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Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)

Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

Pure and Applied Chemistry

Atomic weights of the elements 2013 (IUPAC Technical Report)

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of 19 elements. The standard atomic weights of four elements have been revised based on recent determinations of isotopic abundances in natural terrestrial materials: cadmium to 112.414(4) from 112.411(8), molybdenum to 95.95(1) from 95.96(2), selenium to 78.971(8) from 78.96(3), and thorium to 232.0377(4) from 232.038 06(2). The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) also revised the standard atomic weights of fifteen elements based on the 2012 Atomic Mass Evaluation: aluminium (aluminum) to 26.981 5385(7) from 26.981 5386(8), arsenic to 74.921 595(6) from 74.921 60(2), beryllium to 9.012 1831(5) from 9.012 182(3), caesium (cesium) to 132.905 451 96(6) from 132.905 4519(2), cobalt to 58.933 194(4) from 58.933 195(5), fluorine to 18.998 403 163(6) from 18.998 4032(5), gold to 196.966 569(5) from 196.966 569(4), holmium to 164.930 33(2) from 164.930 32(2), manganese to 54.938 044(3) from 54.938 045(5), niobium to 92.906 37(2) from 92.906 38(2), phosphorus to 30.973 761 998(5) from 30.973 762(2), praseodymium to 140.907 66(2) from 140.907 65(2), scandium to 44.955 908(5) from 44.955 912(6), thulium to 168.934 22(2) from 168.934 21(2), and yttrium to 88.905 84(2) from 88.905 85(2). The Commission also recommends the standard value for the natural terrestrial uranium isotope ratio, N ( 238 U)/ N ( 235 U)=137.8(1).

Pure and Applied Chemistry

Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Any desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.

Pure and Applied Chemistry

Clarification of the term “normal material” used for standard atomic weights (IUPAC Technical Report)

The standard atomic weights of the elements apply to normal materials. Since 1984, the Commission on Isotopic Abundances and Atomic Weights (Commission) has defined a normal material as: “The material is a reasonably possible source for this element or its compounds in commerce, for industry or science; the material is not itself studied for some extraordinary anomaly and its isotopic composition has not been modified significantly in a geologically brief period.” The term “a geologically brief period” in this definition is confusing, and confusion can be reduced by revising this definition to the following, which was accepted by the Commission on Isotopic Abundances and Atomic Weights at its meeting in Groningen, Netherlands in September 2017: “ Normal materials include all substances, except (1) those subjected to substantial deliberate, undisclosed, or inadvertent artificial isotopic modification, (2) extraterrestrial materials, and (3) isotopically anomalous specimens, such as natural nuclear reactor products from Oklo (Gabon) or other unique occurrences.”

Pure and Applied Chemistry

Variation of lead isotopic composition and atomic weight in terrestrial materials (IUPAC Technical Report)

The isotopic composition and atomic weight of lead are variable in terrestrial materials because its three heaviest stable isotopes are stable end-products of the radioactive decay of uranium ( 238 U to 206 Pb; 235 U to 207 Pb) and thorium ( 232 Th to 208 Pb). The lightest stable isotope, 204 Pb, is primordial. These variations in isotope ratios and atomic weights provide useful information in many areas of science, including geochronology, archaeology, environmental studies, and forensic science. While elemental lead can serve as an abundant and homogeneous isotopic reference, deviations from the isotope ratios in other lead occurrences limit the accuracy with which a standard atomic weight can be given for lead. In a comprehensive review of several hundred publications and analyses of more than 8000 samples, published isotope data indicate that the lowest reported lead atomic weight of a normal terrestrial materials is 206.1462 ± 0.0028 ( k = 2), determined for a growth of the phosphate mineral monazite around a garnet relic from an Archean high-grade metamorphic terrain in north-western Scotland, which contains mostly 206 Pb and almost no 204 Pb. The highest published lead atomic weight is 207.9351 ± 0.0005 ( k = 2) for monazite from a micro-inclusion in a garnet relic, also from a high-grade metamorphic terrain in north-western Scotland, which contains almost pure radiogenic 208 Pb. When expressed as an interval, the lead atomic weight is [206.14, 207.94]. It is proposed that a value of 207.2 be adopted for the single lead atomic-weight value for education, commerce, and industry, corresponding to previously published conventional atomic-weight values.

