minerals participating in ore formation. They differ from lead isotopic variations which result from the decay of uranium and thorium and reflect the geochemical properties and the tectonic age of the possible ore sources. A remarkable property of Ag isotopes is the very narrow range of isotopic variations in silver bullion used for coinage (±1×10−4) with respect to the range of ores (±1×10−3). To test the practical usefulness of the technique, we analyzed the Ag isotopic abundances of 29 ore samples from ancient mining districts in the Aegean with major and minor Ag-bearing mineralizations, and of 34 ancient Greek coins minted from the sixth to late fourth centuries BC. We distinguished two groups among the coins: a dominant population (93% of the samples) with 109Ag/107Ag consistent with literature data (ε109Ag = −1 to +1) and an isotopically lighter population (ε109Ag = −2 to −1) which we show originated from Ag-bearing mineralizations in Lavrion (Attica). We further found that sulfur (also analyzed in this study) and silver isotope compositions in Aegean ores do not correlate, a finding that we confirmed on a selection of Iberian galena samples. This shows that the genetic ore type (whether hypo, meso, or epithermal) and silver productivity are not related. Finally, we undertook chemical analysis of the Aegean ore samples and confirmed that Ag-rich ores are also Sb-rich in both Greece and Iberia.A remarkable outcome of the present Ag isotope studies of galena ores from Iberia and Greece is that silver isotope compositions can exclude, with a high degree of reliability, the majority of mines identified by lead isotope analysis as sources from which coinage silver could plausibly have been extracted and thus significantly narrow down the actual source(s). Silver isotope data on galena ores are thus a useful tool for deciding which Pb isotope data included in ore databases should be included in provenance assessment studies. Contrary to some earlier assessments, subtle silver isotope variations can occasionally help determine ore provenance within a single mining district such as Lavrion.

A modern snapshot of the isotopic composition of lacustrine biogenic carbonates – records of seasonal water temperature variability

Abstract. Carbonate shells and encrustations from lacustrine organisms provide proxy records of past environmental and climatic changes. The carbon isotopic composition (δ13C) of such carbonates depends on the δ13C of dissolved inorganic carbon (DIC). Their oxygen isotopic composition (δ18O) is controlled by the δ18O of the lake water and by water temperature during carbonate precipitation. Lake water δ18O, in turn, reflects the δ18O of atmospheric precipitation in the catchment area, water residence time and mixing, and evaporation. A paleoclimatic interpretation of carbonate isotope records requires a site-specific calibration based on an understanding of these local conditions. For this study, samples of different biogenic carbonate components and water were collected in the littoral zone of Lake Locknesjön, central Sweden (62.99∘ N, 14.85∘ E, 328 ma.s.l.) along a water depth gradient from 1 to 8 m. Carbonate samples of living organisms and subfossil remains in surface sediments were taken from the calcifying alga Chara hispida, from bivalve mollusks of the genus Pisidium, and from adult and juvenile instars of two ostracod species, Candona candida and Candona neglecta. Our results show that neither the isotopic composition of carbonates nor the δ18O of water vary significantly with water depth, indicating a well-mixed epilimnion. The mean δ13C of Chara hispida encrustations is 4 ‰ higher than the other carbonates. This is due to fractionation related to photosynthesis, which preferentially incorporates 12C into the organic matter and increases the δ13C of the encrustations. A small effect of photosynthetic 13C enrichment in DIC is seen in contemporaneously formed valves of juvenile ostracods. The largest differences in the mean carbonate δ18O between species are caused by vital offsets, i.e., the species-specific deviations from the δ18O of inorganic carbonate which would have been precipitated in isotopic equilibrium with the water. After subtraction of these offsets, the remaining differences in the mean carbonate δ18O between species can mainly be attributed to seasonal water temperature changes. The lowest δ18O values are observed in Chara hispida encrustations, which form during the summer months when photosynthesis is most intense. Adult ostracods, which calcify their valves during the cold season, display the highest δ18O values. The seasonal and interannual variability in lake water δ18O is small (∼ 0.5 ‰) due to the long water residence time in the lake. Seasonal changes in the temperature-dependent fractionation are therefore the dominant cause of carbonate δ18O differences between species when vital offsets are corrected. Temperature reconstructions based on paleotemperature equations for equilibrium carbonate precipitation using the mean δ18O of each species and the mean δ18O of lake water are well in agreement with the observed seasonal water temperature range. The high carbonate δ18O variability of samples within a species, on the other hand, leads to a large scatter in the reconstructed temperatures based on individual samples. This implies that care must be taken to obtain a representative sample size for paleotemperature reconstructions.

