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1.
Sci Adv ; 10(39): eadp2426, 2024 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-39331721

RESUMO

The isotopic compositions of samples returned from Cb-type asteroid Ryugu and Ivuna-type (CI) chondrites are distinct from other carbonaceous chondrites, which has led to the suggestion that Ryugu/CI chondrites formed in a different region of the accretion disk, possibly around the orbits of Uranus and Neptune. We show that, like for Fe, Ryugu and CI chondrites also have indistinguishable Ni isotope anomalies, which differ from those of other carbonaceous chondrites. We propose that this unique Fe and Ni isotopic composition reflects different accretion efficiencies of small FeNi metal grains among the carbonaceous chondrite parent bodies. The CI chondrites incorporated these grains more efficiently, possibly because they formed at the end of the disk's lifetime, when planetesimal formation was also triggered by photoevaporation of the disk. Isotopic variations among carbonaceous chondrites may thus reflect fractionation of distinct dust components from a common reservoir, implying CI chondrites/Ryugu may have formed in the same region of the accretion disk as other carbonaceous chondrites.

2.
Metallomics ; 16(9)2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39217098

RESUMO

The Alzheimer's disease (AD)-affected brain purges K with concurrently increasing serum K, suggesting brain-blood K transferal. Here, natural stable K isotope ratios-δ41K-of human serum samples were characterized in an AD biomarker pilot study (plus two paired Li-heparin and potassium ethylenediaminetetraacetic acid [K-EDTA] plasma samples). AD serum was found to have a significantly lower mean δ41K relative to controls. To mechanistically explore this change, novel ab initio calculations (density functional theory) of relative K isotope compositions between hydrated K+ and organically bound K were performed, identifying hydrated K+ as isotopically light (lower δ41K) compared to organically bound K. Taken together with literature, serum δ41K and density functional theory results are consistent with efflux of hydrated K+ from the brain to the bloodstream, manifesting a measurable decrease in serum δ41K. These data introduce serum δ41K for further investigation as a minimally invasive AD biomarker, with cost, scalability, and stability advantages over current techniques.


Assuntos
Doença de Alzheimer , Biomarcadores , Potássio , Doença de Alzheimer/sangue , Doença de Alzheimer/metabolismo , Humanos , Biomarcadores/sangue , Potássio/sangue , Idoso , Masculino , Feminino , Isótopos/sangue , Idoso de 80 Anos ou mais , Projetos Piloto , Pessoa de Meia-Idade
3.
Sci Adv ; 10(33): eadl1007, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39141733

RESUMO

Volatile element abundances vary substantially among terrestrial planetary bodies like Earth, Mars, Moon, and differentiated asteroids, leading to intense debate about the governing processes. howardites-eucrites-diogenites (HED) meteorites, most likely from asteroid 4-Vesta, represent highly volatile-depleted Solar System samples, offering critical insights into these processes. Zinc is a moderately volatile element and its isotopic composition reveals sources of volatiles in planetary bodies. Our study finds Zn isotopic anomalies in diogenites overlapping with noncarbonaceous reservoirs, indicating negligible contributions of outer solar system materials to 4-Vesta's volatiles. Besides, zinc isotopic composition of 4-Vesta is lighter than that of chondrites, contrary to the expected signature of evaporation-based volatile depletion. This suggests that after 4-Vesta lost all its volatiles through evaporation during the magma ocean stage, partial kinetic recondensation occurred that produced the observed isotopically light composition. These insights, combined with previous data, underscore the process of global evaporation followed by partial condensation as a key factor influencing the final volatile budget of planetary bodies.

4.
Sci Adv ; 10(22): eadn9830, 2024 May 31.
Artigo em Inglês | MEDLINE | ID: mdl-38820147

RESUMO

Highly siderophile element abundances and Os isotopes of nakhlite and chassignite meteorites demonstrate that they represent a comagmatic suite from Mars. Nakhlites experienced variable assimilation of >2-billion-year-old altered high Re/Os basaltic crust. This basaltic crust is distinct from the ancient crust represented by meteorites Allan Hills 84001 or impact-contaminated Northwest Africa 7034/7533. Nakhlites and chassignites that did not experience crustal assimilation reveal that they were extracted from a depleted lithospheric mantle distinct from the deep plume source of depleted shergottites. The comagmatic origin for nakhlites and chassignites demonstrates a layered martian interior comprising ancient enriched basaltic crust derived from trace element-rich shallow magma ocean cumulates, a variably metasomatized mantle lithosphere, and a trace element-depleted deep mantle sampled by plume magmatism.

