In the last decade, several studies have reported enrichments of the heavy isotopes of moderately volatile elements in lunar mare basalts. However, the mechanisms controlling the isotope fractionation are still debated and may differ for elements with variable geochemical behaviour. Here, we present a new comprehensive dataset of mass-dependent copper isotope compositions (delta 65Cu) of 30 mare basalts sampled during the Apollo missions. The new delta 65Cu data range from +0.14 %o to +1.28 %o (with the exception of two samples at 0.01 %o and -1.42 %o), significantly heavier than chondrites and the bulk silicate Earth. A comparison with mass fractions of major and trace elements and thermodynamic constraints reveals that Cu isotopic variations within different mare basalt suites are mostly unrelated to fractional crystallisation of silicates or oxides and late-stage magmatic degassing. Instead, we propose that the delta 65Cu average of each suite is representative of the composition of its respective mantle source. The observed differences across geographically and temporally distinct mare basalt suites, suggest that this variation relates to large-scale processes that formed isotopically distinct mantle sources. Based on a Cu isotope fractionation model during metal melt saturation in crystal mush zones of the lunar magma ocean, we propose that distinct delta 65Cu compositions and Cu abundances of mare basalt mantle sources reflect local metal melt-silicate melt equilibration and trapping of metal in mantle cumulates during lunar magma ocean solidification. Differences in delta 65Cu and mass fractions and ratios of siderophile elements between low- and high-Ti mare basalt sources reflect the evolving compositions of both metal and silicate melt during the late cooling stages of the lunar magma ocean.

Distinguishing the origin of lunar water ice requires in situ isotopic measurements with high sensitivity and robustness under extreme lunar conditions; however, challenges such as uncertain water contents and isotopic fractionation induced by regolith particles restrict isotopic analysis. Herein, we present a miniaturized tunable diode laser absorption spectrometer (TDLAS) developed as the core prototype for the Chang'E-7 Lunar Soil Water Molecule Analyzer (LSWMA). The wavelength range of the instrument is 3659.5-3662.0 cm-1, and the system integrates a Herriott cell for stable multi-isotope (H2 16O, H2 18O, H2 17O, and HD16O) detection and employs regolith samples of known isotopic experiments to quantify adsorption-induced fractionation. Performance evaluations demonstrated a dynamic water detection range of 0.01-2 wt % and isotope precision up to 1.3 parts per thousand for delta D (30.5 s), 0.77 parts per thousand for delta 18O (36 s), and 0.75 parts per thousand for delta 17O (21.5 s) with extended averaging. Repeated injections of three types of standard water revealed a volume-dependent deviation (Delta delta D up to -59.5 parts per thousand) attributed to multilayer adsorption effects, while simulated lunar soil experiments identified additional isotopic fractionation (Delta delta D up to -12.8 parts per thousand) caused by particle binding. These results validate the ability of the spectrometer to resolve subtle isotopic shifts under lunar conditions, providing critical data for distinguishing water origins and advancing future resource utilization strategies.

The extent of moderately volatile elements (MVE) depletion and its effects on the Moon's evolutionary history remain contentious, partly due to unintentionally biased sampling by the Apollo missions from the Procellarum KREEP Terrane. In this study, we analyzed the Zn and K isotope compositions of a series of lunar basaltic meteorites, which vary in Th content and are likely to represent a broader sampling range than previous studies, including samples from the far side of the Moon. Our findings indicate remarkably consistent Zn and K isotope compositions across all lunar basalt types, despite significant variations in Th content. This consistency suggests a relatively homogeneous isotopic composition of volatile elements within the Moon, unaffected by subsequent impact events that formed major basins. Our results suggest that the estimates of MVE abundance and isotopic compositions from the Apollo returned samples are likely representative of the bulk Moon, supporting a globally volatile-depleted lunar interior.

