One may wonder how a paper discussing medical applications of metal isotopes got lost in a review journal dedicated to mineralogy and geochemistry. The justifications are multiple. First, the coming of age of metal isotopic analysis in the mid ‘90s is largely due to the analytical creativity of the geochemical community and to corporate technical skills allowing the rise of new technologies. Second, many concepts, which can be imbedded in quantitative models testable from their predictions, are common to geochemistry, biochemistry, physiology, and nutrition: a cell, with its organelles, a body with its organ and body fluids, are systems liable to treatments similar to those used to model a lake, the ocean–atmosphere, and the mantle–crust systems. Of course, time scales and length scales differ, the complexity of biology is immense compared to that of the mineral world. Geological systems lack the hallmarks of life, genes and cell signaling. In spite of the overall complexity of the biological systems, pathways, kinetics, and chemical dynamics are better understood than their counterpart in earth sciences. Like in many fields of engineering, comparing the records of inputs and outputs is a powerful tool to identify the internal ‘knobs’ controlling a given system and learn how to tweak them. Third, although some of the most sophisticated techniques such as ab initio calculations of molecular configurations, energetics, and isotopic properties are still limited to molecules with less than a few dozens of atoms, the time is getting closer to when simulations of large molecules will become available for application to ‘real’ proteins with large molecular weights. The present article reviews some of the basic features of what is now known as Metallomics and the preliminary applications of stable isotopes to some medical cases, a discipline for which we suggest the simple term of Isotope Metallomics . …
{"title":"Medical applications of isotope metallomics","authors":"F. Albarède, P. Télouk, V. Balter","doi":"10.2138/RMG.2017.82.20","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.20","url":null,"abstract":"One may wonder how a paper discussing medical applications of metal isotopes got lost in a review journal dedicated to mineralogy and geochemistry. The justifications are multiple. First, the coming of age of metal isotopic analysis in the mid ‘90s is largely due to the analytical creativity of the geochemical community and to corporate technical skills allowing the rise of new technologies. Second, many concepts, which can be imbedded in quantitative models testable from their predictions, are common to geochemistry, biochemistry, physiology, and nutrition: a cell, with its organelles, a body with its organ and body fluids, are systems liable to treatments similar to those used to model a lake, the ocean–atmosphere, and the mantle–crust systems. Of course, time scales and length scales differ, the complexity of biology is immense compared to that of the mineral world. Geological systems lack the hallmarks of life, genes and cell signaling. In spite of the overall complexity of the biological systems, pathways, kinetics, and chemical dynamics are better understood than their counterpart in earth sciences. Like in many fields of engineering, comparing the records of inputs and outputs is a powerful tool to identify the internal ‘knobs’ controlling a given system and learn how to tweak them. Third, although some of the most sophisticated techniques such as ab initio calculations of molecular configurations, energetics, and isotopic properties are still limited to molecules with less than a few dozens of atoms, the time is getting closer to when simulations of large molecules will become available for application to ‘real’ proteins with large molecular weights. The present article reviews some of the basic features of what is now known as Metallomics and the preliminary applications of stable isotopes to some medical cases, a discipline for which we suggest the simple term of Isotope Metallomics . …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"29 1","pages":"851-885"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85440582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In contrast to many other stable isotopes of the elements discussed in this book, those of silicon are not strictly speaking “Non-Traditional Stable Isotopes” because they have been studied for more than 60 years. After the pioneering works of Reynolds and Verhoogen (1953) and Allenby (1954), a steady increase in silicon isotope studies of geological materials has led to a substantial corpus of data. These data were compiled by Ding et al. (1996) alongside new measurements that, collectively, included over a thousand samples of rocks, minerals, waters and biological materials. Most of these data were produced using the well established method of gas source mass spectrometry after sample decomposition and silicon purification via fluorination techniques. As for many non-traditional stable isotopes, silicon isotope research has flourished with the advent of second generation of multicollector plasma source mass spectrometers (MC–ICP–MS). These instruments eliminated the requirement of hazardous gaseous fluorine sample preparation methods while permitting improved analytical precision in both