Pure and Applied Chemistry

Reference materials for phase equilibrium studies. 2. Solid–liquid equilibria (IUPAC Technical Report)

This article is the second of three projected IUPAC Technical Reports on reference materials for phase equilibrium studies. The goal of this project was to select reference systems with critically evaluated property values for the verification of instruments and techniques used in phase equilibrium studies of mixtures. This report proposes seven systems for solid–liquid equilibrium studies, covering the four most common categories of binary mixtures: aqueous systems with organic solutes, aqueous systems with inorganic solutes, non-aqueous systems, and systems with low solubility. For each system, the available literature sources, accepted data, smoothing equations, and estimated uncertainties are given.

Pure and Applied Chemistry

Impact of pore fluid chemistry on fine-grained sediment fabric and compressibility

Fines, defined here as grains or particles, less than 75 μm in diameter, exist nearly ubiquitously in natural sediment, even those classified as coarse. Macroscopic sediment properties, such as compressibility, which relates applied effective stress to the resulting sediment deformation, depend on the fabric of fines. Unlike coarse grains, fines have sizes and masses small enough to be more strongly influenced by electrical interparticle forces than by gravity. These electrical forces acting through pore fluids are influenced by pore fluid chemistry changes. Macroscopic property dependence on pore fluid chemistry must be accounted for in sediment studies involving subsurface flow and sediment stability analyses, as well as in engineered flow situations such as groundwater pollutant remediation, hydrocarbon migration, or other energy resource extraction applications. This study demonstrates how the liquid limit‐based electrical sensitivity index can be used to predict sediment compressibility changes due to pore fluid chemistry changes. Laboratory tests of electrical sensitivity, sedimentation, and compressibility illustrate mechanisms linking microscale and macroscale processes for selected pure, end‐member fines. A specific application considered here is methane extraction via depressurization of gas hydrate‐bearing sediment, which causes a dramatic pore water salinity drop concurrent with sediment being compressed by the imposed effective stress increase.

Journal of Geophysical Research

Special issue: Terrestrial fluids, earthquakes and volcanoes: The Hiroshi Wakita volume I

Terrestrial Fluids, Earthquakes and Volcanoes: The Hiroshi Wakita Volume I is a special publication to honor Professor Hiroshi Wakita for his scientific contributions. This volume consists of 17 original papers dealing with various aspects of the role of terrestrial fluids in earthquake and volcanic processes, which reflect Prof. Wakita’s wide scope of research interests. Professor Wakita co-founded the Laboratory for Earthquake Chemistry in 1978 and served as its director from 1988 until his retirement from the university in 1997. He has made the laboratory a leading world center for studying earthquakes and volcanic activities by means of geochemical and hydrological methods. Together with his research team and a number of foreign guest researchers that he attracted, he has made many significant contributions in the above-mentioned scientific fields of interest. This achievement is a testimony to not only his scientific talent, but also his enthusiasm, his open mindedness, and his drive in obtaining both human and financial support.

Pure and Applied Geophysics

Transport of chromium and selenium in a pristine sand and gravel aquifer: Role of adsorption processes

Field transport experiments were conducted in an oxic sand and gravel aquifer using Br (bromide ion), Cr (chromium, injected as Cr(VI)), Se (selenium, injected as Se(VI)), and other tracers. The aquifer has mildly acidic p H values and low concentrations of dissolved salts. Within analytical errors, all mobile Cr was present as Cr(VI). All mobile Se was probably present as Se(VI). Adsorption of Cr and Se onto aquifer sediments caused retardation of both tracers. Breakthrough curves for Cr and Se had extensive tails, which caused large decreases in their maximum concentrations relative to the nonreactive Br tracer after only 2.0 m of transport. A surface complexation model was applied to the results of laboratory studies of Cr(VI) adsorption on aquifer solids from the site based on adsorption onto hydrous ferric oxide. The modeling results suggested that the dominant adsorbents in the aquifer solids have lower affinities for anion adsorption than pure hydrous ferric oxide. The steep rising limbs and extensive tails observed in most of the breakthrough curves are qualitatively consistent with the equilibrium surface complexation model; however, slow rates of adsorption and desorption may have contributed to these features. Variations during transport in the concentrations of Cr, Se, and other anions competing for adsorption sites likely gave rise to variations in the extent of adsorption. Adequate description of the observed retardation of Cr and Se would require a coupled transport-adsorption model that can account for these effects. Companion experiments in the mildly reducing zone of the aquifer (Kent et al., 1994) showed a loss of Cr mass, probably resulting from reduction to Cr(III), and little retardation of mobile Cr and Se during transport; this contrast illustrates the influence of aquifer chemistry on the transport of redox-sensitive solutes.