5.
Metallomics ; 16(5)2024 05 02.
Artigo em Inglês | MEDLINE | ID: mdl-38289854

RESUMO

Aging is the main risk factor for Alzheimer's disease (AD). AD is linked to alterations in metal homeostasis and changes in stable metal isotopic composition can occur, possibly allowing the latter to serve as relevant biomarkers for potential AD diagnosis. Copper stable isotopes are used to investigate changes in Cu homeostasis associated with various diseases. Prior work has shown that in AD mouse models, the accumulation of 63Cu in the brain is associated with the disease's progression. However, our understanding of how the normal aging process influences the brain's isotopic composition of copper remains limited. In order to determine the utility and predictive power of Cu isotopes in AD diagnostics, we aim-in this study-to develop a baseline trajectory of Cu isotopic composition in the normally aging mouse brain. We determined the copper concentration and isotopic composition in brains of 30 healthy mice (WT) ranging in age from 6 to 12 mo, and further incorporate prior data obtained for 3-mo-old healthy mice; this range approximately equates to 20-50 yr in human equivalency. A significant 65Cu enrichment has been observed in the 12-mo-old mice compared to the youngest group, concomitant with an increase in Cu concentration with age. Meanwhile, literature data for brains of AD mice display an enrichment in 63Cu isotope compared to WT. It is acutely important that this baseline enrichment in 65Cu is fully constrained and normalized against if any coherent diagnostic observations regarding 63Cu enrichment as a biomarker for AD are to be developed.


Assuntos
Envelhecimento , Encéfalo , Cobre , Animais , Cobre/metabolismo , Cobre/análise , Envelhecimento/metabolismo , Camundongos , Encéfalo/metabolismo , Doença de Alzheimer/metabolismo , Camundongos Endogâmicos C57BL , Masculino , Humanos
6.
Anal Chem ; 96(5): 2199-2205, 2024 02 06.
Artigo em Inglês | MEDLINE | ID: mdl-38179926

RESUMO

We present a new approach to Cu isotopic measurements using a state-of-the-art Nu Sapphire multicollector inductively coupled plasma source mass spectrometer equipped with a collision/reaction cell (CRC-MC-ICPMS). We investigate the effects of Na doping and Cu concentration mismatch between bracketing standard and unknown samples and demonstrate the efficacy of introducing a He-H2 gas mix into the CRC to efficiently eliminate the sample matrix-based 40Ar23Na+ isobaric interference on 63Cu+. This capability is crucial when measuring samples with high Na/Cu ratios, such as some biological samples, which have significantly different chemical compositions compared to most geological samples. Moreover, considering the necessity of obtaining large data sets for biological samples to ensure reliable interpretations, the implementation of a CRC for mitigating the 40Ar23Na+ interference offers the advantage of minimizing the requirement for extensive Cu chemical separation procedure prior to Cu isotopic measurements. Our results demonstrate that the accurate determination of the δ65Cu values is achievable for samples with Na/Cu concentration ratios of up to ∼65, even when measuring 100 ppb Cu solutions (equivalent to a signal of ∼3.5-4 V total Cu). Furthermore, our results showcase a good short-term repeatability on δ65Cu for pure Cu standard solutions (NIST SRM 976 and Cu-IPGP), typically of 0.05‰ (2 SD) when measuring >50 ppb Cu solutions. Our long-term external reproducibility stands at approximately 0.07‰ (2 SD). This value accounts for the variable Cu concentrations analyzed across the different analytical sequences (from 10 to 100 ppb Cu solutions). To validate the robustness of our analytical method, we first conduct a comparison between data sets from mice brains processed twice through column chemistry using a Thermo Finnigan Neptune MC-ICPMS and a Nu Sapphire CRC-MC-ICPMS in CRC mode. This comparison serves to verify the reliability of our method for measuring Cu isotopic composition using the CRC on samples with a low Na/Cu ratio after traditional chemical processing. Then, we compare the data sets obtained for biological standards (tuna fish ERM-CE 464 (IRMM) and human serum Seronorm Trace Elements Serum L-1) processed either once, or twice, through column chemistry and demonstrate that the CRC allows accurate Cu isotopic measurements of the samples processed only once and therefore with a higher Na/Cu ratio.