wet plasma (De La Rocha 2002) and in dry plasma (Cardinal et al. 2003). Subsequent analytical developments involving high mass resolution MC–ICP–MS combined with improved silicon purification methods (Georg et al. 2006) made this analytical technique more robust and precise enough to study even the subtle silicon isotope variations produced during high temperature geological processes (Savage et al. 2014). Silicon is the fourteenth element of the Periodic Table. Its atomic mass was precisely determined to be 28.08553 ± 0.00039 in atomic mass units (a.m.u.) on a pure silicon reference material (NIST SRM–990, Barnes et al. 1975). This 95% confidence limit error includes the overall natural isotopic variation range for 30Si/28Si known by the time, estimated to be about 5‰ from the analysis of biological, meteoritic and terrestrial materials (Tilles 1961). As detailed below, the current database suggests …
与本书中讨论的许多其他元素的稳定同位素相比，硅的稳定同位素严格来说并不是“非传统稳定同位素”，因为它们已经被研究了60多年。在Reynolds和Verhoogen(1953)以及Allenby(1954)的开创性工作之后，对地质材料的硅同位素研究稳步增加，产生了大量数据。这些数据是由Ding等人(1996)与新的测量数据一起汇编而成的，这些测量数据总共包括了一千多个岩石、矿物、水和生物材料的样本。这些数据大多是在经过样品分解和氟化技术的硅净化后，使用成熟的气源质谱法产生的。对于许多非传统稳定同位素，随着第二代多收集器等离子体源质谱仪(MC-ICP-MS)的出现，硅同位素的研究得到了蓬勃发展。这些仪器消除了对危险气态氟样品制备方法的要求，同时提高了湿等离子体(De La Rocha 2002年)和干等离子体(Cardinal et al. 2003年)的分析精度。随后的分析发展涉及高质量分辨率MC-ICP-MS结合改进的硅净化方法(Georg et al. 2006)，使该分析技术更加稳健和精确，甚至可以研究高温地质过程中产生的细微硅同位素变化(Savage et al. 2014)。硅是元素周期表中的第十四种元素。在纯硅基准材料上，精确测定其原子量为28.08553±0.00039原子量单位(a.m.u) (NIST SRM-990, Barnes et al. 1975)。95%置信限误差包括当时已知的30Si/28Si的总体自然同位素变化范围，根据生物、陨石和陆地材料的分析估计约为5‰(Tilles 1961)。如下所述，目前的数据库表明……
{"title":"Silicon Isotope Geochemistry","authors":"F. Poitrasson","doi":"10.2138/RMG.2017.82.8","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.8","url":null,"abstract":"In contrast to many other stable isotopes of the elements discussed in this book, those of silicon are not strictly speaking “Non-Traditional Stable Isotopes” because they have been studied for more than 60 years. After the pioneering works of Reynolds and Verhoogen (1953) and Allenby (1954), a steady increase in silicon isotope studies of geological materials has led to a substantial corpus of data. These data were compiled by Ding et al. (1996) alongside new measurements that, collectively, included over a thousand samples of rocks, minerals, waters and biological materials. Most of these data were produced using the well established method of gas source mass spectrometry after sample decomposition and silicon purification via fluorination techniques. As for many non-traditional stable isotopes, silicon isotope research has flourished with the advent of second generation of multicollector plasma source mass spectrometers (MC–ICP–MS). These instruments eliminated the requirement of hazardous gaseous fluorine sample preparation methods while permitting improved analytical precision in both wet plasma (De La Rocha 2002) and in dry plasma (Cardinal et al. 2003). Subsequent analytical developments involving high mass resolution MC–ICP–MS combined with improved silicon purification methods (Georg et al. 2006) made this analytical technique more robust and precise enough to study even the subtle silicon isotope variations produced during high temperature geological processes (Savage et al. 2014). Silicon is the fourteenth element of the Periodic Table. Its atomic mass was precisely determined to be 28.08553 ± 0.00039 in atomic mass units (a.m.u.) on a pure silicon reference material (NIST SRM–990, Barnes et al. 1975). This 95% confidence limit error includes the overall natural isotopic variation range for 30Si/28Si known by the time, estimated to be about 5‰ from the analysis of biological, meteoritic and terrestrial materials (Tilles 1961). As detailed below, the current database suggests …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"35 1","pages":"289-344"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81511145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In 1986, O’Neil wrote a Reviews in Mineralogy chapter on experimental aspects of isotopic fractionation. He noted that in order to fully understand and interpret the natural variations of light stable isotope ratios in nature, it was essential to know the magnitude and temperature dependence of the isotopic fractionation factor amongst minerals and fluids. At that time it was difficult to imagine that this would become true for the heavier, so called non-traditional stable isotopes, as well. Since the advent of the multiple collector inductively coupled plasma-source mass spectrometer (MC–ICP–MS), natural variations of stable isotope ratios have been found for almost any polyisotopic element measured. Although it has been known that as temperature and mass increase, isotope fractionation decreases very quickly, the MC–ICP–MS has revolutionized the ability of a geochemist to measure very small differences in isotope ratios. It was then that the field of experimental non-traditional stable isotope geochemistry was born. As O’Neil (1986) pointed out there are three ways to obtain isotopic fractionation factors: theoretical calculations, measurements of natural samples with well-known formation conditions, and laboratory calibration studies. This chapter is devoted to explaining the techniques involved with laboratory experiments designed to measure equilibrium isotope fractionation factors as well as the best practices that have been learned. Although experimental petrology has been around for a long time and basic experimental methods have been well-refined, there are additional considerations that must be taken into account when the goal is to measure isotopic compositions at the end of the experiment. It has been only about ten years since these initial studies were published, but much has been learned in that time about how best to conduct experiments aimed at determining equilibrium fractionation factors. We will not focus on the scientific results that have been determined by such experiments, as each …