Water Resources Research

Summary of the history and research of the U.S. Geological Survey gas hydrate properties laboratory in Menlo Park, California, active from 1993 to 2022

The U.S. Geological Survey (USGS) Clathrate Hydrate Properties Project, active from 1993 to 2022 in Menlo Park, California, stemmed from an earlier project on the properties of planetary ices supported by the National Aeronautics and Space Administration’s (NASA’s) Planetary Geology and Geophysics Program. We took a material science approach in both projects, emphasizing chemical purity of samples, having controlled grain size and grain texture, and having verified crystal structures and phase relations. A foundational contribution from our USGS Gas Hydrate Properties Laboratory (GHPL) was in demonstrating the ability to reproducibly create such pure clathrate hydrate samples for study. Clathrate sample synthesis was achieved by heating sieved and weighed pure granular water ice in the presence of cold clathrate-forming gas or liquid. During heating, the ice melts at the grain scale and reacts with the gas to form clathrate. The resulting material has the desired uniformity and purity, with known intergranular porosity; our subsequent measurements showed that these clathrates exhibited the established clathrate structures and phase relations. This novel synthesis method was successful in creating clathrates of pure methane, ethane, propane, carbon dioxide, and multi-component gases. By mixing sand or silt with granular ice, we were also able to make clathrate-sediment aggregates with controlled grain textures. This simple method, adopted by many others in the community, permitted us to measure the physical and chemical properties of well-characterized and well-crystallized clathrates and clathrate/sediment aggregates. At about the same time, we adapted conventional scanning electron microscopy to cryogenic conditions for analysis of grain-scale characteristics of clathrates made in the GHPL as well as those collected from nature by drill core. The uniformity and reproducibility of our samples also allowed us to investigate how clathrates respond to environmental changes in chemistry, temperature, and pressure: we measured chemical exchange rates with dissolved gas species—such as noble gases and chlorofluorocarbons—as well as rates of clathrate dissolution and decomposition. These advances include the first accurate mapping of the conditions that promote the remarkable process of “anomalous preservation” at room pressure, a metastability that offers potential application for low-cost and safe transportation of natural gas from gas fields far from pipelines. Another advancement stemming from the GHPL was the compaction of as-synthesized porous clathrates to nearly full density by applying external pressure using three different techniques. Compaction allows for high-accuracy measurements of many fundamental physical and chemical properties of these materials, such as elastic wavespeeds and moduli, complete thermal properties, decomposition rates, thermal expansion, and clathrate equations of state. These properties and others, in turn, have helped USGS scientists to interpret geophysical well logs and active geophysical surveys, as well as model the rates of gas production from hydrate deposits in nature. Studying this class of icy minerals that occur in abundance on Earth and in the outer solar system has been a fascinating laboratory journey. Here, we summarize the history and major findings of the USGS GHPL in Menlo Park, including both in-house research as well as findings from the synergistic collaborations with other agencies and institutes that were key to the success of our laboratory. The Menlo Park GHPL was more formally incorporated within the USGS Gas Hydrates Project, a collaboration among multiple USGS Science Centers, in the early 2000s under the leadership of Deborah Hutchinson, and now under the leadership of Carolyn Ruppel and Timothy Collett.

Open-File Report

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Applied Geochemistry

Characteristics and environmental aspects of slag: a review

Slag is a waste product from the pyrometallurgical processing of various ores. Based on over 150 published studies, this paper provides an overview of mineralogical and geochemical characteristics of different types of slag and their environmental consequences, particularly from the release of potentially toxic elements to water. This chapter reviews the characteristics of both ferrous (steel and blast furnace Fe) and non-ferrous (Ag, Cu, Ni, Pb, Sn, Zn) slag. Interest in slag has been increasing steadily as large volumes, on the order of hundreds of millions of tonnes, are produced annually worldwide. Research on slag generally focuses on potential environmental issues related to the weathering of slag dumps or on its utility as a construction material or reprocessing for secondary metal recovery. The chemistry and mineralogy of slag depend on the metallurgical processes that create the material and will influence its fate as waste or as a reusable product. The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO 2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

Applied Geochemistry