Local circulation of elites punctuated by transregional mobility enabled steppe political consolidation in the Xiongnu nomadic state.

The Xiongnu polity (ca. 200 BC- 150 AD) emerged out of indigenous community-centered socio-political structures to forge a powerful state that commanded the Mongolian steppe and beyond. Underpinned by a highly mobile pastoralist population, accustomed to seasonally rhythmic moves and embedded in an equestrian culture that facilitated rapid transport over long-distances, it remains unclear precisely how the movement of commoners, local aristocrats and regional elites abetted the formation and organization of Xiongnu state structures. Here, we evaluate Xiongnu movement and dietary intake through multi-stable isotopic analyses of tooth enamel from directly dated Xiongnu intermediate elites recovered from the mortuary center of Baga Gazaryn Chuluu-a prominent granite outcrop set in the Gobi Desert. Carbon isotope (δ13C) analysis indicates millet was consumed by some individuals, but whether or not this C4 cultivar contributed to the diets of most elites remains ambiguous in this C3/C4 desert-steppe environment. The effectiveness of oxygen isotopes (δ18O) to establish mobility appears much reduced in steppe environments, where geospatially sensitive information appears disrupted by extraordinary seasonality in meteoric water oxygen isotopes, pronounced oxygen isotopic variation in potential drinking water sources, and culturally mediated drinking practices. Most revealing, strontium isotopes (87Sr/86Sr) indicate circulation of local elites around this central place and beyond, a mobility format that helped leaders cement their own position through political consolidation of spatially dispersed mobile pastoralist communities. The consistent presence at Baga Gazaryn Chuluu of extra-local intermediate elites also points toward the importance of transregional mobility in binding together the Xiongnu polity over the vast distances of the eastern steppe.

Clumped isotopes reveal relationship between mussel growth and river discharge.

Freshwater mussels preserve valuable information about hydrology, climate, and population dynamics, but developing seasonal chronologies can be problematic. Using clumped isotope thermometry, we produced high-resolution reconstructions of modern and historic (~ 1900) temperatures and δ18Owater from mussel shells collected from an impounded river, the Brazos in Texas, before and after damming. We also performed high-resolution growth band analyses to investigate relationships between mussel growth rate, rainfall, and seasonal temperature. Reconstructed δ18Owater and temperature vary little between the modern (3R5) and historic shell (H3R). However, a positive relationship between reconstructed δ18Owater and growth rate in H3R indicates that aside from diminished growth in winter, precipitation and flow rate are the strongest controls on mussel growth in both modern and pre-dam times. Overall, our results demonstrate (1) the impact, both positive and negative, of environmental factors such as flow alteration and temperature on mussel growth and (2) the potential for clumped isotopes in freshwater mussels as a paleohydrology and paleoclimate proxies in terrestrial environments.

Effects of particle size, storage conditions, and chemical pretreatments on carbon and oxygen isotopic measurements of modern tooth enamel.

Isotopic analysis of human tooth enamel can provide life history information useful in forensic identification. These applications depend on the availability of reference data documenting isotopic values for individuals with known life history and on the comparability of data from reference and case work samples. Here we build on previous methodological research, which has largely focused on paleontological and archaeological samples, and conduct experiments using enamel from modern human teeth targeting three sample preparation variables (sample particle size, storage conditions, and chemical pretreatments). Our results suggest that differences in particle size affect the efficiency of sample reactions during pretreatment and analysis, with coarse particles giving reduced loss of enamel carbonate during acid pretreatments but producing slightly higher oxygen isotope values than fine particles during analysis. Data for samples stored in dry and ambient environments following pretreatment were indistinguishable, suggesting no exchange of oxygen between samples and ambient water vapor. Finally, chemical pretreatments with a range of commonly used reactants and conditions showed a pervasive, moderate oxygen isotope shift associated with acetic acid treatment, which may be caused by exchange of enamel hydroxyl groups with reagents or rinse waters. Collectively, the results emphasize the importance of methodological standardization to improve comparability and reduce potential for bias in the forensic application of tooth enamel isotope data.

