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.

Lunar regolith samples contain fragments of endogenic rocks and exogenous meteorites. We report the first discovery of a chondrule fragment preserved in Chang'e-5 (CE-5) regolith samples. Forsterite and enstatite phenocrysts have extremely high Mg# (> 99) and high Mn/Fe ratios in this chondrule fragment. Its glass mesostasis is heterogeneous and contains hydrogen and carbon, as indicated by Raman peaks. The mineral assemblage, chemical composition, and oxygen isotope anomaly of this fragment are similar to those of type-I chondrules from carbonaceous chondrites. This fragment and other chondritic relics with 3.4 Ga. This contrast suggests that there may have been a change of impactors to the Earth-Moon system during the Imbrian period. Furthermore, this CE-5 chondrule fragment is a direct record of volatile addition to the Moon's surface from meteorites during the Eratosthenian period.

The Moon formed 4.5 Ga ago through a collision between proto-Earth and a planetesimal known as Theia. The compositional similarity of Earth and Moon puts tight limits on the isotopic contrast between Theia and proto- Earth, or it requires intense homogenization of Theia and proto-Earth material during and in the aftermath of the Moon- forming impact, or a combination of both. We conducted precise measurements of oxygen isotope ratios of lunar and terrestrial rocks. The absence of an isotopic difference between the Moon and Earth on the sub-ppm level, as well as the absence of isotope heterogeneity in Earth's upper mantle and the Moon, is discussed in relation to published Moon formation scenarios and the collisional erosion of Theia's silicate mantles prior to colliding with proto- Earth. The data provide valuable insights into the origin of volatiles in the Earth and Moon as they suggest that the water on the Earth may not have been delivered by the late veneer. The study also highlights the scientific value of samples returned by space missions, when compared to analyses of meteorite material, which may have interacted with terrestrial water.

Nitrate (NO3-) is a prominent atmospheric pollutant and a key chemical constituent of snow and ice, which plays a crucial role in the atmosphere and significantly impacts regional climate and environment conditions through a series of complex chemical processes. By summarizing the recent research progress on the nitrate chemical process (particularly on the isotopic measurements of NO3- (delta 15N, Delta 17O and delta 18O)) in atmosphere and glacier snow, this study mainly investigated the chemical compositions and chemical processes, formation pathways, and photochemical reactions of nitrate in snow and atmosphere. Our results identified that the main ways of atmospheric nitrate formation are the hydrolysis of N2O5 and the reaction of center dot OH with NO2; the spatial distribution of Delta 17O and delta 18O values of atmospheric nitrate have a significant latitudinal trend between 30 degrees N-60 degrees N; the study of stable isotopes (delta 15N and delta 18O) and the oxygen isotope anomaly (Delta 17O) of nitrate have mainly been carried out over the densely populated and coastal mega cities; there exist significant gaps in the study of chemistry processes of nitrate in snow and ice and the air-snow interfaces across glaciated regions. This study provides a basic reference for more robust observations and research of nitrate in glacier areas in the future.

Intra-annual variability of tree-ring oxygen stable isotopes (delta O-18) can record seasonal climate variability and a tree's ecophysiological response to it. Variability of sub-annual tree-ring delta O-18 maxima and minima, which usually occur in different parts of the growing season, may exhibit different climatic signals and can help in understanding past seasonal moisture conditions, especially in Asian monsoon areas. We developed minimum and maximum tree-ring delta O-18 series based on sub-annual tree-ring delta O-18 measurements ofPinus massonianaat a humid site in southeastern China. We found that interannual variability in minimum tree-ring delta O-18 is primarily controlled by the July-September soil water supply and source water delta O-18, whereas the maximum latewood tree-ring delta O-18 is primarily controlled by the relative humidity (RH) in October. The maximum of variability of earlywood tree-ring delta O-18 records the RH of October of the previous year. We used minimum and maximum tree-ring delta O-18 to develop two reconstructions (1900-2014) of seasonal moisture availability. The summer soil water supply (July-September self-calibrated Palmer drought severity index) and the RH in fall show contrasting trends, which may be related to late-growing seasonal warming leading to a high vapor capacity and high atmospheric moisture. Our findings are valuable for research that aims to explore seasonal moisture changes under anthropogenic climate change and the ecological implications of such contrasting trends.