Assuntos
Cobre , Isótopos , Animais , Camundongos , Humanos , Reprodutibilidade dos Testes , Isótopos/química , Espectrometria de Massas/métodos , Análise Espectral
7.
Anal Chem ; 96(1): 170-178, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38155534

RESUMO

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca2+ and Mn2+ on the Mg2+- and Fe2+-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca2+, Mg2+, and Fe2+ + Mn2+) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe2+ + Mn2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

8.
Proc Natl Acad Sci U S A ; 121(1): e2311402121, 2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-38147555

RESUMO

The planetesimals in the solar system exhibit varying degrees of moderately volatile elements (MVEs) depletion compared to the protosolar composition. Revealing the relevant mechanisms is crucial for exploring early solar system evolution. Most volatile-depleted materials in the solar system exhibit enrichments in the heavier isotopes of MVEs, which have traditionally been attributed to the loss of volatiles through partial evaporation. Angrites are so far an exception as they are enriched in the lighter isotopes of K. This has been interpreted as reflecting condensation processes. Here, we present Rb isotopic data of angrites and find that they have lighter Rb isotopic compositions than Vesta, Mars, and the Moon. The δ87Rb value of the angrite parent body (APB) is estimated to range between -1.19‰ and -0.67‰. The extremely light Rb isotopic composition of the APB is likely a result of the kinetic recondensation of Rb after near-complete evaporation during the magma ocean stage. This finding provides further support for the partial recondensation model to explain the light Rb and K isotopic compositions of the APB. In addition, the APB, alongside other terrestrial planetary bodies (e.g., Earth, Mars, Moon, and Vesta), exhibit a strong correlation between their Rb and K isotopic compositions. This coupling of Rb and K isotopes is indicative of a volatility-driven isotopic fractionation rather than nucleosynthetic anomalies. The extremely light Rb-K isotopic signatures of the APB suggest that beyond evaporation, condensation plays an equally significant role in shaping the planetary-scale distributions of volatile elements.

9.
Sci Adv ; 9(45): eadi7048, 2023 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-37939187

RESUMO

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred [Formula: see text] after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.

10.
Anal Bioanal Chem ; 415(27): 6839-6850, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37755490

RESUMO

The stable calcium (Ca) isotopes offer a minimally invasive method for assessing Ca balance in the body, providing a new avenue for research and clinical applications. In this study, we measured the Ca isotopic composition of soft tissues (brain, muscle, liver, and kidney), mineralized tissue (bone), and blood (plasma) from 10 mice (5 females and 5 males) with three different genetic backgrounds and same age (3 months old). The results reveal a distinctive Ca isotopic composition in different body compartments of mice, primally controlled by each compartment's unique Ca metabolism and genetic background, independent of sex. The bones are enriched in the lighter Ca isotopes (δ44/40Cabone = - 0.10 ± 0.55 ‰) compared to blood and other soft tissues, reflecting the preferential incorporation of lighter Ca isotopes through bone formation, while heavier Ca isotopes remain preferentially in blood. The brain and muscle are enriched in lighter Ca isotopes (δ44/40Cabrain = - 0.10 ± 0.53 ‰; δ44/40Camuscle = 0.19 ± 0.41 ‰) relative to blood and other soft tissues, making the brain the isotopically lightest soft tissues of the mouse body. In contrast, the kidney is enriched in heavier isotopes (δ44/40Cakidney = 0.86 ± 0.31 ‰) reflecting filtration and reabsorption by the kidney. This study provides important insight into the Ca isotopic composition of various body compartments and fluids.

11.
Sci Adv ; 9(28): eadh1003, 2023 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-37450600

RESUMO

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.


Assuntos
Carbono , Meteoroides , Carbono/análise , Sistema Solar , Silicatos
12.
Metallomics ; 15(7)2023 07 10.
Artigo em Inglês | MEDLINE | ID: mdl-37197928

RESUMO

Potassium (K) is an essential electrolyte for cellular functions in living organisms, and disturbances in K+ homeostasis could lead to various chronic diseases (e.g. hypertension, cardiac disease, diabetes, and bone health). However, little is known about the natural distribution of stable K isotopes in mammals and their application to investigate bodily homeostasis and/or as biomarkers for diseases. Here, we measured K isotopic compositions (δ41K, per mil deviation of 41K/39K from the NIST SRM 3141a standard) of brain, liver, kidney, and red blood cells (RBCs) from 10 mice (five females and five males) with three different genetic backgrounds. Our results reveal that different organs and RBCs have distinct K isotopic signatures. Specifically, the RBCs have heavy K isotopes enrichment with δ41K ranging from 0.67 to 0.08‰, while the brains show lighter K isotopic compositions with δ41K ranging from -1.13 to -0.09‰ compared to the livers (δ41K = -0.12 ± 0.58‰) and kidneys (δ41K = -0.24 ± 0.57‰). We found that the K isotopic and concentration variability is mostly controlled by the organs, with a minor effect of the genetic background and sex. Our study suggests that the K isotopic composition could be used as a biomarker for changes in K+ homeostasis and related diseases such as hypertension, cardiovascular, and neurodegenerative diseases.