{"title":"Equilibrium Fractionation of Non-traditional Stable Isotopes: an Experimental Perspective","authors":"A. Shahar, S. Elardo, C. Macris","doi":"10.2138/RMG.2017.82.3","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.3","url":null,"abstract":"In 1986, O’Neil wrote a Reviews in Mineralogy chapter on experimental aspects of isotopic fractionation. He noted that in order to fully understand and interpret the natural variations of light stable isotope ratios in nature, it was essential to know the magnitude and temperature dependence of the isotopic fractionation factor amongst minerals and fluids. At that time it was difficult to imagine that this would become true for the heavier, so called non-traditional stable isotopes, as well. Since the advent of the multiple collector inductively coupled plasma-source mass spectrometer (MC–ICP–MS), natural variations of stable isotope ratios have been found for almost any polyisotopic element measured. Although it has been known that as temperature and mass increase, isotope fractionation decreases very quickly, the MC–ICP–MS has revolutionized the ability of a geochemist to measure very small differences in isotope ratios. It was then that the field of experimental non-traditional stable isotope geochemistry was born. As O’Neil (1986) pointed out there are three ways to obtain isotopic fractionation factors: theoretical calculations, measurements of natural samples with well-known formation conditions, and laboratory calibration studies. This chapter is devoted to explaining the techniques involved with laboratory experiments designed to measure equilibrium isotope fractionation factors as well as the best practices that have been learned. Although experimental petrology has been around for a long time and basic experimental methods have been well-refined, there are additional considerations that must be taken into account when the goal is to measure isotopic compositions at the end of the experiment. It has been only about ten years since these initial studies were published, but much has been learned in that time about how best to conduct experiments aimed at determining equilibrium fractionation factors. We will not focus on the scientific results that have been determined by such experiments, as each …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"16 1","pages":"65-83"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74463927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This contribution summarizes the current state of understanding and recent advances made in the field of stable thallium (Tl) isotope geochemistry. High precision measurements of Tl isotope compositions were developed in the late 1990s with the advent of multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS) and subsequent studies revealed that Tl, despite the small relative mass difference of the two isotopes, exhibits substantial stable isotope fractionation, especially in the marine environment. The most fractionated reservoirs identified are ferromanganese sediments with ɛ 205 Tl ≈ +15 and low temperature altered oceanic crust with ɛ 205 Tl ≈ −20. The total isotopic variability of more than 35 ɛ 205 Tl-units hence exceeds the current analytical reproducibility of the measurement technique by more than a factor of 70. This isotopic variation can be explained by invoking a combination of conventional mass dependent equilibrium isotope effects and nuclear field shift isotope fractionation, but the specific mechanisms are still largely unaccounted for. Thallium isotopes have been applied to investigate paleoceanographic processes in the Cenozoic and there is evidence to suggest that Tl isotopes may be utilized as a monitor of the marine manganese oxide burial flux over million year time scales. In addition, Tl isotopes can be used to calculate the magnitude of hydrothermal fluid circulation through ocean crust. It has also been shown that the subduction of marine ferromanganese sediments can be detected with Tl isotopes in lavas erupted in subduction zone settings as well as in ocean island basalts. Meteorite samples display Tl isotope variations that exceed the terrestrial range with a total variability of about 50 ɛ 205 Tl. The large isotopic diversity, however, is generated by both stable Tl isotope fractionations, which reflect the highly volatile and labile cosmochemical nature of the element, and radiogenic decay of extinct 205 Pb to 205 Tl with a half-life of about 15 Ma. The difficulty of deconvolving these two sources of isotopic variability restricts the utility of both the 205 Pb– 205 Tl chronometer and the Tl stable isotope system to inform on early solar system processes.
