Reaction Energetics and ¹³C Fractionation of Alanine Transamination in the Aqueous and Gas Phases

The alanine transaminase (ALT) enzyme catalyzes the transfer of an amino group from alanine to α-ketoglutarate to produce pyruvate and glutamate. Isotope fractionation factors (IFFs) for the reaction ⁺H₃NCH(CH₃)COO⁻ + ⁻OOCCH₂CH₂C(O)COO⁻ ↔ CH₃C(O)COO⁻ + ⁻H₃NCH(CH₂CH₂COO⁻)COO⁻ (zwitterionic neutral alanine + doubly deprotonated α-ketoglutarate ↔ pyruvate + zwitterionic glutamate anion) were calculated from the partition functions of explicitly and implicitly solvated molecules at 298 K. Calculations were done for alanine (non-charge separated, zwitterion, deprotonated,), pyruvic acid (neutral, deprotonated), glutamic acid (non-charge separated, zwitterion, deprotonated, doubly deprotonated), and α-ketoglutaric acid (neutral, deprotonated, doubly deprotonated). The computational results, calculated from gas phase and aqueous optimized clusters with explicit H₂O molecules at the MP₂/aug-cc-pVDZ and MP₂/aug-cc-pVDZ/COSMO levels, respectively, predict that substitution of ¹³C at the C2 position of alanine and pyruvic acid and their various forms leads to the C2 position of pyruvic acid/pyruvate being enriched in ¹³C/¹²C ratio by 9 ‰. Simpler approaches that estimate the IFFs based solely on changes in the zero-point energies (ZPEs) are consistent with the higher-level model. ZPE-based IFFs calculated for simple analogues formaldehyde and methylamine (analogous to the C₂ positions of pyruvate and alanine, respectively) predict a ¹³C enrichment in formaldehyde of 7 to 8 ‰ at the MP₂/aug-cc-pVDZ and aug-cc-pVTZ levels. A simple predictive model using canonical functional group frequencies and reduced masses for ¹³C exchange between R₂C=O and R₂CH-NH₂ predicted enrichment in R₂C=O that is too large by a factor of two, but is qualitatively accurate compared with the more sophisticated models. Our models are all in agreement with the expectation that pyruvate and formaldehyde will be preferentially enriched in ¹³C due to the strength of their >C=O bond relative to that of the ≡C-NH₂ in alanine and methylamine. ¹³C/¹²C substitution is also modeled at the methyl and carboxylic acid sites of alanine and pyruvic acid, respectively

The chlorine isotope fingerprint of the lunar magma ocean

The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free (“dry”) Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because ^(37)Cl/^(35)Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, ^(37)Cl/^(35)Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high ^(37)Cl/^(35)Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon’s history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets

Calibration and applications of the dolomite clumped isotope thermometer to high temperatures

Carbonate clumped isotope paleothermometry is based on the temperature-dependent formation of ^(13)C^(18)O^(16)O_2 ^(2-) ion groups within solid carbonate minerals. This thermometer has now been calibrated for various synthetic and natural biogenic and abiogenic minerals (calcite, aragonite and carbonateapatites [e.g., 1, 2]) at temperatures below ~ 50°C. Here we extend the use of the carbonate clumped isotope thermometer to shallow crustal environments by determining the Δ_(47) values of CO_2 extracted from natural and synthetic dolomites grown at know temperatures from 25 to 350ºC. The experimental temperature dependance is not linear in the Δ_(47) vs T^(-2) plot and resembles the predicted theoretical temperature dependence, both in shape and absolute value [3]. These data for synthetic dolomites overlap the previous calibrations for inorganic calcite and some forms of biogenic carbonates between 25 and 50˚C, and are consistent with a single trend that also intersects data for synthetic calcite equilibrated at 1200˚C. These observations suggest that a single temperature dependant relationship reasonably approximates the calibration for both phases. Data from a variety of slowly-cooled (i.e., over geological timescales) natural marbles and rapid (i.e., laboratory timescales) heating experiments provide insights into the kinetics of solid-state ^(13)C-^(18)O bond reordering in carbonates and its closure temperature. More generally, our new calibration and constraints on high-temperature kinetics have implications for the application of this technique to burial and metamorphic processes. These issues will be illustrated through estimates of the thermal history and oxygen isotopic compositions and abundances of pore fluids for several suites of late Neoproterozoic carbonates [e.g., 4]