Space weathering has long been known to alter the chemical and physical properties of the surfaces of airless bodies such as the Moon. The isotopic compositions of moderately volatile elements in lunar regolith samples could serve as sensitive tracers for assessing the intensity and duration of space weathering. In this study, we develop a new quantitative tool to study space weathering and constrain surface exposure ages based on potassium isotopic compositions of lunar soils. We first report the K isotopic compositions of 13 bulk lunar soils and 20 interval soil samples from the Apollo 15 deep drill core (15004-15006). We observe significant K isotope fractionation in these lunar soil samples, ranging from 0.00 %o to + 11.77 %o, compared to the bulk silicate Moon (-0.07 +/- 0.09 %o). Additionally, a strong correlation between soil maturity (Is/FeO) and K isotope fractionation is identified for the first time, consistent with other isotope systems of moderately volatile elements such as S, Cu, Zn, Se, Rb, and Cd. Subsequently, we conduct numerical modeling to better constrain the processes of volatile element depletion and isotope fractionation on the Moon and calculate a new K Isotope Model Exposure Age (KIMEA) through this model. We demonstrate that this KIMEA is most sensitive to samples with an exposure age lower than 1,000 Ma and becomes less effective for older samples. This novel K isotope tool can be utilized to evaluate the surface exposure ages of regolith samples on the Moon and potentially on other airless bodies if calibrated using other methods (e.g., cosmogenic noble gases) or experimental data.

The abundances and isotopic signatures of volatile elements provide critical information for understanding the delivery of water and other essential life-giving compounds to planets. It has been demonstrated that the Moon is depleted in moderately volatile elements (MVE), such as Zn, Cl, S, K and Rb, relative to the Earth. The isotopic compositions of these MVE in lunar rocks suggest loss of volatile elements during the formation of the Moon, as well as their modification during later differentiation and impact processes. Due to its moderately volatile and strongly chalcophile behaviour, copper (Cu) provides a distinct record of planetary accretion and differentiation processes relative to Cl, Rb, Zn or K. Here we present Cu isotopic compositions of Apollo 11, 12, 14 and 15 mare basalts and lunar basaltic meteorites, which range from delta 65Cu of +0.55 +/- 0.01 %o to +3.94 +/- 0.04 %o (per mil deviation of the 65Cu/63Cu from the NIST SRM 976 standard), independent of mare basalt Ti content. The delta 65Cu values of the basalts are negatively correlated with their Cu contents, which is interpreted as evidence for volatile loss upon mare basalt emplacement, plausibly related to the presence Cl- and S-bearing ligands in the vapour phase. This relationship can be used to determine the Cu isotopic composition of the lunar mantle to a delta 65Cu of +0.57 +/- 0.15 %o. The bulk silicate Moon (BSM) is 0.5%o heavier than the bulk silicate Earth (+0.07 +/- 0.10 %o) or chondritic materials (from -1.45 +/- 0.08 %o to 0.07 +/- 0.06 %o). Owing to the ineffectiveness of sulfide segregation and lunar core formation in inducing Cu isotopic fractionation, the isotopic difference between the Moon and the Earth is attributed to volatile loss during the Moon-forming event, which must have occurred at- or nearequilibrium.

Space weathering alters the surface materials of airless planetary bodies; however, the effects on moderately volatile elements in the lunar regolith are not well constrained. For the first time, we provide depth profiles for stable K and Fe isotopes in a continuous lunar regolith core, Apollo 17 double drive tube 73001/2. The top of the core is enriched in heavy K isotopes (delta 41K = 3.48 +/- 0.05 parts per thousand) with a significant trend toward lighter K isotopes to a depth of 7 cm; while the lower 44 cm has only slight variation with an average delta 41K value of 0.15 +/- 0.05 parts per thousand. Iron, which is more refractory, shows only minor variation; the delta 56Fe value at the top of the core is 0.16 +/- 0.02 parts per thousand while the average bottom 44 cm is 0.11 +/- 0.03 parts per thousand. The isotopic fractionation in the top 7 cm of the core, especially the K isotopes, correlates with soil maturity as measured by ferromagnetic resonance. Kinetic fractionation from volatilization by micrometeoroid impacts is modeled in the double drive tube 73001/2 using Rayleigh fractionation and can explain the observed K and Fe isotopic fractionation. Effects from cosmogenic 41K (from decay of 41Ca) were calculated and found to be negligible in 73001/2. In future sample return missions, researchers can use heavy K isotope signatures as tracers of space weathering effects.