{"title":"Investigation and Application of Thallium Isotope Fractionation","authors":"S. Nielsen, M. Rehkämper, J. Prytulak","doi":"10.2138/RMG.2017.82.18","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.18","url":null,"abstract":"This contribution summarizes the current state of understanding and recent advances made in the field of stable thallium (Tl) isotope geochemistry. High precision measurements of Tl isotope compositions were developed in the late 1990s with the advent of multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS) and subsequent studies revealed that Tl, despite the small relative mass difference of the two isotopes, exhibits substantial stable isotope fractionation, especially in the marine environment. The most fractionated reservoirs identified are ferromanganese sediments with ɛ 205 Tl ≈ +15 and low temperature altered oceanic crust with ɛ 205 Tl ≈ −20. The total isotopic variability of more than 35 ɛ 205 Tl-units hence exceeds the current analytical reproducibility of the measurement technique by more than a factor of 70. This isotopic variation can be explained by invoking a combination of conventional mass dependent equilibrium isotope effects and nuclear field shift isotope fractionation, but the specific mechanisms are still largely unaccounted for. Thallium isotopes have been applied to investigate paleoceanographic processes in the Cenozoic and there is evidence to suggest that Tl isotopes may be utilized as a monitor of the marine manganese oxide burial flux over million year time scales. In addition, Tl isotopes can be used to calculate the magnitude of hydrothermal fluid circulation through ocean crust. It has also been shown that the subduction of marine ferromanganese sediments can be detected with Tl isotopes in lavas erupted in subduction zone settings as well as in ocean island basalts. Meteorite samples display Tl isotope variations that exceed the terrestrial range with a total variability of about 50 ɛ 205 Tl. The large isotopic diversity, however, is generated by both stable Tl isotope fractionations, which reflect the highly volatile and labile cosmochemical nature of the element, and radiogenic decay of extinct 205 Pb to 205 Tl with a half-life of about 15 Ma. The difficulty of deconvolving these two sources of isotopic variability restricts the utility of both the 205 Pb– 205 Tl chronometer and the Tl stable isotope system to inform on early solar system processes.","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"60 1","pages":"759-798"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84676694","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Funding during the compilation of this manuscript was provided by the NASA postdoctoral program.
本文的编写经费由NASA博士后项目提供。
{"title":"Selenium Isotopes as a Biogeochemical Proxy in Deep Time","authors":"E. Stüeken","doi":"10.2138/RMG.2017.82.15","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.15","url":null,"abstract":"Funding during the compilation of this manuscript was provided by the NASA postdoctoral program.","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"40 1","pages":"657-682"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81469425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Copper, a native metal found in ores, is the principal metal in bronze and brass. It is a reddish metal with a density of 8920 kg m−3. All of copper’s compounds tend to be brightly colored: for example, copper in hemocyanin imparts a blue color to blood of mollusks and crustaceans. Copper has three oxidation states, with electronic configurations of Cu([Ar]3 d 104 s 1), Cu+([Ar]3 d 10), and Cu2+([Ar]3 d 9). Cu does not react with aqueous hydrochloric or sulfuric acids, but is soluble in concentrated nitric acid due to its lesser tendency to be oxidized. Cu(I) exists as the colorless cuprous ion, Cu+. Cu(II) is found as the sky-blue cupric ion, Cu2+. The Cu+ ion is unstable, and tends to disproportionate to Cu and Cu2+. Nevertheless, Cu(I) forms compounds such as Cu2O. Cu(I) bonds more readily to carbon than Cu(II), hence Cu(I) has an extensive chemistry with organic compounds. In aqueous solutions, Cu2+ ion occurs as an aquacomplex. There is no clearly predominant structure among the four-, five-, and six-fold coordinated Cu(II) species (Chaboy et al. 2006). Hydrated Cu(II) ion has been represented as the hexaaqua complex Cu(H2O)62+, which shows the Jahn–Teller distortion effect (Sherman 2001; Bersuker 2006), whereby the two Cu–O distances of the vertical axial bond (Cu–Oax) are longer than four Cu–O distances in the equatorial plane (Cu–Oeq). The Jahn–Teller effect lowers the symmetry of Cu(H2O)62+ from octahedral Th to D2h. The sixfold coordination of hydrated Cu(II) species is questioned by a finding of fivefold coordination (Pasquarello et al. 2001; Chaboy et al. 2006; Little et al. 2014b …