Comparing autonomous underwater vehicle (AUV) and vessel-based tracking performance for locating acoustically tagged fish

Autonomous underwater vehicles (AUV’s) are increasingly used to collect physical, chemical, and biological information in the marine environment. Recent efforts include merging AUV technology with acoustic telemetry to provide information on the distribution and movements of marine fish. We compared surface vessel and AUV tracking capabilities under rigorous conditions in coastal waters near Juneau, Alaska. Tracking surveys were conducted with a REMUS 100 AUV equipped with an integrated acoustic receiver and hydrophone. The AUV was programmed to navigate along predetermined routes to detect both reference transmitters at 20–500 m depths and tagged fish and crabs in situ. Comparable boat surveys were also conducted. Transmitter depth had a major impact on tracking performance. The AUV was equally effective or better than the boat at detecting reference transmitters in shallow water, and significantly better for transmitters at deeper depths. Similar results were observed for tagged animals. Red king crab, Paralithodes camtschaticus, at moderate depths were recorded by both tracking methods, while only the AUV detected Sablefish, Anoplopoma fimbria, at depths exceeding 500 m. Strong currents and deep depths caused problems with AUV navigation, position estimation, and operational performance, but reflect problems encountered by other AUV applications that will likely diminish with future advances, enhanced methods, and increased use

Distribution of recycled crust within the upper mantle : insights from the oxygen isotope composition of MORB from the Australian-Antarctic Discordance

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 10 (2009): Q12004, doi:10.1029/2009GC002728Geochemical heterogeneity within the mantle has long been recognized through the diversity of trace element and radiogenic isotopic compositions of mantle-derived rocks, yet the specific origin, abundance, and distribution of enriched material within the mantle have been difficult to quantify. In particular, the origin of the distinctive geochemical characteristics of Indian mantle has been debated for decades. We present new laser fluorination oxygen isotope measurements of mid-ocean ridge basalt from the Australian-Antarctic Discordance (AAD), an area where a particularly abrupt transition occurs between Pacific-type mid-ocean ridge basalts (MORB) and Atlantic-type MORB. These data show no distinction in average δ18O between Pacific- and Atlantic-type MORB, indicating that the origin of Indian-type mantle cannot be attributed to the presence of pelagic sediment. The combined radiogenic isotope, δ18O, and trace element characteristics of Indian-type MORB at the AAD are consistent with contamination of the Indian upper mantle by lower crustal material. We also present a compilation of available laser fluorination δ18O data for MORB and use these data to evaluate the nature and percentage of enriched material within the upper mantle globally. Data for each ocean basin fit a normal distribution, with indistinguishable means and standard deviations, implying that the variation in δ18O of MORB reflects a stochastic process that operates similarly across all ocean basins. Monte Carlo simulations show that the mean and standard deviation of the MORB data are robust indicators of the mean and standard deviation of the parent distribution of data. Further, although some skewness in the data cannot be ruled out, Monte Carlo results are most consistent with a normal parent distribution. This similarity in characteristics of the δ18O data between ocean basins, together with correlations of δ18O with radiogenic isotope and trace element characteristics of subsets of the data, suggest that the upper mantle globally contains an average of ∼5–10% recycled crustal material and that the depleted mantle in the absence of this component would have δ18O of ∼5.25‰. The Monte Carlo simulations also suggest that additional oxygen isotope data may be used in the future to test the ability of geodynamical models to predict the physical distribution of enriched domains within the upper mantle