Assuntos
Hipertensão , Potássio , Masculino , Feminino , Animais , Camundongos , Isótopos , Isótopos de Potássio , Eritrócitos , Mamíferos
13.
Science ; 379(6634): eabn7850, 2023 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-35679354

RESUMO

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about [Formula: see text] million (statistical) or [Formula: see text] million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun's photosphere than other natural samples do.

14.
Sci Adv ; 8(50): eade2067, 2022 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-36525483

RESUMO

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here, we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16O-rich (associated with refractory inclusions) and 16O-poor (associated with chondrules). Both the 16O-rich and 16O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outward. The abundance ratios of the 16O-rich to 16O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

15.
Nat Commun ; 13(1): 7669, 2022 12 12.
Artigo em Inglês | MEDLINE | ID: mdl-36509778

RESUMO

Volatiles are vital ingredients for a habitable planet. Angrite meteorites sample the most volatile-depleted planetesimal in the Solar System, particularly for the alkali elements. They are prime targets for investigating the formation of volatile-poor rocky planets, yet their exceptionally low volatile content presents a major analytical challenge. Here, we leverage improved sensitivity and precision of K isotopic analysis to constrain the mechanism of extreme K depletion (>99.8%) in angrites. In contrast with the isotopically heavy Moon and Vesta, we find that angrites are strikingly depleted in the heavier K isotopes, which is best explained by partial recondensation of vaporized K following extensive evaporation on the angrite parent body (APB) during magma-ocean stage. Therefore, the APB may provide a rare example of isotope fractionation controlled by condensation, rather than evaporation, at a planetary scale. Furthermore, nebula-wide K isotopic variations primarily reflect volatility-driven fractionations instead of presolar nucleosynthetic heterogeneity proposed previously.


Assuntos
Meio Ambiente Extraterreno , Meteoroides , Sistema Solar , Planetas , Isótopos , Isótopos de Potássio
16.
Sci Adv ; 8(46): eabp8415, 2022 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-36383650

RESUMO

The terrestrial planets endured a phase of bombardment following their accretion, but the nature of this late accreted material is debated, preventing a full understanding of the origin of inner solar system volatiles. We report the discovery of nucleosynthetic chromium isotope variability (µ54Cr) in Martian meteorites that represent mantle-derived magmas intruded in the Martian crust. The µ54Cr variability, ranging from -33.1 ± 5.4 to +6.8 ± 1.5 parts per million, correlates with magma chemistry such that samples having assimilated crustal material define a positive µ54Cr endmember. This compositional endmember represents the primordial crust modified by impacting outer solar system bodies of carbonaceous composition. Late delivery of this volatile-rich material to Mars provided an exotic water inventory corresponding to a global water layer >300 meters deep, in addition to the primordial water reservoir from mantle outgassing. This carbonaceous material may also have delivered a source of biologically relevant molecules to early Mars.

17.
Metallomics ; 14(12)2022 12 08.
Artigo em Inglês | MEDLINE | ID: mdl-36416864

RESUMO

Natural stable metal isotopes have shown utility in differentiation between healthy and diseased brain states (e.g. Alzheimer's disease, AD). While the AD brain accumulates some metals, it purges others, namely K (accompanied by increased serum K, suggesting brain-blood transferal). Here, K isotope compositions of Göttingen minipig brain regions for two AD models at midlife are reported. Results indicate heavy K isotope enrichment where amyloid beta (Aß) accumulation is observed, and this enrichment correlates with relative K depletion. These results suggest preferential efflux of isotopically light K+ from the brain, a linkage between brain K concentrations and isotope compositions, and linkage to Aß (previously shown to purge cellular brain K+). Brain K isotope compositions differ from that for serum and brain K is much more abundant than in serum, suggesting that changes in brain K may transfer a measurable K isotope excursion to serum, thereby generating an early AD biomarker.