Tree-ring intra-annual stable isotopes (delta C-13 and delta O-18) are powerful tools for revealing plant ecophysiological responses to climatic extremes. We analyzed interannual and fine-scale intra-annual variability of tree-ring delta C-13 and delta O-18 in Chinese red pine (Pinus massoniana) from southeastern China to explore environmental drivers and potential trade-offs between the main physiological controls. We show that wet season relative humidity (May-October RH) drove interannual variability of delta O-18 and intra-annual variability of tree-ring delta O-18. It also drove intra-annual variability of tree-ring delta C-13, whereas interannual variability was mainly controlled by February-May temperature and September-October RH. Furthermore, intra-annual tree-ring delta O-18 variability was larger during wet years compared with dry years, whereas delta C-13 variability was lower during wet years compared with dry years. As a result of these differences in intra-annual variability amplitude, process-based models (we used the Roden model for delta O-18 and the Farquhar model for delta C-13) captured the intra-annual delta O-18 pattern better in wet years compared with dry years, whereas intra-annual delta C-13 pattern was better simulated in dry years compared with wet years. This result suggests a potential asymmetric bias in process-based models in capturing the interplay of the different mechanistic processes (i.e., isotopic source and leaf-level enrichment) operating in dry versus wet years. We therefore propose an intra-annual conceptual model considering a dynamic trade-off between the isotopic source and leaf-level enrichment in different tree-ring parts to understand how climate and ecophysiological processes drive intra-annual tree-ring stable isotopic variability under humid climate conditions.

Understanding varying climate responses in tree-ring data across tree ages is important, but little is known about tree-age effects on climate responses in tree-ring stable isotopes. To detect whether age differences in tree-ring delta C-13 and delta O-18 could lead to differing climate responses, we measured tree-ring cellulose delta C-13 and delta O-18 (1901-2010) from Schrenk spruce (Picea schrenkiana) trees in northwestern China with ages ranging from 110 to 470 years, which we binned into three age groups. Tree-ring delta C-13 (pin-corrected) and delta O-18 exhibited similar year-to-year variability between age groups and did not feature age-related trends. delta C-13 series from old trees (270-470 years) showed stronger legacy effects, reflecting influences from the antecedent period (due to carbohydrate reserves and climate), compared to young trees (110-125 years). Both tree-ring delta C-13 and delta O-18 values decreased with increasing relative humidity (RH) and precipitation and with decreasing mean and maximum temperatures during the main growing season (May-August). delta C-13 and delta O-18 exhibited age-dependent climate responses: Young trees had a stronger climate response in delta C-13 but a weaker or similar climate response in delta O-18 compared to old trees. We developed multiple growing-season RH reconstructions based on composite chronologies using delta C-13 and delta O-18 series from different age groups. In particular, we found that including delta C-13 from young trees improved the skill of RH reconstructions because of the age-specific mechanisms driving the delta C-13-climate relationship, but that caution is warranted with regard to extreme values. We therefore suggest that young trees should be considered when using stable isotopes, particularly in delta C-13, for climate reconstruction.

Recycled moisture, mainly originated from evapotranspiration (surface evaporation and transpiration), is the main sources of precipitation. Influenced on the different regional/local environments, the contributions of recycled moisture to precipitation present as different proportions. Recycled moisture has an important impact on the hydrological cycle, further occurred a series of environmental effect for regional/local. Aimed to estimate the contribution of recycled moisture to precipitation in an enclosed basin, Guanzhong Basin of northern China, precipitation and lake/reservoir samples were collected. The isotope ratio analysis was done for the summer season, and a three-component mixing model based on the stable hydrogen and oxygen isotopes was applied. The results indicated that the averaged contribution of recycled moisture to precipitation was 17.44% in Guanzhong Basin of northern China, while the mean proportions of surface evaporation moisture and transpiration moisture were found to be 0.38% and 16.97%, respectively. Comparatively, most of the recycled moisture mainly comes from transpiration moisture rather than evaporation moisture, suggesting that transpiration moisture from cropland, vegetation, and plants instead of evaporation is dominant in moisture recycling of the Guanzhong Basin.