铜是一种在矿石中发现的天然金属，是青铜和黄铜的主要金属。它是一种微红色的金属，密度为8920 kg m−3。所有铜的化合物都倾向于呈现鲜艳的颜色:例如，血青素中的铜使软体动物和甲壳类动物的血液呈现蓝色。铜有三种氧化态，电子构型为Cu([Ar]3 d 104 s 1)、Cu+([Ar]3 d 10)和Cu2+([Ar]3 d 9)。Cu不与盐酸或硫酸反应，但由于不易被氧化，可溶于浓硝酸。Cu(I)以无色的铜离子Cu+存在。Cu(II)被发现为天蓝色的铜离子Cu2+。Cu+离子不稳定，倾向于与Cu和Cu2+不成比例。然而，Cu(I)形成Cu2O等化合物。Cu(I)比Cu(II)更容易与碳成键，因此Cu(I)与有机化合物具有广泛的化学作用。在水溶液中，Cu2+离子以水化络合物的形式存在。四重、五重和六重配位Cu(II)物种之间没有明显的优势结构(Chaboy et al. 2006)。水合Cu(II)离子被表示为六水络合物Cu(H2O)62+，表现出Jahn-Teller畸变效应(Sherman 2001;Bersuker 2006)，其中垂直轴向键(Cu-Oax)的两个Cu-O距离比赤道面(Cu-Oeq)的四个Cu-O距离长。Jahn-Teller效应降低了Cu(H2O)62+从八面体Th到D2h的对称性。五重配位的发现对水合铜(II)物种的六重配位提出了质疑(Pasquarello等人，2001;Chaboy et al. 2006;Little et al. 2014b…
{"title":"The Isotope Geochemistry of Zinc and Copper","authors":"F. Moynier, D. Vance, T. Fujii, P. Savage","doi":"10.2138/RMG.2017.82.13","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.13","url":null,"abstract":"Copper, a native metal found in ores, is the principal metal in bronze and brass. It is a reddish metal with a density of 8920 kg m−3. All of copper’s compounds tend to be brightly colored: for example, copper in hemocyanin imparts a blue color to blood of mollusks and crustaceans. Copper has three oxidation states, with electronic configurations of Cu([Ar]3 d 104 s 1), Cu+([Ar]3 d 10), and Cu2+([Ar]3 d 9). Cu does not react with aqueous hydrochloric or sulfuric acids, but is soluble in concentrated nitric acid due to its lesser tendency to be oxidized. Cu(I) exists as the colorless cuprous ion, Cu+. Cu(II) is found as the sky-blue cupric ion, Cu2+. The Cu+ ion is unstable, and tends to disproportionate to Cu and Cu2+. Nevertheless, Cu(I) forms compounds such as Cu2O. Cu(I) bonds more readily to carbon than Cu(II), hence Cu(I) has an extensive chemistry with organic compounds. In aqueous solutions, Cu2+ ion occurs as an aquacomplex. There is no clearly predominant structure among the four-, five-, and six-fold coordinated Cu(II) species (Chaboy et al. 2006). Hydrated Cu(II) ion has been represented as the hexaaqua complex Cu(H2O)62+, which shows the Jahn–Teller distortion effect (Sherman 2001; Bersuker 2006), whereby the two Cu–O distances of the vertical axial bond (Cu–Oax) are longer than four Cu–O distances in the equatorial plane (Cu–Oeq). The Jahn–Teller effect lowers the symmetry of Cu(H2O)62+ from octahedral Th to D2h. The sixfold coordination of hydrated Cu(II) species is questioned by a finding of fivefold coordination (Pasquarello et al. 2001; Chaboy et al. 2006; Little et al. 2014b …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"8 1","pages":"543-600"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84746288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chromium consists of four stable isotopes (50Cr, 52Cr, 53Cr and 54Cr) with natural abundances of 4.35%, 83.79%, 9.50% and 2.36%, respectively (Rossman and Taylor 1998). Among these four isotopes, 50Cr, 52Cr and 54Cr are non-radiogenic, whereas 53Cr is a radiogenic product of the extinct nuclide 53Mn, which has a half-life of 3.7 Myr (Honda and Imamura 1971). Chromium isotope systems have a wide range of applications in geochemistry and cosmochemistry. They have been used to study early solar system processes (e.g., Rotaru et al. 1992); the oxidation/reduction (redox) potential of underground systems, which governs the transport and fate of many contaminants (e.g., Ellis et al. 2002); and more recently, the redox evolution of Earth’s early ocean-atmosphere system, which is intimately linked to the evolution of life (Frei et al. 2009; Crowe et al. 2013; Planavsky et al. 2014; Cole et al. 2016). ### Chemical properties of Cr Chromium is redox-sensitive. In Earth’s near-surface environments, Cr has two main valence states, +3 and + 6, which are expressed as Cr(III) and Cr(VI), respectively. The valence state of Cr is controlled by the prevailing redox potential (Eh) and pH conditions (Fig. 1). Cr(VI) is always bound with O2− to form the oxyanion species CrO42− (chromate), HCrO4− (bichromate), and Cr2O72−(dichromate), all of which are water-soluble. In contrast, Cr3+ usually forms oxyhydroxides or oxides, which are insoluble and immobile in the natural pH range. During oxidative weathering, Cr(III) in minerals can be oxidized by O2 to Cr(VI), a process that is catalyzed by manganese oxides (Fendorf and Zasoski 1992; Economou-Eliopoulos et al. 2014). The Cr(VI) migrates to rivers and eventually to the ocean. In the modern ocean, Cr occurs as both Cr(VI) and …