Visible-Light-Driven Inactivation of Bacteria and H2 Generation Catalyzed by Oxygen-Vacancy-Rich One-Dimensional/Two-Dimensional W18O49/g-C3N4 Z-Scheme Heterostructures.

Z-scheme heterostructure-based photocatalysts consist of a reduction photocatalyst and an oxidation photocatalyst, enabling them to possess a high capacity for both reduction and oxidation. However, the coupling reaction between photocatalytic H2 generation through water reduction and sterilization using Z-scheme systems has been rarely reported. Herein, 1D W18O49 nanowires embedded over 2D g-C3N4 nanosheets are well-constructed as an integrated Z-scheme heterojunction. Experimental results and density functional theory calculations not only demonstrate the achievement of efficient interfacial charge separation and transport, leading to prolonged lifetime of photogenerated charge carriers, but also directly confirm the mechanism of Z-scheme charge transfer. As expected, the optimized W18O49/g-C3N4 nanostructure exhibits superior photocatalytic sterilization activity against Staphylococcus aureus as well as excellent H2 generation performance under visible-light irradiation (λ ≥ 420 nm). Due to its nontoxic nature, W18O49/g-C3N4 holds great potential in eradicating bacterial infections in living organisms.

Evaluation of Phosphorus Enrichment in Groundwater by Legacy Phosphorus in Orchard Soils with High Phosphorus Adsorption Capacity Using Phosphate Oxygen Isotope Analysis.

Long-term phosphorus (P) fertilization results in P accumulation in agricultural soil and increases the risk of P leaching into water bodies. However, evaluating P leaching into groundwater is challenging, especially in clay soil with a high P sorption capacity. This study examined whether the combination of PO4 oxygen isotope (δ18OPO4) analysis and the P saturation ratio (PSR) was useful to identify P enrichment mechanisms in groundwater. We investigated the groundwater and possible P sources in Kubi, western Japan, with intensive citrus cultivation. Shallow groundwater had oxic conditions with high PO4 concentrations, and orchard soil P accumulation was high compared with forest soil. Although the soil had a high P sorption capacity, the PSR was above the threshold, indicating a high risk of P leaching from the surface orchard soil. The shallow groundwater δ18OPO4 values were higher than the expected isotopic equilibrium with pyrophosphatase. The high PSR and δ18OPO4 orchard soil values indicated that P leaching from orchard soil was the major P enrichment mechanism. The Bayesian mixing model estimated that 76.6% of the P supplied from the orchard soil was recycled by microorganisms. This demonstrates the utility of δ18OPO4 and the PSR to evaluate the P source and biological recycling in groundwater.

Isotopic biographies reveal horse rearing and trading networks in medieval London.

This paper reports a high-resolution isotopic study of medieval horse mobility, revealing their origins and in-life mobility both regionally and internationally. The animals were found in an unusual horse cemetery site found within the City of Westminster, London, England. Enamel strontium, oxygen, and carbon isotope analysis of 15 individuals provides information about likely place of birth, diet, and mobility during the first approximately 5 years of life. Results show that at least seven horses originated outside of Britain in relatively cold climates, potentially in Scandinavia or the Western Alps. Ancient DNA sexing data indicate no consistent sex-specific mobility patterning, although three of the five females came from exceptionally highly radiogenic regions. Another female with low mobility is suggested to be a sedentary broodmare. Our results provide direct and unprecedented evidence for a variety of horse movement and trading practices in the Middle Ages and highlight the importance of international trade in securing high-quality horses for medieval London elites.

Regional heterothermies recorded in the oxygen isotope composition of harbour seal skeletal elements.