The discharge of fertilizers and untreated sewage from the Indian subcontinent was attributed to damage the coastal ecosystem and threat to the fishery resources. Based on the recent data collected along the Indian coasts, the issues were reanalyzed to identify potential mechanisms responsible. Carbon, nitrogen and oxygen isotopes revealed that the fertilizers used in the agricultural soil contaminate groundwaters, then fluxed to the coastal ocean. Similarly, the impact of municipal sewage is restricted close to the coast rather than spreading to the international waters. This reanalysis suggests that the occurrence of coastal eutrophication, hypoxia or shift in the ecosystem was mainly caused by natural processes such as coastal upwelling, stratification and reversing of coastal currents than hitherto hypothesized as the discharge of fertilizers and municipal sewage.

Despite early hydrological studies of 234U/238U in groundwaters, their utilization as a paleoclimatic proxy in stalagmites has remained sporadic. This study explores uranium isotope ratios in 235 datings (230Th) from six stalagmites in Ejulve cave, northeastern Iberia, covering the last 260 ka. The observed 234U enrichment is attributed to selective leaching of 234U from damaged lattice sites, linked to the number of microfractures in the drip route and wetness frequency, which under certain conditions, may result in the accumulation of 234U recoils. This selective leaching process diminishes with enhanced bedrock dissolution, leading to low S234U. Temperature variations significantly influence bedrock dissolution intensity. During stadial periods and glacial maxima, lower temperatures likely reduced vegetation and respiration rates, thereby decreasing soil CO2 and overall rock dissolution rates. This reduction could enhance the preferential leaching of 234U from bedrock surfaces due to lower bulk rock dissolution. Additionally, the temperature regime during cold periods may have facilitated more frequent freeze-thaw cycles, resulting in microfracturing and exposure of fresh surfaces. Conversely, warmer temperatures increased soil respiration rates and soil CO2, accelerating rock dissolution rates during interstadials and interglacials, when low S 234 U is consistent with high bedrock dissolution rates. The contribution of a number of variables sensitive to bedrock dissolution and wetness frequency processes successfully explains 57% and 74% of the variability observed in the S 234 U in Andromeda stalagmite during MIS 3-4 and MIS 5b-5e, respectively. Among these variables, the growth rate has emerged as crucial to explain S 234 U variability, highlighting the fundamental role of soil respiration and soil CO2 in S 234 U through bedrock dissolution. I-STAL simulations provides the potential for a combination of Prior Calcite Precipitation (PCP) indicators like Mg/Ca with PCP- insensitive indicators of bedrock dissolution such as S234U, along with growth rate data, may be useful to diagnose when PCP variations reflect predominantly changes in drip intervals and when changes in bedrock dissolution intensity contribute. The relationship between stalagmite S234U, bedrock dissolution, and initial dripwater oversaturation suggests two significant advancements in paleoclimate proxies. First, S 234 U could serve as a valuable complement to S13C since it is significantly influenced by soil respiration and soil CO2, thereby reflecting soil and vegetation productivity sensitive to both humidity and temperature. Secondly, since PCP does not fractionate uranium isotopes, S 234 U could be used in combination with Mg/Ca or S44Ca to deconvolve PCP variations due to changing drip rates from those due to changes in initial saturation state. This study emphasizes the overriding climatic control on S234U, regardless of the absolute 234U/238U activity ratios among samples and their proximity or distance from secular equilibrium, and advocates for its application in other cave sites.

