Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 degrees C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 degrees C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product gamma Gamma of activity coefficients x evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta's building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and delta K-41 and delta Rb-87 isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (similar to 1050 degrees C) in a medium similar to 98.8% saturated.

The isotopic compositions of alkali metal elements are powerful tracers of various geological processes. Coupled K and Rb isotopic studies can potentially yield new clues on the mechanisms responsible for the depletions in moderately volatile elements in planetary objects, global surface geochemical cycles, and mechanistic aspects of water-rock interactions. Rubidium isotopic studies have however been hampered by difficulties in purifying Rb from rocks, notably due to its similar chemical behavior to K. Here we characterize the properties of three different types of resins (AMP-PAN resin; AG50W-X8 and AG50W-X12 cation-exchange resins; Sr resin) for Rb and K purification. We show that AMP-PAN resin and Sr resin can readily separate Rb from K and other matrix elements. However, AMP-PAN resin has a high Rb blank (similar to 80 ng) and is cumbersome to use, which limits its applicability. For cation resins, we test the effects of column length, acid molarity, temperature, pressure drop (flow rate), and resin cross-linkage on the Rb separation using a Fluoropolymer Pneumatic Liquid Chromatography (FPLC) unit built in our laboratory. Increasing column length or resin cross-linkage has a positive effect on the separation, while increasing acid molarity, temperature, or pressure drop (flow rate) has negative impacts. Gravity-driven cation-exchange resin columns fail to cleanly separate Rb from K, but an AG50W-X12 resin column of 150 cm length and 0.16 cm inner diameter installed on a FPLC unit can cleanly separate Rb from K. We separated Rb from synthetic and natural rock samples using three different purification schemes designed based on the three types of resins, and measured the Rb isotopic compositions of the Rb separates by MC-ICPMS. The three methods yielded consistent results, demonstrating the efficacy of our Rb separation and the accuracy of our Rb isotopic analyses. The Rb isotopic compositions of several geostandards were analyzed (BCR-2, BHVO-2, BE-N, AGV-2, GS-N, G-3, and G-A), which can be used in future studies for ground-truthing methodologies used for studying natural samples. Among the three methods, the Sr resin method is the most straightforward for purifying Rb and K simultaneously, and measuring their isotopic compositions in natural samples.

Rare Earth Elements (REEs) are commonly utilized in Earth and environmental sciences to study a variety of geological processes due to their distinct patterns and radioactive-radiogenic decay systems (147Sm-143Nd, 146Sm-142Nd, 138La-138Ce). Advances in analytical techniques now enable the use of REE stable isotopic fractionations to clarify lingering ambiguities in REE systematics. In this study, we employed Nuclear Resonant Inelastic X-ray Scattering (NRIXS) to study the phonon density of states of 151Eu and 161Dy in several pure compounds, as well as in synthetic basalt and andesite glasses, and rhyolite glasses produced under various redox conditions, to determine equilibrium isotopic fractionation factors for the REEs. We additionally utilized Density Functional Theory with a Hubbard U correction (DFT+U) to calculate these factors. Our findings indicate that the directionally averaged mean force constant of Dy3+ is -270 N/m across various compounds, while those of Eu2+ and Eu3+ are -83 and 214 N/m, respectively, in geologically relevant glasses and other pure compounds. These force constants were then used to estimate those of all REEs using scaling arguments. The results suggest that equilibrium isotopic fractionation should be limited for REEs in igneous rocks, allowing for the interpretation of REE isotopic fractionation in these rocks and minerals as a result of kinetic effects. This could facilitate understanding the role of diffusion in igneous rocks and ore formation. Additionally, our results imply that significant Eu isotopic fractionation could exist in hydrothermal fluids, which could aid in understanding the formation of ore deposits and REE cycling in the oceans.

Aerosols interact with radiation and clouds. Substantial progress made over the past 40 years in observing, understanding, and modeling these processes helped quantify the imbalance in the Earth's radiation budget caused by anthropogenic aerosols, called aerosol radiative forcing, but uncertainties remain large. This review provides a new range of aerosol radiative forcing over the industrial era based on multiple, traceable, and arguable lines of evidence, including modeling approaches, theoretical considerations, and observations. Improved understanding of aerosol absorption and the causes of trends in surface radiative fluxes constrain the forcing from aerosol-radiation interactions. A robust theoretical foundation and convincing evidence constrain the forcing caused by aerosol-driven increases in liquid cloud droplet number concentration. However, the influence of anthropogenic aerosols on cloud liquid water content and cloud fraction is less clear, and the influence on mixed-phase and ice clouds remains poorly constrained. Observed changes in surface temperature and radiative fluxes provide additional constraints. These multiple lines of evidence lead to a 68% confidence interval for the total aerosol effective radiative forcing of -1.6 to -0.6Wm(-2), or -2.0 to -0.4Wm(-2) with a 90% likelihood. Those intervals are of similar width to the last Intergovernmental Panel on Climate Change assessment but shifted toward more negative values. The uncertainty will narrow in the future by continuing to critically combine multiple lines of evidence, especially those addressing industrial-era changes in aerosol sources and aerosol effects on liquid cloud amount and on ice clouds.