Regional heterothermy is a strategy used by marine mammals to maintain a high and stable core body temperature, but its identification needs in situ measurements difficult to set up in extant wild organisms and inapplicable to extinct ones. We have analysed the oxygen isotope composition of bioapatite phosphate (δ18Op) from one permanent tooth and from thirty-six skeletal elements of one adult male harbour seal (Phoca vitulina) from the Baie de Somme (Hauts-de-France, France). We propose that the observed intra-skeletal δ18Op variability reflects tissue temperature heterogeneities typical of the pinniped regional heterothermy strategy. Our δ18Op data indicate that bone hydroxylapatite from harbour seal autopod skeletal elements (metacarpals, metatarsals, and phalanxes) mineralises at a lower temperature than that of the bone from the axial skeleton (e.g. vertebrae, ribs, and girdle bones). The results suggest that it is possible to locate a history of regional heterothermies in amphibious marine vertebrates using the δ18Op values of their mineralised tissues. This enables direct evaluation of the thermophysiology of both modern and fossil Pinnipedia from their skeletons opening perspectives on understanding their thermal adaptation to the marine environment in the fossil record. In addition to thermophysiology, oxygen isotope data from the permanent teeth of Pinnipedia, which are formed during the in utero phase from body fluid of the mother and at a stable temperature, could be valuable for locating the geographical areas inhabited by existing Pinnipedia females during their gestation period.

The Pleistocene high-elevation environments between 2.02 and 0.6 Ma at Melka Kunture (Upper Awash Valley, Ethiopia) based upon stable isotope analysis.

Pleistocene environments are among the most studied issues in paleoecology and human evolution research in eastern Africa. Many data have been recorded from archaeological sites located at low and medium elevations (≤ 1500 m), whereas few contexts are known at 2000 m and above. Here, we present a substantial isotopic study from Melka Kunture, a complex of prehistoric sites located at 2000-2200 m above sea level in the central Ethiopian highlands. We analyzed the stable carbon and oxygen isotopic composition of 308 faunal tooth enamel samples from sites dated between 2.02 and 0.6 Ma to investigate the animal diets and habitats. The carbon isotopic results indicate that the analyzed taxa had C4-dominated and mixed C3-C4 diets with no significant diachronic changes in feeding behavior with time. This is consistent with faunal and phytolith analyses, which suggested environments characterized by open grasslands (with both C3 and C4 grasses), patches of bushes and thickets, and aquatic vegetation. However, palynological data previously documented mountain forests, woodlands, and high-elevation grasslands. Additionally, the carbon isotopic comparison with other eastern African localities shows that differences in elevation did not influence animal feeding strategies and habitat partitioning, even though plant species vary according to altitudinal gradients. In contrast, the oxygen isotopic comparison suggests significant differences consistent with the altitude effect. Our approach allows us to detect diverse aspects of animal behavior, habitat, and vegetation that should be considered when reconstructing past environments.

Finding balance: Tree-ring isotopes differentiate between acclimation and stress-induced imbalance in a long-term irrigation experiment.

Scots pine (Pinus sylvestris L.) is a common European tree species, and understanding its acclimation to the rapidly changing climate through physiological, biochemical or structural adjustments is vital for predicting future growth. We investigated a long-term irrigation experiment at a naturally dry forest in Switzerland, comparing Scots pine trees that have been continuously irrigated for 17 years (irrigated) with those for which irrigation was interrupted after 10 years (stop) and non-irrigated trees (control), using tree growth, xylogenesis, wood anatomy, and carbon, oxygen and hydrogen stable isotope measurements in the water, sugars and cellulose of plant tissues. The dendrochronological analyses highlighted three distinct acclimation phases to the treatments: irrigated trees experienced (i) a significant growth increase in the first 4 years of treatment, (ii) high growth rates but with a declining trend in the following 8 years and finally (iii) a regression to pre-irrigation growth rates, suggesting the development of a new growth limitation (i.e. acclimation). The introduction of the stop treatment resulted in further growth reductions to below-control levels during the third phase. Irrigated trees showed longer growth periods and lower tree-ring δ13 C values, reflecting lower stomatal restrictions than control trees. Their strong tree-ring δ18 O and δ2 H (O-H) relationship reflected the hydrological signature similarly to the control. On the contrary, the stop trees had lower growth rates, conservative wood anatomical traits, and a weak O-H relationship, indicating a physiological imbalance. Tree vitality (identified by crown transparency) significantly modulated growth, wood anatomical traits and tree-ring δ13 C, with low-vitality trees of all treatments performing similarly regardless of water availability. We thus provide quantitative indicators for assessing physiological imbalance and tree acclimation after environmental stresses. We also show that tree vitality is crucial in shaping such responses. These findings are fundamental for the early assessment of ecosystem imbalances and decline under climate change.

