Male mastodon landscape use changed with maturation (late Pleistocene, North America).

Under harsh Pleistocene climates, migration and other forms of seasonally patterned landscape use were likely critical for reproductive success of mastodons (Mammut americanum) and other megafauna. However, little is known about how their geographic ranges and mobility fluctuated seasonally or changed with sexual maturity. We used a spatially explicit movement model that coupled strontium and oxygen isotopes from two serially sampled intervals (5+ adolescent years and 3+ adult years) in a male mastodon tusk to test for changes in landscape use associated with maturation and reproductive phenology. The mastodon's early adolescent home range was geographically restricted, with no evidence of seasonal preferences. Following inferred separation from the matriarchal herd (starting age 12 y), the adolescent male's mobility increased as landscape use expanded away from his natal home range (likely central Indiana). As an adult, the mastodon's monthly movements increased further. Landscape use also became seasonally structured, with some areas, including northeast Indiana, used only during the inferred mastodon mating season (spring/summer). The mastodon died in this area (>150 km from his core, nonsummer range) after sustaining a craniofacial injury consistent with a fatal blow from a competing male's tusk during a battle over access to mates. Northeast Indiana was likely a preferred mating area for this individual and may have been regionally significant for late Pleistocene mastodons. Similarities between mammutids and elephantids in herd structure, tusk dimorphism, tusk function, and the geographic component of male maturation indicate that these traits were likely inherited from a common ancestor.

Chert oxygen isotope ratios are driven by Earth's thermal evolution.

The 18O/16O ratio of cherts (δ18Ochert) increases nearly monotonically by ~15‰ from the Archean to present. Two end-member explanations have emerged: cooling seawater temperature (TSW) and increasing seawater δ18O (δ18Osw). Yet despite decades of work, there is no consensus, leading some to view the δ18Ochert record as pervasively altered. Here, we demonstrate that cherts are a robust archive of diagenetic temperatures, despite metamorphism and exposure to meteoric fluids, and show that the timing and temperature of quartz precipitation and thus δ18Ochert are determined by the kinetics of silica diagenesis. A diagenetic model shows that δ18Ochert is influenced by heat flow through the sediment column. Heat flow has decreased over time as planetary heat is dissipated, and reasonable Archean-modern heat flow changes account for ~5‰ of the increase in δ18Ochert, obviating the need for extreme TSW or δ18Osw reconstructions. The seawater oxygen isotope budget is also influenced by solid Earth cooling, with a recent reconstruction placing Archean δ18OSW 5 to 10‰ lower than today. Together, this provides an internally consistent view of the δ18Ochert record as driven by solid Earth cooling over billion-year timescales that is compatible with Precambrian glaciations and biological constraints and satisfyingly accounts for the monotonic nature of the δ18Ochert trend.

The triple oxygen isotope composition of marine sulfate and 130 million years of microbial control.

The triple oxygen isotope composition (Δ'17O) of sulfate minerals is widely used to constrain ancient atmospheric pO2/pCO2 and rates of gross primary production. The utility of this tool is based on a model that sulfate oxygen carries an isotope fingerprint of tropospheric O2 incorporated through oxidative weathering of reduced sulfur minerals, particularly pyrite. Work to date has targeted Proterozoic environments (2.5 billion to 0.542 billion years ago) where large isotope anomalies persist; younger timescale records, which would ground ancient environmental interpretation in what we know from modern Earth, are lacking. Here we present a high-resolution record of the [Formula: see text]O and Δ'17O in marine sulfate for the last 130 million years of Earth history. This record carries a Δ'17O close to 0o, suggesting that the marine sulfate reservoir is under strict control by biogeochemical cycling (namely, microbial sulfate reduction), as these reactions follow mass-dependent fractionation. We identify no discernible contribution from atmospheric oxygen on this timescale. We interpret a steady fractional contribution of microbial sulfur cycling (terrestrial and marine) over the last 100 million years, even as global weathering rates are thought to vary considerably.