Despite being essentially water-free, nominally anhydrous minerals such as plagioclase and pyroxene represent the biggest reservoir of water in most lunar rocks due to their sheer abundance. Apatite, which incorporates F, Cl, and OH into its mineral structure as essential crystal components, on the other hand, is the only other volatile-bearing phase common in lunar samples. Here, we present the first coordinated study of volatiles (e.g., H2O, Cl, F, and S) in nominally anhydrous minerals combined with isotopic measurements in apatite from the ancient lunar basalt fragments from meteorite Miller Range (MIL) 13317. Apatite in MIL 13317 basalt contains similar to 2000 ppm H2O and has an elevated SD values (+ 523-737 parts per thousand), similar to Apollo mare basalts, but has high delta Cl-37 values (+ 29-36 parts per thousand), similar to apatite found in several KREEP-rich samples. MIL 13317 is unique compared with other lunar basalts; it has both elevated SD and delta Cl-37 values currently only observed in highlands sample 79215 (a granulitic impactite). Based on measurements of H2O in nominally anhydrous minerals and in apatite, the source magma of MIL 13317 basalt is estimated to contain similar to 130-330 ppm H2O. Assuming reasonable levels of partial melting of the lunar mantle and magmatic degassing during eruption of the basalt, the Moon contained at least one reservoir with < 100 ppm H2O, a delta D value of < 0 parts per thousand similar to carbonaceous chondrites, and extensively fractionated Cl isotopes prior to 4.332 Gyr, the crystallization age of the MIL 13317 basalt.

Pleistocene loess records of the Khovaling Loess Plateau (KLP) in Tajikistan provide rich collections of lithic artifacts demonstrating past human presence in the region. To understand the timing of human activity and environmental conditions prevailing at that time U-Th dating and clumped/stable C/O isotope measurements have been applied to modern and Pleistocene soil carbonates (SCs) collected at several sites on the KLP and surroundings. U-Th ages were corrected by two methods: 1) assuming an initial [Th-230/Th-232] activity ratio of 0.85 +/- 0.25 based on gamma spectrometry of loess/paleosol samples, and 2) the isochron technique using leachates and fully dissolved subsamples. Diagenetic alteration and potential U/Th mobilization and related isotope fractionation due to alpha-recoil was also modelled and found to be minor in the studied soil carbonates. Compared to model ages as references, uncorrected 230 Th ages are only acceptable if measured [Th-230/Th-232] activity ratios of leachates are high (>30), while Th-230 ages derived using method 1 are mostly overcorrected. It appears that SCs can be reliably dated by the U-series disequilibrium method in this sedimentary setting, but isochron dating cannot be spared. Application of the isochron method is required to derive (230)Thmodel ages, which ensures that the non-zero initial (230) Th and possible U-Th gain/loss due to alpha-recoil can be simultaneously corrected and reliable U-Th ages obtained. U-Th ages of Pleistocene SCs clearly demonstrate postpedogenic ingrowth of multiple, non-contemporaneous populations of SCs within loess/paleosol units, and that SC formation happened in many cases under cold, presumably dry glacial climate conditions. Considering that U-Th ages of SCs provide minimum ages of the sediment in which they form, these ages can be useful in developing loess stratigraphic models and for correlation of paleosols with marine isotope stages. This implies that the age of a given paleosol and any lithic artifacts it may contain, indicating human activity, cannot be younger than the age of SCs formed in that paleosol. This is due to the nature of soil carbonates, which can be the product of both syn- and post-depositional processes. Clumped isotope thermometry of SCs collected from modern soils at three sites in Tajikistan provide evidence for SCs dominantly recording summer season soil temperatures, while the calculated soil water oxygen isotope signatures reflect annual signals and carbonate precipitation from source waters incorporating rainfall from prior to and during SC formation. In contrast, some Pleistocene SCs record soil temperatures and stable isotope compositions more appropriate to glacial conditions, confirming the findings of U-Th ages, and highlighting the primary role of aridity-driven soil moisture changes in SC precipitation in this setting. Considering the interpretative complexities of SC stable isotope compositions, involving issues such as SC formation depth within a soil/paleosol profile, seasonality of SC growth and violation of the law of superposition, SC stable isotope proxy records of past climates cannot be considered as a set of clearly sequential data through time. This implies that such SC-based stable isotope records must be accompanied by U-Th dating of carbonates to be meaningful.