Quantifying isotope parameters associated with carbonyl-water oxygen exchange during sucrose translocation in tree phloem.

Stable oxygen isotope ratio of tree-ring α-cellulose (δ18Ocel) yields valuable information on many aspects of tree-climate interactions. However, our current understanding of the mechanistic controls on δ18Ocel is incomplete, with a knowledge gap existent regarding the fractionation effect characterizing carbonyl-water oxygen exchange during sucrose translocation from leaf to phloem. To address this insufficiency, we set up an experimental system integrating a vapor 18O-labeling feature to manipulate leaf-level isotopic signatures in tree saplings enclosed within whole-canopy gas-exchange cuvettes. We applied this experimental system to three different tree species to determine their respective relationships between 18O enrichment of sucrose in leaf lamina (Δ18Ol_suc) and petiole phloem (Δ18Ophl_suc) under environmentally/physiologically stable conditions. Based on the determined Δ18Ophl_suc-Δ18Ol_suc relationships, we estimated that on average, at least 25% of the oxygen atoms in sucrose undergo isotopic exchange with water along the leaf-to-phloem translocation path and that the biochemical fractionation factor accounting for such exchange is c. 34‰, markedly higher than the conventionally assumed value of 27‰. Our study represents a significant step toward quantitative elucidation of the oxygen isotope dynamics during sucrose translocation in trees. This has important implications with respect to improving the δ18Ocel model and its related applications in paleoclimatic and ecophysiological contexts.

Contrasting physiological strategies explain heterogeneous responses to severe drought conditions within local populations of a widespread conifer.

Understanding how trees prioritize carbon gain at the cost of drought vulnerability under severe drought conditions is crucial for predicting which genetic groups and individuals will be resilient to future climate conditions. In this study, we investigated variations in growth, tree-ring anatomy as well as carbon and oxygen isotope ratios to assess the sensitivity and the xylem formation process in response to an episode of severe drought in 29 mature white spruce (Picea glauca [Moench] Voss) families grown in a common garden trial. During the drought episode, the majority of families displayed decreased growth and exhibited either sustained or increased intrinsic water-use efficiency (iWUE), which was largely influenced by reduced stomatal conductance as revealed by the dual carbon­oxygen isotope approach. Different water-use strategies were detected within white spruce populations in response to drought conditions. Our results revealed intraspecific variation in the prevailing physiological mechanisms underlying drought response within and among populations of Picea glauca. The presence of different genetic groups reflecting diverse water-use strategies within this largely-distributed conifer is likely to lessen the negative effects of drought and decrease the overall forest ecosystems' sensitivity to it.

The stable isotope hydrology of Sable Island, Nova Scotia, Canada with implications for evaluating the water budget of wild horses.

We investigated the stable isotope hydrology of Sable Island, Nova Scotia, Canada over a five year period from September, 2017 to August, 2022. The δ2H and δ18O values of integrated monthly precipitation were weakly seasonal and ranged from -66 to -15 ‰ and from -9.7 to -1.9 ‰, respectively. Fitting these monthly precipitation data resulted in a local meteoric water line (LMWL) defined by: δ2H = 7.22 ± 0.21 · δ18O + 7.50 ± 1.22 ‰. Amount-weighted annual precipitation had δ2H and δ18O values of -36 ± 11 ‰ and -6.1 ± 1.4 ‰, respectively. Deep groundwater had more negative δ2H and δ18O values than mean annual precipitation, suggesting recharge occurs mainly in the winter, while shallow groundwater had δ2H and δ18O values more consistent with mean annual precipitation or mixing of freshwater with local seawater. Surface waters had more positive values and showed evidence of isolation from the groundwater system. The stable isotopic compositions of plant (leaf) water, on the other hand, indicate plants use groundwater as their source. Fog had δ2H and δ18O values that were significantly more positive than those of local precipitation, yet had similar 17O-excess values. δ2H values of horsehair from 4 individuals lacked seasonality, but had variations typical to those of precipitation on the island. Differences in mean δ2H values of horsehair were statistically significant and suggest variations in water use may exist between spatially disparate horse communities. Our results establish an important initial framework for ongoing isotope studies of feral horses and other wildlife on Sable Island.