Uncoupling of stomatal conductance and photosynthesis at high temperatures: mechanistic insights from online stable isotope techniques.

The strong covariation of temperature and vapour pressure deficit (VPD) in nature limits our understanding of the direct effects of temperature on leaf gas exchange. Stable isotopes in CO2 and H2 O vapour provide mechanistic insight into physiological and biochemical processes during leaf gas exchange. We conducted combined leaf gas exchange and online isotope discrimination measurements on four common European tree species across a leaf temperature range of 5-40°C, while maintaining a constant leaf-to-air VPD (0.8 kPa) without soil water limitation. Above the optimum temperature for photosynthesis (30°C) under the controlled environmental conditions, stomatal conductance (gs ) and net photosynthesis rate (An ) decoupled across all tested species, with gs increasing but An decreasing. During this decoupling, mesophyll conductance (cell wall, plasma membrane and chloroplast membrane conductance) consistently and significantly decreased among species; however, this reduction did not lead to reductions in CO2 concentration at the chloroplast surface and stroma. We question the conventional understanding that diffusional limitations of CO2 contribute to the reduction in photosynthesis at high temperatures. We suggest that stomata and mesophyll membranes could work strategically to facilitate transpiration cooling and CO2 supply, thus alleviating heat stress on leaf photosynthetic function, albeit at the cost of reduced water-use efficiency.

Harnessing photosynthetic C18O16O discrimination dynamics under leaf water nonsteady state to estimate mesophyll conductance: a new, regression-based method.

Mesophyll conductance (gm) is a crucial plant trait that can significantly limit photosynthesis. Measurement of photosynthetic C18O16O discrimination (Δ18O) has proved to be the only viable means of resolving gm in both C3 and C4 plants. However, the currently available methods to exploit Δ18O for gm estimation are error prone due to their inadequacy in constraining the degree of oxygen isotope exchange (θ) during mesophyll CO2 hydration. Here, we capitalized on experimental manipulation of leaf water isotopic dynamics to establish a novel, nonsteady state, regression-based approach for simultaneous determination of gm and θ from online Δ18O measurements. We demonstrated the methodological and theoretical robustness of this new Δ18O-gm estimation approach and showed through measurements on several C3 and C4 species that this approach can serve as a benchmark method against which to identify previously-unrecognized biases of the existing Δ18O-gm methods. Our results highlight the unique value of this nonsteady state-based approach for contributing to ongoing efforts toward quantitative understanding of mesophyll conductance for crop yield improvement and carbon cycle modeling.

Effects of increasing atmospheric CO2 on leaf water δ18O values are small and are attenuated in grasses and amplified in dicotyledonous herbs and legumes when transferred to cellulose δ18O values.

The oxygen isotope composition of cellulose (δ18O values) has been suggested to contain information on stomatal conductance (gs) responses to rising pCO2. The extent by which pCO2 affects leaf water and cellulose δ18O values (δ18OLW and δ18OC) and the isotope processes that determine pCO2 effects on δ18OLW and δ18OC are, however, unknown. We tested the effects of pCO2 on gs, δ18OLW and δ18OC in a glasshouse experiment, where six plant species were grown under pCO2 ranging from 200 to 500 ppm. Increasing pCO2 caused a decline in gs and an increase in δ18OLW, as expected. Importantly, the effects of pCO2 on gs and δ18OLW were small and pCO2 effects on δ18OLW were not directly transferred to δ18OC but were attenuated in grasses and amplified in dicotyledonous herbs and legumes. This is likely because of functional group-specific pCO2 effects on the model parameter pxpex. Our study highlights important uncertainties when using δ18OC as a proxy for gs. Specifically, pCO2-triggered gs effects on δ18OLW and δ18OC are possibly too small to be detected in natural settings and a pCO2 effect on pxpex may render the commonly assumed negative linkage between δ18OC and gs to be incorrect, potentially confounding δ18OC based gs reconstructions.