The clumped and stable isotope (Delta(47), delta O-18, and delta C-13) composition of pedogenic (soil) carbonates from cold, arid environments may be a valuable paleoclimate archive for climate change-sensitive areas at high latitudes or elevations. However, previous work suggests that the isotopic composition of cold-climate soil carbonates is susceptible to kinetic isotope effects (KIE). To evaluate the conditions under which KIE occur in cold-climate soil carbonates, we examine the Delta(47), delta O-18, and delta C-13 composition of soil carbonate pendants from Antarctica (Dry Valleys, 77 degrees S), the High Arctic (Svalbard 79 degrees N), the Chilean and Argentinian Andes, and the Tibetan plateau (3800-4800 m), and compare the results to local climate and water delta O-18 records. At each site we calculate the expected equilibrium soil carbonate Delta(47) and delta O-18 values and estimate carbonate Delta(47) and delta O-18 anomalies (observed Delta(47) or delta O-18 minus the expected equilibrium Delta(47) or delta O-18). Additionally, we compare the measured carbonate delta C-13 to the expected range of equilibrium soil carbonate delta C-13 values. To provide context for interpreting the Delta(47) and delta O-18 anomalies, the soil carbonate results are compared to results for sub-glacial carbonates from two different sites, which exhibit large Delta(47) anomalies (up to -0.29 parts per thousand). The Antarctic and 4700 masl Chilean Andes samples have negative Delta(47) anomalies and positive delta O-18 anomalies consistent with KIE due to rapid bicarbonate dehydration during cryogenic carbonate formation. In contrast, the lower elevation Chilean Andes, Argentinian Andes, Tibetan Plateau and High Arctic results are consistent with equilibrium, summer carbonate formation. We attribute the differences in Delta(47) and delta O-18 anomalies to variations in inter-cobble matrix grain size and its effects on the effective soil pore space, permeability (hydraulic conductivity), moisture, and bicarbonate dehydration rate. The Antarctic and 4700 masl Chilean Andean soils have coarse-grained matrices that facilitate rapid bicarbonate dehydration. In contrast, the lower elevation Chilean Andes, Argentinian Andes, High Arctic and Tibetan Plateau soils have finer-grained matrices that decrease the soil pore space, soil permeability and CO2 gas flux, promoting equilibrium carbonate formation. The sub-glacial carbonate samples yield highly variable Delta(47) and delta O-18 anomalies, and we propose that the differences between the two glacier sites may be due to variations in local sub-glacial drainage conditions, pCO(2), and pH. Our findings suggest that carbonates from soils with coarse-grained matrices may exhibit KIE in cold climates, making them poor paleoclimate proxies. Soils with fine-grained matrices are more likely to yield equilibrium carbonates suitable for paleoclimate reconstructions regardless of climate. Paleosol matrix grain size should therefore be taken into account in the evaluation of carbonate stable and clumped isotope values in paleoclimate studies. (C) 2018 Elsevier Ltd. All rights reserved.

Declining sea-ice extent is currently amplifying climate warming in the Arctic. Instrumental records at high latitudes are too short-term to provide sufficient historical context for these trends, so paleoclimate archives are needed to better understand the functioning of the sea ice-albedo feedback. Here we use the oxygen isotope values of wood cellulose in living and sub-fossil willow shrubs (delta O-18(wc)) (Salix spp.) that have been radiocarbon-dated (C-14) to produce a multi-millennial record of climatic change on Alaska's North Slope during the Pleistocene-Holocene transition (13,500-7500 calibrated 14C years before present; 13.5-7.5 ka). We first analyzed the spatial and temporal patterns of delta O-18(wc) in living willows growing at upland sites and found that over the last 30 years delta O-18(wc) values in individual growth rings correlate with local summer temperature and inter-annual variations in summer sea-ice extent. Deglacial delta O-18(wc) values from 145 samples of subfossil willows clearly record the Allerod warm period (similar to 13.2 ka), the Younger Dryas cold period (12.9-11.7 ka), and the Holocene Thermal Maximum (11.7-9.0 ka). The magnitudes of isotopic changes over these rapid climate oscillations were similar to 4.5 parts per thousand, which is about 60% of the differences in delta O-18(wc) between those willows growing during the last glacial period and today. Modeling of isotope-precipitation relationships based on Rayleigh distillation processes suggests that during the Younger Dryas these large shifts in 6180,c values were caused by interactions between local temperature and changes in evaporative moisture sources, the latter controlled by sea ice extent in the Arctic Ocean and Bering Sea. Based on these results and on the effects that sea-ice have on climate today, we infer that ocean-derived feedbacks amplified temperature changes and enhanced precipitation in coastal regions of Arctic Alaska during warm times in the past. Today, isotope values in willows on the North Slope of Alaska are similar to those growing during the warmest times of the Pleistocene-Holocene transition, which were times of widespread permafrost thaw and striking ecological changes. (C) 2017 Elsevier Ltd. All rights reserved.