Vittrup Man-The life-history of a genetic foreigner in Neolithic Denmark.

The lethally maltreated body of Vittrup Man was deposited in a Danish bog, probably as part of a ritualised sacrifice. It happened between c. 3300 and 3100 cal years BC, i.e., during the period of the local farming-based Funnel Beaker Culture. In terms of skull morphological features, he differs from the majority of the contemporaneous farmers found in Denmark, and associates with hunter-gatherers, who inhabited Scandinavia during the previous millennia. His skeletal remains were selected for transdisciplinary analysis to reveal his life-history in terms of a population historical perspective. We report the combined results of an integrated set of genetic, isotopic, physical anthropological and archaeological analytical approaches. Strontium signature suggests a foreign birthplace that could be in Norway or Sweden. In addition, enamel oxygen isotope values indicate that as a child he lived in a colder climate, i.e., to the north of the regions inhabited by farmers. Genomic data in fact demonstrates that he is closely related to Mesolithic humans known from Norway and Sweden. Moreover, dietary stable isotope analyses on enamel and bone collagen demonstrate a fisher-hunter way of life in his childhood and a diet typical of farmers later on. Such a variable life-history is also reflected by proteomic analysis of hardened organic deposits on his teeth, indicating the consumption of forager food (seal, whale and marine fish) as well as farmer food (sheep/goat). From a dietary isotopic transect of one of his teeth it is shown that his transfer between societies of foragers and farmers took place near to the end of his teenage years.

The determining factors of hydrogen isotope offsets between plants and their source waters.

A fundamental assumption when using hydrogen and oxygen stable isotopes to understand ecohydrological processes is that no isotope fractionation occurs during plant water uptake/transport/redistribution. A growing body of evidence has indicated that hydrogen isotope fractionation occurs in certain environments or for certain plant species. However, whether the plant water source hydrogen isotope offset (δ2 H offset) is a common phenomenon and how it varies among different climates and plant functional types remains unclear. Here, we demonstrated the presence of positive, negative, and zero offsets based on extensive observations of 12 plant species of 635 paired stable isotopic compositions along a strong climate gradient within an inland river basin. Both temperature and relative humidity affected δ2 H offsets. In cool and moist environments, temperature mainly affected δ2 H offsets negatively due to its role in physiological activity. In warm and dry environments, relative humidity mainly affected δ2 H offsets, likely by impacting plant leaf stomatal conductance. These δ2 H offsets also showed substantial linkages with leaf water 18 O enrichment, an indicator of transpiration and evaporative demand. Further studies focusing on the ecophysiological and biochemical understanding of plant δ2 H dynamics under specific environments are essential for understanding regional ecohydrological processes and for conducting paleoclimate reconstructions.

Effects of sampling time and location on the geographical origin traceability of protected geographical indication (PGI) Hongyuan yak milk: Based on stable isotope ratios.

Hongyuan yak milk is a protected geographical indication (PGI) product of rich nutritional value, which is popular among consumers. Stable isotope ratio analysis (SIRA) is an effective way to protect the authenticity of the geographical origin of PGI products, and it is crucial to study the factors affecting stable isotopes. Firstly, we proved that the SIRA could be used to identify the geographical origin of Hongyuan yak milk, and that the identification accuracy in combination with δ13C and δ18O was 100 %. Secondly, we analyzed the effect of sampling selection on the stable isotopes of Hongyuan yak milk in practical applications, which showed that sampling time influenced the δ13C, δ2H, and δ18O, while the sampling locations did not. There were interactions between the effect of sampling time and location on δ2H and δ18O. These results provide a reliable method for identifying PGI products and also provide new guidance on sampling models.

Fog controls biological cycling of soil phosphorus in the Coastal Cordillera of the Atacama Desert.