铬由四种稳定同位素(50Cr、52Cr、53Cr和54Cr)组成，自然丰度分别为4.35%、83.79%、9.50%和2.36% (Rossman and Taylor 1998)。在这四种同位素中，50Cr、52Cr和54Cr是非放射性成因的，而53Cr是已灭绝核素53Mn的放射性成因产物，其半衰期为3.7 Myr (Honda and Imamura 1971)。铬同位素系统在地球化学和宇宙化学中有着广泛的应用。它们已被用于研究早期的太阳系过程(例如，Rotaru et al. 1992);地下系统的氧化/还原(氧化还原)电位，它控制着许多污染物的运输和归宿(例如，Ellis et al. 2002);最近，地球早期海洋-大气系统的氧化还原演化与生命的演化密切相关(Frei et al. 2009;Crowe et al. 2013;Planavsky et al. 2014;Cole et al. 2016)。CrChromium的化学性质对氧化还原敏感。在地球近地表环境中，Cr主要有+3和+ 6两种价态，分别表示为Cr(III)和Cr(VI)。Cr的价态受当前氧化还原电位(Eh)和pH条件的控制(图1)。Cr(VI)总是与O2 -结合形成氧化离子CrO42−(铬酸盐)、HCrO4−(重铬酸盐)和Cr2O72−(重铬酸盐)，它们都是水溶性的。相反，Cr3+通常形成氢氧化物或氧化物，在自然pH范围内不溶且不移动。在氧化风化过程中，矿物中的Cr(III)可被O2氧化为Cr(VI)，这一过程由锰氧化物催化(Fendorf and Zasoski 1992;Economou-Eliopoulos et al. 2014)。Cr(VI)迁移到河流，最终进入海洋。在现代海洋中，Cr以Cr(VI)和…
{"title":"Chromium Isotope Geochemistry","authors":"L. Qin, Xiangli Wang","doi":"10.2138/RMG.2017.82.10","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.10","url":null,"abstract":"Chromium consists of four stable isotopes (50Cr, 52Cr, 53Cr and 54Cr) with natural abundances of 4.35%, 83.79%, 9.50% and 2.36%, respectively (Rossman and Taylor 1998). Among these four isotopes, 50Cr, 52Cr and 54Cr are non-radiogenic, whereas 53Cr is a radiogenic product of the extinct nuclide 53Mn, which has a half-life of 3.7 Myr (Honda and Imamura 1971). Chromium isotope systems have a wide range of applications in geochemistry and cosmochemistry. They have been used to study early solar system processes (e.g., Rotaru et al. 1992); the oxidation/reduction (redox) potential of underground systems, which governs the transport and fate of many contaminants (e.g., Ellis et al. 2002); and more recently, the redox evolution of Earth’s early ocean-atmosphere system, which is intimately linked to the evolution of life (Frei et al. 2009; Crowe et al. 2013; Planavsky et al. 2014; Cole et al. 2016). ### Chemical properties of Cr Chromium is redox-sensitive. In Earth’s near-surface environments, Cr has two main valence states, +3 and + 6, which are expressed as Cr(III) and Cr(VI), respectively. The valence state of Cr is controlled by the prevailing redox potential (Eh) and pH conditions (Fig. 1). Cr(VI) is always bound with O2− to form the oxyanion species CrO42− (chromate), HCrO4− (bichromate), and Cr2O72−(dichromate), all of which are water-soluble. In contrast, Cr3+ usually forms oxyhydroxides or oxides, which are insoluble and immobile in the natural pH range. During oxidative weathering, Cr(III) in minerals can be oxidized by O2 to Cr(VI), a process that is catalyzed by manganese oxides (Fendorf and Zasoski 1992; Economou-Eliopoulos et al. 2014). The Cr(VI) migrates to rivers and eventually to the ocean. In the modern ocean, Cr occurs as both Cr(VI) and …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"84 1","pages":"379-414"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73430398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Magnesium (Mg) has an atomic number of 12 and belongs to the alkaline earth element (Group II) of the Periodic Table. The pure Mg is a silvery white metal and has a melting point of 650 °C and boiling point of 1090 °C at 1 standard atmosphere (Lide 1993–1994). The electronic configuration of Mg is [Ne]3s2, with low ionization energies, which makes Mg ionic in character with a common valance state of 2+ and a typical ionic radius of 0.72 A (Shannon 1976). Magnesium is a major element and widely distributed in the silicate Earth, hydrosphere and biosphere (Fig. 1a). It is the fourth most abundant element in the Earth (after O, Fe and Si, MgO = 25.5 wt%) (McDonough and Sun 1995), the fifth most abundant element in the bulk continental crust (MgO = 4.66 wt%) (Rudnick and Gao 2003) and the second most abundant cation in seawater (after Na, Mg = 0.128 wt%) (Pilson 2013). Nonetheless, the mantle has > 99.9% of Mg in the Earth because of its high MgO content (37.8 wt%, McDonough and Sun 1995) and mass fraction. The high abundance of Mg in the silicate Earth makes it a major constituent of minerals (e.g., olivine, pyroxene, garnet, amphibole, mica, spinel, carbonate, sulfate, and clay minerals) in igneous, metamorphic and sedimentary rocks. Magnesium has three stable isotopes, with mass numbers of 24, 25 and 26, and typical abundances of 78.99%, 10.00% and 11.01%, respectively (Berglund and Wieser 2011) (Fig. 1b), and a standard atomic weight of 24.305 (CIAAW 2015). Because of the limitations in the mass spectrometry, many previous Mg isotopic studies have concentrated on either mass independent isotope anomalies to look for the radiogenic 26Mg produced by the decay of short-lived 26Al (Gray and Compston 1974; Lee and …