Sims Analysis of Water Abundance and Hydrogen Isotope in Lunar Highland Plagioclase

The detection of indigenous water in mare basaltic glass beads has challenged the view established since the Apollo era of a "dry" Moon. Since this discovery, measurements of water in lunar apatite, olivine-hosted melt inclusions, agglutinates, and nominally anhydrous minerals have confirmed that lunar igneous materials contain water, implying that some parts of lunar mantle may have as much water as Earth's upper mantle. The interpretation of hydrogen (H) isotopes in lunar samples, however, is controversial. The large variation of H isotope ratios in lunar apatite (delta Deuterium = -202 to +1010 per mille) has been taken as evidence that water in the lunar interior comes from the lunar mantle, solar wind protons, and/or comets. The very low deuterium/H ratios in lunar agglutinates indicate that solar wind protons have contributed to their hydrogen content. Conversely, H isotopes in lunar volcanic glass beads and olivine-hosted melt inclusions being similar to those of common terrestrial igneous rocks, suggest a common origin for water in both Earth and Moon. Lunar water could be inherited from carbonaceous chondrites, consistent with the model of late accretion of chondrite-type materials to the Moon as proposed by. One complication about the sources of lunar water, is that geologic processes (e.g., late accretion and magmatic degassing) may have modified the H isotope signatures of lunar materials. Recent FTIR analyses have shown that plagioclases in lunar ferroan anorthosite contain approximately 6 ppm H2O. So far, ferroan anorthosite is the only available lithology that is believed to be a primary product of the lunar magma ocean (LMO). A possible consequence is that the LMO could have contained up to approximately 320 ppm H2O. Here we examine the possible sources of water in the LMO through measurements of water abundances and H isotopes in plagioclase of two ferroan anorthosites and one troctolite from lunar highlands

A heterogeneous lunar interior for hydrogen isotopes as revealed by the lunar highlands samples

Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth–Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from −280 to +310‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H_2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about −280‰, evolving to about +310‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes

Distribution, Stock Composition and Timing, and Tagging Response of Wild Chinook Salmon Returning to a Large, Free-Flowing River Basin

Chinook Salmon Oncorhynchus tshawytscha returns to the Yukon River basin have declined dramatically since the late 1990s, and detailed information on the spawning distribution, stock structure, and stock timing is needed to better manage the run and facilitate conservation efforts. A total of 2,860 fish were radio-tagged in the lower basin during 2002–2004 and tracked upriver. Fish traveled to spawning areas throughout the basin, ranging from several hundred to over 3,000 km from the tagging site. Similar distribution patterns were observed across years, suggesting that the major components of the run were identified. Daily and seasonal composition estimates were calculated for the component stocks. The run was dominated by two regional components comprising over 70% of the return. Substantially fewer fish returned to other areas, ranging from 2% to 9% of the return, but their collective contribution was appreciable. Most regional components consisted of several principal stocks and a number of small, spatially isolated populations. Regional and stock composition estimates were similar across years even though differences in run abundance were reported, suggesting that the differences in abundance were not related to regional or stock-specific variability. Run timing was relatively compressed compared with that in rivers in the southern portion of the species’ range. Most stocks passed through the lower river over a 6-week period, ranging in duration from 16 to 38 d. Run timing was similar for middle- and upper-basin stocks, limiting the use of timing information for management. The lower-basin stocks were primarily later-run fish. Although differences were observed, there was general agreement between our composition and timing estimates and those from other assessment projects within the basin, suggesting that the telemetry-based estimates provided a plausible approximation of the return. However, the short duration of the run, complex stock structure, and similar stock timing complicate management of Yukon River returns

Calibration of the dolomite clumped isotope thermometer from 25 to 350°C, and implications for a universal calibration for all (Ca, Mg, Fe)CO_3 carbonates