Soils in hyper-arid climates, such as the Chilean Atacama Desert, show indications of past and present forms of life despite extreme water limitations. We hypothesize that fog plays a key role in sustaining life. In particular, we assume that fog water is incorporated into soil nutrient cycles, with the inland limit of fog penetration corresponding to the threshold for biological cycling of soil phosphorus (P). We collected topsoil samples (0-10 cm) from each of 54 subsites, including sites in direct adjacency (<10 cm) and in 1 m distance to plants, along an aridity gradient across the Coastal Cordillera. Satellite-based fog detection revealed that Pacific fog penetrates up to 10 km inland, while inland sites at 10-23 km from the coast rely solely on sporadic rainfall for water supply. To assess biological P cycling we performed sequential P fractionation and determined oxygen isotope of HCl-extractable inorganic P δ 18 O HCl - P i $$ \mathrm{P}\ \left({\updelta}^{18}{\mathrm{O}}_{\mathrm{HCl}-{\mathrm{P}}_{\mathrm{i}}}\right) $$ . Total P (Pt ) concentration exponentially increased from 336 mg kg-1 to a maximum of 1021 mg kg-1 in inland areas ≥10 km. With increasing distance from the coast, soil δ 18 O HCl - P i $$ {\updelta}^{18}{\mathrm{O}}_{\mathrm{HCl}-{\mathrm{P}}_{\mathrm{i}}} $$ values declined exponentially from 16.6‰ to a constant 9.9‰ for locations ≥10 km inland. Biological cycling of HCl-Pi near the coast reached a maximum of 76%-100%, which could only be explained by the fact that fog water predominately drives biological P cycling. In inland regions, with minimal rainfall (<5 mm) as single water source, only 24 ± 14% of HCl-Pi was biologically cycled. We conclude that biological P cycling in the hyper-arid Atacama Desert is not exclusively but mainly mediated by fog, which thus controls apatite dissolution rates and related occurrence and spread of microbial life in this extreme environment.

Topographic influence on ecohydrology in volcanic watersheds of the western Pacific monsoon area: evidence from water stable isotope composition of meteoric water, thermal water, and plants.

In Taiwanese volcanic watersheds, we investigated stable water isotopes in meteoric water, plants, and thermal water. Meteoric water exhibited a seasonal cycle, with heavier isotopes in winter and lighter ones in summer, especially in the southern region. The northern monsoon signal lagged the south by two weeks. In the Tatun mountains, young water fractions indicated prevalent old water sources. In the northern watershed, streamwater mainly came from the winter monsoon, while the southern one was influenced by alternating monsoons. Both indices indicated that winter plants depended on summer rainfall. Streamwater and plants had distinct sources in winter, supporting ecohydrological separation. Thermal spring water's d-excess helped identify water-rock interactions, with low d value signaling such interactions. The topographic wetness index showed a higher summer monsoon contribution to southern streamwater but a lower one to plants. The mean linear channel direction significantly affected the monsoon contribution fraction, with northeast-oriented channels vulnerable to northeastward winter monsoons. Finally, we developed a model illustrating hydrological processes on short and long timescales. Our findings enhance our understanding of hydrological disturbances' impact on water resources and ecosystems.

Oxygen-18 Labeling Reveals a Mixed Fe-O Mechanism in the Last Step of Cytochrome P450 51 Sterol 14α-Demethylation.

The 14α-demethylation step is critical in eukaryotic sterol biosynthesis, catalyzed by cytochrome P450 (P450) Family 51 enzymes, for example, with lanosterol in mammals. This conserved three-step reaction terminates in a C-C cleavage step that generates formic acid, the nature of which has been controversial. Proposed mechanisms involve roles of P450 Compound 0 (ferric peroxide anion, FeO2 - ) or Compound I (perferryl oxygen, FeO3+ ) reacting with either the aldehyde or its hydrate, respectively. Analysis of 18 O incorporation into formic acid from 18 O2 provides a means of distinguishing the two mechanisms. Human P450 51A1 incorporated 88 % 18 O (one atom) into formic acid, consistent with a major but not exclusive FeO2 - mechanism. Two P450 51 orthologs from amoeba and yeast showed similar results, while two orthologs from pathogenic trypanosomes showed roughly equal contributions of both mechanisms. An X-ray crystal structure of the human enzyme showed the aldehyde oxygen atom 3.5 Šaway from the heme iron atom. Experiments with human P450 51A1 and H2 18 O yielded primarily one 18 O atom but 14 % of the formic acid product with two 18 O atoms, indicative of a minor contribution of a Compound I mechanism. LC-MS evidence for a Compound 0-derived Baeyer-Villiger reaction product (a 14α-formyl ester) was also found.

