To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Systeme International d'Unites, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/rcm.5129

Guidelines and recommended terms for expression of stable‐isotope‐ratio and gas‐ratio measurement results

The composition of the primitive mantle derived here shows that Earth was assembled from material that shows many of the same chemical fractionation processes as chondritic meteorites. These processes occurred at the initial stage of the solar system formation, under conditions thought to be present in the solar nebula. But the stable isotope record excludes chondritic meteorites as the ‘building blocks’ of Earth. Meteorites formed in local environments separated from that part of the inner solar system where much of the material forming the terrestrial planets was sourced.

https://booksite.elsevier.com/brochures/treatiseongeochemistry/contents/sample2.pdf

Cosmochemical Estimates of Mantle Composition

A-type granites in northeastern China: age and geochemical constraints on their petrogenesis

Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 continue to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 depends on its shorter atmospheric lifetime, stronger warming potential, and variations in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the atmospheric growth rate arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations).

For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (a top-down approach) to be 576 Tg CH4 yr−1 (range 550–594, corresponding to the minimum and maximum estimates of the model ensemble). Of this total, 359 Tg CH4 yr−1 or ∼ 60 % is attributed to anthropogenic sources, that is emissions caused by direct human activity (i.e. anthropogenic emissions; range 336–376 Tg CH4 yr−1 or 50 %–65 %). The mean annual total emission for the new decade (2008–2017) is 29 Tg CH4 yr−1 larger than our estimate for the previous decade (2000–2009), and 24 Tg CH4 yr−1 larger than the one reported in the previous budget for 2003–2012 (Saunois et al., 2016). Since 2012, global CH4 emissions have been tracking the warmest scenarios assessed by the Intergovernmental Panel on Climate Change. Bottom-up methods suggest almost 30 % larger global emissions (737 Tg CH4 yr−1, range 594–881) than top-down inversion methods. Indeed, bottom-up estimates for natural sources such as natural wetlands, other inland water systems, and geological sources are higher than top-down estimates. The atmospheric constraints on the top-down budget suggest that at least some of these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric observation-based emissions indicates a predominance of tropical emissions (∼ 65 % of the global budget, < 30∘ N) compared to mid-latitudes (∼ 30 %, 30–60∘ N) and high northern latitudes (∼ 4 %, 60–90∘ N). The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters.

Some of our global source estimates are smaller than those in previously published budgets (Saunois et al., 2016; Kirschke et al., 2013). In particular wetland emissions are about 35 Tg CH4 yr−1 lower due to improved partition wetlands and other inland waters. Emissions from geological sources and wild animals are also found to be smaller by 7 Tg CH4 yr−1 by 8 Tg CH4 yr−1, respectively. However, the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of emissions from inland waters, highlighting the need for more detailed research on emissions factors. Priorities for improving the methane budget include (i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; (ii) further development of process-based models for inland-water emissions; (iii) intensification of methane observations at local scales (e.g., FLUXNET-CH4 measurements) and urban-scale monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane to improve source partitioning.

/pdf/the-global-methane-budget-2000-2017-mbxchwmkf5.pdf

The global methane budget 2000–2017

The Central Asian Orogenic Belt (CAOB), also known as the Altaid Tectonic Collage, is characterised by a vast distribution of Paleozoic and Mesozoic granitic intrusions. The granitoids have a wide range of compositions and roughly show a temporal evolution from calcalkaline to alkaline to peralkaline series. The emplacement times for most granitic plutons fall between 500 Ma and 100 Ma, but only a small proportion of plutons have been precisely dated. The Nd-Sr isotopic compositions of these granitoids suggest their juvenile characteristics, hence implying a massive addition of new continental crust in the Phanerozoic. In this paper we document the available isotopic data to support this conclusion. Most Phanerozoic granitoids of Central Asia are characterised by low initial Sr isotopic ratios, positive eNd(T) values and young Sm—Nd model ages (TDM) of 300-1200 Ma. This is in strong contrast with the coeval granitoids emplaced in the European Caledonides and Hercynides. The isotope data indicate their ‘juvenile’ character and suggest their derivation from source rocks or magmas separated shortly before from the upper mantle. Granitoids with negative eNd(T) values also exist, but they occur in the environs of Precambrian microcontinental blocks and their isotope compositions may reflect contamination by the older crust in the magma generation processes. The evolution of the CAOB is probably related to accretion of young arc complexes and old terranes (microcontinents). However, the emplacement of large volumes of post-tectonic granites requires another mechanism, probably through a series of processes including underplating of massive basaltic magma, intercalation of basaltic magma with lower crustal granulites, partial melting of the mixed lithologic assemblages leading to generation of granitic liquids, followed by extensive fractional crystallisation. The proportions of the juvenile or mantle component for most granitoids of Central Asia are estimated to vary from 70% to 100%.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0263593300007367