Carbonate clumped isotope thermometry is based on the temperature-dependent formation of ^(13)C^(18)O^(16)O_2^(2-) ion groups within the lattice of solid carbonate minerals. At low temperatures the bonds between rare, heavy ^(13)C and ^(18)O isotopes are thermodynamically favored, and thus at equilibrium they are present in higher than random abundances. Here we calibrate the use of this temperature proxy in a previously uncalibrated carbonate phase — dolomite [CaMg(CO_3)_2] — over a temperature range that extends to conditions typical of shallow crustal environments, by determining the Δ_(47) values of CO_2 extracted from synthetic or natural (proto)dolomites grown at known temperatures from 25 to 350°C and analyzed in two different laboratories using different procedures for sample analysis, purification and post-measurement data treatment. We found that the Δ_(47) – 1/T^2 dependence for (proto)dolomite is linear between 25 and 350°C, independent of their Mg/Ca compositions or cation order (or the laboratory in which they were analyzed), and offset from, but parallel to, the theoretical predictions of the Δ_(63) dependence to temperature of the abundance of the ^(13)C^(18)O^(16)O_2 isotopologue inside the dolomite and calcite mineral lattices as expected from ab-initio calculations (Schauble et al., 2006). This suggests that neither the equilibrium constant for ^(13)C–^(18)O clumping in (proto)dolomite lattice, nor the experimental fractionation associated with acid digestion to produce CO_2, depend on their formation mechanism, degree of cation order and/or stoichiometry (ie., Mg/Ca ratio) and/or δ^(18)O and δ^(13)C compositions (at least over the range we explored). Thus, we suggest the following single Δ_(47) – 1/T^2 linear regression for describing all dolomite minerals: with T in kelvin and Δ_(47) in the Carbon Dioxide Equilibrium Scale (CDES) of Dennis et al. (2011) and referring to CO_2 extracted by phosphoric acid digestion at 90°C. The listed uncertainties on slope and intercept are 95% confidence intervals. The temperature sensitivity (slope) of this relation is lower than those based on low temperature acid digestion of carbonates, but comparable to most of those based on high temperature acid digestion (with however significantly better constraints on the slope and intercept values, notably due to the large range in temperature investigated and the large number of Δ_(47) measurements performed here, n = 67). We also use this dataset to empirically determine that the acid fractionation factor associated with phosphoric acid digestion of dolomite at 90°C (Δ∗_(dolomite90)) is about + 0.176‰. This is comparable to the Δ∗_(calcite90) experimentally obtained for calcite (Guo et al., 2009), suggesting that the acid fractionation Δ∗ for acid digestion of dolomite and calcite are the same within error of measurement, with apparently no influence of the cation identity. This hypothesis is also supported by the fact that our dolomite calibration data are indistinguishable from published calibration data for calcite, aragonite and siderite generated in similar analytical conditions (ie., carbonate digested at T ⩾ 70°C and directly referenced into CDES), demonstrating excellent consistency among the four (Ca,Mg,Fe)CO_3 mineral phases analyzed in seven different laboratories (this represents a total of 103 mean Δ_(47) values resulting from more than 331 Δ_(47) measurements). These data are used to calculate a composite Δ_(47)–T universal relation for those carbonate minerals of geological interest, for temperatures between -1 and 300°C, that is found to be statistically indistinguishable from the one described by dolomite only: Thus, in order to standardize the temperature estimates out of different laboratories running high temperature digestion of (Ca,Mg,Fe)CO_3 carbonate minerals, we recommend the use of this single Δ_(47)-T calibration to convert Δ_(47CDES) data into accurate and precise temperature estimates. More widely, this study extends the use of the Δ_(47) thermometry to studies of diagenesis and low-grade metamorphism of carbonates with unprecedented precision on temperature estimates based on Δ_(47) measurements — environments where many other thermometers are generally empirical or semi-quantitative