This article presents a critical assessment of 40 years of research that may be brought under the umbrella of energy efficiency, spanning different aggregations and domains-from individual producing and consuming agents to economy-wide effects to the role of innovation to the influence of policy. After 40 years of research, energy efficiency initiatives are generally perceived as highly effective. Innovation has contributed to lowering energy technology costs and increasing energy productivity. Energy efficiency programs in many cases have reduced energy use per unit of economic output and have been associated with net improvements in welfare, emission reductions, or both. Rebound effects at the macro level still warrant careful policy attention, as they may be nontrivial. Complexity of energy efficiency dynamics calls for further methodological and empirical advances, multidisciplinary approaches, and granular data at the service level for research in this field to be of greatest societal benefit.

Chlorite has long been considered a mineral group likely to have different trace element chemistry with proximity to mineralization, and therefore can be used to vector towards ore bodies. However, due to their geochemical complexity, it has proven challenging to develop a simple vectoring method based on the variation in abundance of one or a few chemical elements or isotopes. Machine learning, specifically cluster analysis, provides a potential mathematical tool for characterizing multidimensional geochemical correlations with proximity to mineralization. In this contribution we conducted a cluster analysis on 23 elements from 1,679 distinct chlorite sample analyses. The combination of this clustering technique with classification by proximity to the ore body, 1) explores and characterizes the nature of chlorite composition and proximity to ore bodies and 2) tests the efficacy of clustering-classification methods to predict whether a chlorite sample is near to an ore body. We found that chlorite chemistry is more strongly controlled by deposit type than proximity to mineralization and that cluster analysis of chlorite trace element content is likely not a viable way to develop vectors towards porphyry mineralization.

A systematic survey of 161 known and postulated minerals originating on Mars points to 20 different mineral-forming processes (paragenetic modes), which are a subset of formation modes observed on Earth. The earliest martian minerals, as on Earth, were primary phases from mafic igneous rocks and their ultramafic cumulates. Subsequent primary igneous minerals were associated with products of limited fractional crystallization, including alkaline and quartz-normative lithologies. Significant mineral diversification occurred via precipitation of primary phases from aqueous and atmospheric fluids, including authigenesis, hydrothermal and cryogenic precipitation, and evaporites, including freeze drying during eras of low atmospheric pressures. In particular, hydrothermal mineral formation associated with both volcanic fluids and sustained hydrothermal activity in impact fracture zones may have triggered significant mineral diversification, though as yet undocumented. At least 65 such primary minerals have been identified by flown missions to Mars and from martian meteorites. A host of secondary martian minerals were produced by near-surface processes related to water/rock interactions, including hydration/dehydration, oxidation/reduction, serpentinization, metasomatism, and a variety of diagenetic alterations. Additional mineral diversity resulted from metamorphic events, including thermal and shock metamorphism, lightning, and bolide impacts. However, several dominant sources of mineral diversity on Earth, including (a) extensive fluid/rock interactions and element concentration associated with plate tectonics; (b) high-pressure regional metamorphism associated with plate tectonics; and (c) biologically mediated mineralization-are not known to be in play on Mars. Consequently, we estimate the total mineral diversity of Mars to be an order of magnitude smaller than on Earth.Plain Language Summary A half-century of investigations of the martian surface by orbiters, landers, and rovers, amplified by studies of martian meteorites, reveal more than 160 confirmed or likely minerals. These diverse phases represent a range of at least 20 mineral-forming processes, including the production of dozens of primary igneous, sedimentary, and near-surface metamorphic rocks, as well as numerous secondary weathering and alteration minerals. In many respects, the more than 4.5-billion-year mineral evolution of Mars mirrors that of Earth and other terrestrial planets and moons. In each case, the earliest stages of igneous activity are followed by a sequence of primary and secondary mineral formation mechanisms. A key finding is that the mineralogy of Mars is significantly less diverse than that of Earth. Several dominant sources of mineral diversity on Earth, including (a) extensive fluid/rock interactions and element concentration associated with plate tectonics; (b) high-pressure regional metamorphism; and (c) biologically mediated mineralization-are not known to have occurred on Mars. Consequently, we estimate the total mineral diversity of Mars to be an order of magnitude smaller than on Earth.