镁(Mg)的原子序数为12，属于元素周期表中的碱土元素(族II)。纯Mg是一种银白色金属，熔点为650℃，沸点为1090℃，在1个标准大气压下(Lide 1993-1994)。Mg的电子构型为[Ne]3s2，具有较低的电离能，这使得Mg离子具有2+的共价态和0.72 a的典型离子半径(Shannon 1976)。镁是一种主要元素，广泛分布于硅酸盐土、水圈和生物圈中(图1a)。它是地球上第四丰富的元素(仅次于O, Fe和Si, MgO = 25.5 wt%) (McDonough and Sun 1995)，大陆地壳中第五丰富的元素(MgO = 4.66 wt%) (Rudnick and Gao 2003)，海水中第二丰富的阳离子(仅次于Na, Mg = 0.128 wt%) (Pilson 2013)。尽管如此，由于地幔的高MgO含量(37.8 wt%， McDonough and Sun 1995)和质量分数，地球上的Mg含量> 99.9%。镁在硅酸盐土中的高丰度使其成为火成岩、变质岩和沉积岩中矿物(如橄榄石、辉石、石榴石、角闪孔、云母、尖晶石、碳酸盐、硫酸盐和粘土矿物)的主要成分。镁有三种稳定同位素，质量数分别为24、25和26，典型丰度分别为78.99%、10.00%和11.01% (Berglund and Wieser 2011)(图1b)，标准原子量为24.305 (CIAAW 2015)。由于质谱法的局限性，以前的许多Mg同位素研究都集中在与质量无关的同位素异常上，以寻找由短寿命的26Al衰变产生的放射性成因的26Mg (Gray and Compston 1974;李和……
{"title":"Magnesium Isotope Geochemistry","authors":"F. Teng","doi":"10.2138/RMG.2017.82.7","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.7","url":null,"abstract":"Magnesium (Mg) has an atomic number of 12 and belongs to the alkaline earth element (Group II) of the Periodic Table. The pure Mg is a silvery white metal and has a melting point of 650 °C and boiling point of 1090 °C at 1 standard atmosphere (Lide 1993–1994). The electronic configuration of Mg is [Ne]3s2, with low ionization energies, which makes Mg ionic in character with a common valance state of 2+ and a typical ionic radius of 0.72 A (Shannon 1976). Magnesium is a major element and widely distributed in the silicate Earth, hydrosphere and biosphere (Fig. 1a). It is the fourth most abundant element in the Earth (after O, Fe and Si, MgO = 25.5 wt%) (McDonough and Sun 1995), the fifth most abundant element in the bulk continental crust (MgO = 4.66 wt%) (Rudnick and Gao 2003) and the second most abundant cation in seawater (after Na, Mg = 0.128 wt%) (Pilson 2013). Nonetheless, the mantle has > 99.9% of Mg in the Earth because of its high MgO content (37.8 wt%, McDonough and Sun 1995) and mass fraction. The high abundance of Mg in the silicate Earth makes it a major constituent of minerals (e.g., olivine, pyroxene, garnet, amphibole, mica, spinel, carbonate, sulfate, and clay minerals) in igneous, metamorphic and sedimentary rocks. Magnesium has three stable isotopes, with mass numbers of 24, 25 and 26, and typical abundances of 78.99%, 10.00% and 11.01%, respectively (Berglund and Wieser 2011) (Fig. 1b), and a standard atomic weight of 24.305 (CIAAW 2015). Because of the limitations in the mass spectrometry, many previous Mg isotopic studies have concentrated on either mass independent isotope anomalies to look for the radiogenic 26Mg produced by the decay of short-lived 26Al (Gray and Compston 1974; Lee and …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"258 1","pages":"219-287"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77076888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The first Reviews in Mineralogy volume on the Geochemistry of Non-Traditional Stable Isotopes was compiled before it was appropriate to include a chapter on mercury (Hg) stable isotope geochemistry. At that time there were only a few papers on this new topic (Jackson 2001; Lauretta et al. 2001; Hintelmann and Lu 2003), and there were still some important analytical issues that needed to be resolved. But the field has come a long way in a decade. Now we have a different problem; at our last count there were well over 100 publications utilizing mercury stable isotopes and it is becoming very difficult to synthesize this vast amount of exciting and rapidly developing research. Experimental studies have expanded our knowledge of the mechanisms of mercury isotope fractionation and applications of mercury isotope measurements have touched virtually every area of research in mercury biogeochemistry. There have been a number of previous reviews of the mercury stable isotope literature as it has developed (Ridley and Stetson 2006; Bergquist and Blum 2009; Yin et al. 2010; Blum 2011; Hintelmann 2012; Blum et al. 2014). It is our view that the field has become too large to comprehensively review the entire literature on mercury stable isotopes. Ten years ago Hg isotope researchers were just beginning to explore the boundaries of natural Hg isotope variation and the mechanisms that cause this variation in the environment. At that time large and relatively easily measured isotope signals were of great interest and mercury isotope researchers were beginning to develop theories to explain mass dependent isotope fractionation (MDF) and mass independent isotope fractionation of the odd mass-numbered isotopes of mercury (odd-MIF). More recently researchers have discovered a wider range of types of isotopic variability (even-MIF), some of which are subtle and …