Density functional theory calculations of nitrogen and oxygen equilibrium isotope fractionations in NO3−–NO2−–H2O aqueous system reveal inverse kinetic isotope effects during nitrite oxidation

Nitrate and nitrite play key roles in the nitrogen cycle on Earth's surface. The isotope fractionation during nitrate reduction on enzymatic level involves multiple steps, including transfer of free NO3− to the activate site on nitrate reductase and NO2− equilibration with ambient water. However, the isotope fractionation factors of 15N and 18O among NO3−, NO2−, and H2O molecules in aqueous phases are poorly constrained. It strongly impedes the understanding of the involved processes and using stable isotopes to quantitatively examine the biogeochemical nitrogen cycle. In this contribution, we employ the density functional theory method with the Urey-Bigeleisen-Goeppert-Mayer model to predict the nitrogen and oxygen equilibrium isotope fractionation factors of NO3−, NO2−, and H2O molecules in gaseous and aqueous phases. Our calculation results show that the solvent effect has a large influence on equilibrium isotope fractionation for oxygen in water (+10.1‰ between liquid and vapor water at 25 °C), which is different to the little solvent effects on both oxygen and nitrogen in nitrate and nitrite. The calculated temperature-dependent equilibrium isotope fractionations between nitrogen of NO3− and NO2−, and oxygen of H2O and NO2− are consistent with previous laboratory experiments. Our results confirm that the oxygen equilibrium isotope fractionations between NO3− and NO2− should be +9.4‰ at 25 °C. Integrating the new results and previously reported kinetic isotope effects of nitrate reduction, we demonstrate inverse kinetic isotope effects for both nitrogen (+15.4‰) and oxygen (+5.2‰) during nitrite oxidation, which falls in the range of previous experiments. The new results enable us to use both nitrogen and oxygen isotopes as a bonded isotope tool to quantitatively assess the nitrogen cycle in low-temperature environments.

Silver isotope fractionation in ore-forming hydrothermal systems

The behavior of silver in hydrothermal ore-forming systems has been the subject of numerous studies. Equilibrium and Rayleigh-type isotope fractionation of silver during transport- and deposition-related processes in silver-bearing hydrothermal ore-forming systems are investigated experimentally and theoretically in this study. The results of open-system evaporation experiments in a simple Ag+–H2O system show that the transfer kinetics of silver from liquid to vapor follows a second-order kinetic reaction model with activation energy (Ea) values of 131.20 ± 14.63 kJ·mol−1 and 145.38 ± 2.93 kJ·mol−1 in neutral and acidic solutions, respectively. No loss of silver from the solution was observed during surface evaporation, and the rate constant, ka, increased exponentially with temperature above 343 K at ambient pressure. During vapor–liquid separation, the vapor is enriched in 107Ag, whereas the liquid is enriched in 109Ag. The silver isotope fractionation follows a Rayleigh-type fractionation model with αvapor-liquid factors of 0.99936–0.99985 at 373 K under neutral and acidic conditions, respectively, whereas the temperature-dependent equilibrium isotope fractionation follows the relationship, 1000lnαvapor-liquid = −0.0039 × 106/T2 – 0.0037 based on density functional theory (DFT) calculations. This explains the relatively narrow interval of δ109Ag values (from −0.3 to +0.4‰) analyzed in Ag-bearing veins from hydrothermal ore-deposits. Based on the bond-strength of Ag to the nearest atoms in minerals, the 109Ag enrichment decreases in the order pyrargyrite, argentite, proustite, stephanite, native silver, iodargyrite, chlorargyrite. The equilibrium silver isotope fractionation between fluid and mineral during ore formation can be considerable depending on the temperature, the nature of the silver-bearing mineral deposited, whether or not there is vapor–liquid phase separation, and whether there is a reduction of oxidized silver (Ag(+1)) to the reduced form Ag(0). Consequently, the source signatures of δ109Ag are altered significantly by transport- and deposition-related processes during ore formation (e.g., boiling, precipitation and reduction). A new silver isotope-geothermometer is proposed based on the equilibrium silver isotope fractionation between argentite and stephanite. This geothermometer, which employs the relationship 1000lnαargentite-stephanite = 0.0128 × 106/T2 + 0.0014, can be used to constrain temperature in silver-bearing hydrothermal systems provided that argentite and stephanite are in equilibrium.

Melting of subducted slab dictates trace element recycling in global arcs.

Arc magma acquires continental crust-like trace element signatures through selective recycling of incompatible elements from the subducted slab. The long-standing model of element recycling through aqueous fluid from altered oceanic crust (AOC) and sediment melt has been challenged by the resurgence of mélange diapir (a mix of AOC, sediment, and serpentinite) and saline aqueous fluid models. Here, we present experimental data for near-solidus sediment melts and a framework for calculating trace element concentrations in subduction fluids from metamorphosed sediment and oceanic crust. We observe that variation of element ratios in global primitive arc basalts is comparable with that of sediment and/or oceanic crustal melt, rather than (saline) aqueous fluid or mélange melt. In particular, the systematic correlation of element ratios in arc basalt corresponds to element fractionation in slab melt with temperature and therefore follows a power function. Our findings suggest that slab melt is primarily responsible for element recycling to the arc.