Oxygen-Vacancy-Engineered W18 O49-x Nanobrush with a Suitable Band Structure for Highly Efficient Sonodynamic Therapy.

With the rapid development of external minimally invasive or noninvasive therapeutic modalities, ultrasound-based sonodynamic therapy (SDT) is a new alternative for treating deep tumors. However, inadequate sonosensitizer efficiency and poor biosecurity limit clinical applications. In this study, we prepared an oxygen-vacancy-engineered W18 O49-x nanobrush with a band gap of 2.79 eV for highly efficient SDT using a simple solvothermal method. The suitable band structures of the W18 O49-x nanobrush endows it with the potential to simultaneously produce singlet oxygen (1 O2 ), superoxide anions (⋅O2 - ), and hydroxyl radicals (⋅OH) under ultrasound irradiation. Additionally, abundant oxygen vacancies that serve as further charge traps that inhibit electron-hole recombination are incidentally introduced through one-step thermal reduction. Collectively, the in vitro and in vivo results demonstrate that the oxygen-vacancy-engineered W18 O49-x nanobrush delivers highly efficient reactive oxygen species (ROS) for SDT in a very biosafe manner. Overall, this study provides a new avenue for discovering and designing inorganic nanosonosensitizers with enhanced therapeutic efficiencies for use in SDT.

Determination of the water-use patterns for two xerophyte shrubs by hydrogen isotope offset correction.

The stable hydrogen and oxygen isotope technique is typically used to explore plant water uptake; however, the accuracy of the technique has been challenged by hydrogen isotope offsets between plant xylem water and its potential source water. In this study, the soil hydrogen and oxygen isotope waterline was used to correct the hydrogen isotope offsets for Salix psammophila and Caragana korshinskii, two typical shrub species on the Chinese Loess Plateau. Five different types of isotopic data [(i) δ18O, (ii) δ2H, (iii) combination δ18O with δ2H, (iv) corrected δ2H and (v) combination δ18O with corrected δ2H] were separately used to determine the water-use patterns of the two shrubs. The δ2H offset values of S. psammophila and C. korshinskii did not show significant temporal variation among the sampling months (May, July and September) but showed notable differences between the two shrubs (-0.4 ± 0.5‰ in S. psammophila vs -4.3 ± 0.9‰ in C. korshinskii). The obtained water absorption proportion (WAP) of S. psammophila in the different soil layers (0-20, 20-60 and 60-200 cm) did not differ significantly among the five different input data types. However, compared with the input data types (iii) and (v), the data types (i), (ii) and (iv) overestimated the WAP of C. korshinskii in the 0-20 cm soil layer and underestimated that in the 60-200 cm layer. The data type (iii) overestimated the WAP of C. korshinskii in 0-20 cm soil layer (25.9 ± 0.8%) in July in comparison with the WAP calculated based on data type (v) (19.1 ± 1.1%). The combination of δ18O and corrected δ2H, i.e., data type (v), was identified as the best data type to determine the water use patterns of C. korshinskii due to the strong correlation between the calculated WAP and soil water content and soil sand content. In general, S. psammophila mainly used (57.9-62.1%) shallow soil water (0-60 cm), whereas C. korshinskii mainly absorbed (52.7-63.5%) deep soil water (60-200 cm). We confirm that the hydrogen isotope offsets can cause significant errors in determining plant water uptake of C. korshinskii, and provide valuable insights for accurately quantifying plant water uptake in the presence of hydrogen isotope offsets between xylem and source water. This study is significant for facilitating the application of the stable hydrogen and oxygen isotope technique worldwide, and for revealing the response mechanism of shrub key ecohydrological and physiological processes to the drought environment in similar climate regions.