Granitoids of the Central Asian Orogenic Belt and Continental Growth in the Phanerozoic

http://people.earth.yale.edu/sites/default/files/files/Affek/Ghosh%20et%20al%202006%20D47%20carbonate%20method.pdf

13 C- 18 O bonds in carbonate minerals: A new kind of paleothermometer

A basic theoretical understanding of stable isotope fractionations can help researczzzhers plan and interpret both laboratory experiments and measurements on natural samples. The goal of this chapter is to provide an introduction to stable isotope fractionation theory, particularly as it applies to mass-dependent fractionations of non-traditional elements and materials. Concepts are illustrated using a number of worked examples. For most elements, and typical terrestrial temperature and pressure conditions, equilibrium isotopic fractionations are caused by the sensitivities of molecular and condensed-phase vibrational frequencies to isotopic substitution. This is explained using the concepts of vibrational zero-point energy and the partition function, leading to Urey’s (1947) simplified equation for calculating isotopic partition function ratios for molecules, and Kieffer’s (1982) extension to condensed phases. Discussion will focus on methods of obtaining the necessary input data (vibrational frequencies) for partition function calculations. Vibrational spectra have not been measured or are incomplete for most of the substances that Earth scientists are interested in studying, making it necessary to estimate unknown frequencies, or to measure them directly. Techniques for estimating unknown frequencies range from simple analogies to well-studied materials to more complex empirical force-field calculations and ab initio quantum chemistry. Mossbauer spectroscopy has also been used to obtain the vibrational properties of some elements, particularly iron, in a variety of compounds. Some kinetic isotopic fractionations are controlled by molecular or atomic translational velocities; this class includes many diffusive and evaporative fractionations. These fractionations can be modeled using classical statistical mechanics. Other kinetic fractionations may result from the isotopic sensitivity of the activation energy required to achieve a transition state, a process that (in its simplest form) can be modeled using a modification of Urey’s equation (Bigeleisen 1949).

Theoretical estimates of isotopic fractionations are particularly powerful in systems that are difficult to characterize experimentally, or when empirical …

Applying Stable Isotope Fractionation Theory to New Systems

Role of nuclear volume in driving equilibrium stable isotope fractionation of mercury, thallium, and other very heavy elements

Preferential formation of 13C–18O bonds in carbonate minerals, estimated using first-principles lattice dynamics

The Earth and Moon have iron isotopic abundances that are slightly 'heavy' compared with Mars, the asteroid Vesta and primitive meteorites. The reason for this has been unclear. One suggestion is that there was a large-scale isotopic equilibration during the 'giant impact', the collision between the early Earth and a Mars-sized body that created the Moon, but this has seemed unlikely given that most other elements do not show the effect. An analysis of 44 meteorite and terrestrial samples now shows that the silicon isotopic compositions of basaltic rocks from the Earth and Moon are also distinctly heavy. The finding is consistent with the isotopic equilibration model, and it suggests that silicon was already partitioned into the Earth's core as a light element before the Moon formed. The silicon isotopic compositions of basaltic rocks from the Earth and Moon are distinctly 'heavy'. The similar isotopic composition of the bulk silicate Earth and the Moon are consistent with large-scale isotopic equilibration during the 'giant impact', indicating that Si was already a light element in the Earth's core before the Moon formed. Small isotopic differences between the silicate minerals in planets may have developed as a result of processes associated with core formation, or from evaporative losses during accretion as the planets were built up. Basalts from the Earth and the Moon do indeed appear to have iron isotopic compositions that are slightly heavy relative to those from Mars, Vesta and primitive undifferentiated meteorites1,2,3,4 (chondrites). Explanations for these differences have included evaporation during the ‘giant impact’ that created the Moon (when a Mars-sized body collided with the young Earth). However, lithium5 and magnesium6, lighter elements with comparable volatility7,8,9, reveal no such differences, rendering evaporation unlikely as an explanation. Here we show that the silicon isotopic compositions of basaltic rocks from the Earth and the Moon are also distinctly heavy. A likely cause is that silicon is one of the light elements in the Earth’s core. We show that both the direction and magnitude of the silicon isotopic effect are in accord with current theory10 based on the stiffness of bonding in metal and silicate. The similar isotopic composition of the bulk silicate Earth and the Moon is consistent with the recent proposal11 that there was large-scale isotopic equilibration during the giant impact. We conclude that Si was already incorporated as a light element in the Earth’s core before the Moon formed.

Edwin A. Schauble

Papers

13 C- 18 O bonds in carbonate minerals: A new kind of paleothermometer

Applying Stable Isotope Fractionation Theory to New Systems

Role of nuclear volume in driving equilibrium stable isotope fractionation of mercury, thallium, and other very heavy elements

Preferential formation of 13C–18O bonds in carbonate minerals, estimated using first-principles lattice dynamics

Silicon in the Earth's core.