《矿物学评论》第一卷关于非传统稳定同位素的地球化学是在适当地包括汞(Hg)稳定同位素地球化学一章之前编写的。当时关于这个新课题的论文很少(Jackson 2001;Lauretta et al. 2001;Hintelmann and Lu 2003)，还有一些重要的分析问题需要解决。但这一领域在过去十年里取得了长足的进步。现在我们有一个不同的问题;根据我们最近的统计，利用汞稳定同位素的出版物超过100篇，要合成这么多令人兴奋和快速发展的研究成果变得非常困难。实验研究扩大了我们对汞同位素分馏机制的认识，汞同位素测量的应用几乎涉及汞生物地球化学研究的每个领域。随着汞稳定同位素文献的发展，以前已经对汞稳定同位素文献进行了多次审查(Ridley和Stetson 2006;Bergquist and Blum 2009;Yin et al. 2010;布卢姆2011;Hintelmann 2012;Blum et al. 2014)。我们认为，这个领域已经变得太大，无法全面审查有关汞稳定同位素的全部文献。十年前，汞同位素研究人员刚刚开始探索自然汞同位素变化的边界和导致这种环境变化的机制。当时，较大且相对容易测量的同位素信号引起了极大的兴趣，汞同位素研究人员开始发展理论来解释汞的奇质量数同位素的质量依赖同位素分异(MDF)和质量独立同位素分异(odd- mif)。最近，研究人员发现了更广泛类型的同位素变异(甚至是mif)，其中一些是微妙的，而且……
{"title":"Recent Developments in Mercury Stable Isotope Analysis","authors":"J. Blum, Marcus W. Johnson","doi":"10.2138/RMG.2017.82.17","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.17","url":null,"abstract":"The first Reviews in Mineralogy volume on the Geochemistry of Non-Traditional Stable Isotopes was compiled before it was appropriate to include a chapter on mercury (Hg) stable isotope geochemistry. At that time there were only a few papers on this new topic (Jackson 2001; Lauretta et al. 2001; Hintelmann and Lu 2003), and there were still some important analytical issues that needed to be resolved. But the field has come a long way in a decade. Now we have a different problem; at our last count there were well over 100 publications utilizing mercury stable isotopes and it is becoming very difficult to synthesize this vast amount of exciting and rapidly developing research. Experimental studies have expanded our knowledge of the mechanisms of mercury isotope fractionation and applications of mercury isotope measurements have touched virtually every area of research in mercury biogeochemistry. There have been a number of previous reviews of the mercury stable isotope literature as it has developed (Ridley and Stetson 2006; Bergquist and Blum 2009; Yin et al. 2010; Blum 2011; Hintelmann 2012; Blum et al. 2014). It is our view that the field has become too large to comprehensively review the entire literature on mercury stable isotopes. Ten years ago Hg isotope researchers were just beginning to explore the boundaries of natural Hg isotope variation and the mechanisms that cause this variation in the environment. At that time large and relatively easily measured isotope signals were of great interest and mercury isotope researchers were beginning to develop theories to explain mass dependent isotope fractionation (MDF) and mass independent isotope fractionation of the odd mass-numbered isotopes of mercury (odd-MIF). More recently researchers have discovered a wider range of types of isotopic variability (even-MIF), some of which are subtle and …","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"2 1","pages":"733-757"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91203301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Iron is a ubiquitous element with a rich (i.e., complex) chemical behavior. It possesses three oxidation states, metallic iron (Fe), ferrous iron (Fe2+) and ferric iron (Fe3+). The distribution of these oxidation states is markedly stratified in the Earth.
{"title":"Iron Isotope Systematics","authors":"N. Dauphas, S. John, O. Rouxel","doi":"10.2138/RMG.2017.82.11","DOIUrl":"https://doi.org/10.2138/RMG.2017.82.11","url":null,"abstract":"Iron is a ubiquitous element with a rich (i.e., complex) chemical behavior. It possesses three oxidation states, metallic iron (Fe), ferrous iron (Fe2+) and ferric iron (Fe3+). The distribution of these oxidation states is markedly stratified in the Earth.","PeriodicalId":49624,"journal":{"name":"Reviews in Mineralogy & Geochemistry","volume":"10 1","pages":"415-510"},"PeriodicalIF":0.0,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83746073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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