Assuntos
Doença de Alzheimer , Suínos , Animais , Humanos , Peptídeos beta-Amiloides/metabolismo , Porco Miniatura/metabolismo , Encéfalo/metabolismo , Metais , Isótopos
18.
Sci Adv ; 8(46): eadd8141, 2022 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-36264823

RESUMO

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune.

19.
J Trace Elem Med Biol ; 71: 126967, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35259616

RESUMO

BACKGROUND: Copper is a metal that plays a central role in biology, for example, as co-factor in various redox enzymes. Its stable isotopic composition is being used as tracer of its transport in living organisms and as a biomarker for diseases affecting its homeostasis. While the application of copper stable isotopes to biological studies is a growing field, there are presently no biological standards that are systematically analyzed in the different laboratories, as it is the case for geological samples (e.g., by using widely available basalt samples). It is therefore paramount for the community to establish such standard. Copper also binds oxygen in the respiratory protein, hemocyanin, in the hemolymph of mollusks and arthropods and is thus critical to respiration for these species. METHODS: Here, the Cu isotope composition of hemocyanin of different modern species of mollusks and arthropods (Megathura crenulate Keyhole limpet, Limulus polyphemus Horseshoe crab and Concholepas concholepas Chilean abalone), as well as theoretical constraints on the origin of these isotopic fractionations through ab initio calculations are reported. RESULTS: The isotopic fractionation factors for Cu(I) and Cu(II), both in hemocyanin and in seawater, predict an enrichment in the lighter isotope of Cu in the hemocyanin by over 1 permil compared to seawater. The hemocyanin of Chilean abalone and Horseshoe crab have Cu isotope compositions (δ65Cu = +0.63 ± 0.04‰ and +0.61 ± 0.04‰, respectively, with δ65Cu the permil deviation of the 65Cu/63Cu ratio from the NIST SRM 976 standard), similar to that of the octopus reported in literature (+0.62‰), that are undistinguishable from seawater, suggesting quantitative Cu absorption for these organisms. Conversely, the Keyhole limpet is enriched in the lighter isotope of Cu, which is in line with the ab initio calculation and therefore Cu isotopic fractionation during incorporation of Cu into the hemocyanin. CONCLUSIONS: Because these hemocyanin standard samples are widely available, they could serve in the future as inter-laboratory standards to verify the accuracy of the Cu isotopic measurements on biological matrices.


Assuntos
Cobre , Hemocianinas , Animais , Cobre/análise , Isótopos/análise , Chile
20.
Proc Natl Acad Sci U S A ; 119(12): e2120933119, 2022 03 22.
Artigo em Inglês | MEDLINE | ID: mdl-35290127

RESUMO

The formation and differentiation of planetary bodies are dated using radioactive decay systems, including the short-lived 146Sm-142Nd (T½ = 103 or 68 Ma) and long-lived 147Sm-143Nd (T½ = 106 Ga) radiogenic pairs that provide relative and absolute ages, respectively. However, the initial abundance and half-life of the extinct radioactive isotope 146Sm are still debated, weakening the interpretation of 146Sm-142Nd systematics obtained for early planetary processes. Here, we apply the short-lived 26Al-26Mg, 146Sm-142Nd, and long-lived 147Sm-143Sm chronometers to the oldest known andesitic meteorite, Erg Chech 002 (EC 002), to constrain the Solar System initial abundance of 146Sm. The 26Al-26Mg mineral isochron of EC 002 provides a tightly constrained initial δ26Mg* of −0.009 ± 0.005 ‰ and (26Al/27Al)0 of (8.89 ± 0.09) × 10−6. This initial abundance of 26Al is the highest measured so far in an achondrite and corresponds to a crystallization age of 1.80 ± 0.01 Myr after Solar System formation. The 146Sm-142Nd mineral isochron returns an initial 146Sm/144Sm ratio of 0.00830 ± 0.00032. By combining the Al-Mg crystallization age and initial 146Sm/144Sm ratio of EC 002 with values for refractory inclusions, achondrites, and lunar samples, the best-fit half-life for 146Sm is 102 ± 9 Ma, corresponding to the physically measured value of 103 ± 5 Myr, rather than the latest and lower revised value of 68 ± 7 Ma. Using a half-life of 103 Ma for 146Sm, the 146Sm/144Sm abundance of EC 002 translates into an initial Solar System 146Sm/144Sm ratio of 0.00840 ± 0.00032, which represents the most reliable and precise estimate to date and makes EC 002 an ideal anchor for the 146Sm-142Nd clock.

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