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.

Precipitation isotope time series predictions from machine learning applied in Europe.

Hydrogen and oxygen isotope values of precipitation are critically important quantities for applications in Earth, environmental, and biological sciences. However, direct measurements are not available at every location and time, and existing precipitation isotope models are often not sufficiently accurate for examining features such as long-term trends or interannual variability. This can limit applications that seek to use these values to identify the source history of water or to understand the hydrological or meteorological processes that determine these values. We developed a framework using machine learning to calculate isotope time series at monthly resolution using available climate and location data in order to improve precipitation isotope model predictions. Predictions from this model are currently available for any location in Europe for the past 70 y (1950-2019), which is the period for which all climate data used as predictor variables are available. This approach facilitates simple, user-friendly predictions of precipitation isotope time series that can be generated on demand and are accurate enough to be used for exploration of interannual and long-term variability in both hydrogen and oxygen isotopic systems. These predictions provide important isotope input variables for ecological and hydrological applications, as well as powerful targets for paleoclimate proxy calibration, and they can serve as resources for probing historic patterns in the isotopic composition of precipitation with a high level of meteorological accuracy. Predictions from our modeling framework, Piso.AI, are available at https://isotope.bot.unibas.ch/PisoAI/.

A CO2 greenhouse efficiently warmed the early Earth and decreased seawater 18O/16O before the onset of plate tectonics.

The low 18O/16O stable isotope ratios (δ18O) of ancient chemical sediments imply ∼70 °C Archean oceans if the oxygen isotopic composition of seawater (sw) was similar to modern values. Models suggesting lower δ18Osw of Archean seawater due to intense continental weathering and/or low degrees of hydrothermal alteration are inconsistent with the triple oxygen isotope composition (Δ'17O) of Precambrian cherts. We show that high CO2 sequestration fluxes into the oceanic crust, associated with extensive silicification, lowered the δ18Osw of seawater on the early Earth without affecting the Δ'17O. Hence, the controversial long-term trend of increasing δ18O in chemical sediments over Earth's history partly reflects increasing δ18Osw due to decreasing atmospheric pCO2 We suggest that δ18Osw increased from about -5‰ at 3.2 Ga to a new steady-state value close to -2‰ at 2.6 Ga, coinciding with a profound drop in pCO2 that has been suggested for this time interval. Using the moderately low δ18Osw values, a warm but not hot climate can be inferred from the δ18O of the most pristine chemical sediments. Our results are most consistent with a model in which the "faint young Sun" was efficiently counterbalanced by a high-pCO2 greenhouse atmosphere before 3 Ga.

Drought, temperature, and moisture availability: understanding the drivers of isotopic decoupling in native pine species of the Nepalese Himalaya.

The Himalayas experienced long-term climate changes and recent extreme weather events that affected plant growth and the physiology of tree species at high-elevation sites. This study presents the first statistically robust δ18OTR chronologies for two native pine species, Pinus roxburghii, and Pinus wallichiana, in the lower Nepalese Himalaya. The isotope chronologies exhibited 0.88‰ differences in overall mean isotope values attributed to varying elevations (460-2000 m asl). Comparative analysis of climate response using data sets from different sources and resolutions revealed the superiority of the APHRODITE (Asian Precipitation - Highly-Resolved Observational Data Integration Towards Evaluation) data set calibrated for the South Asian Summer Monsoon (SASM)-dominated region. Both species exhibited negative correlations with monsoon precipitation and positive correlations with temperature. However, during the peak monsoon season (July-August), daily resolved climate data disentangled statistically insignificant relationships, and revealed that δ18OTR is influenced by atmospheric moisture. Both congeneric species showed a decoupling between the chronologies after 1995. However, no significant change in air moisture origin and monsoon regime between the study sites was observed, indicating a consistent dominant moisture source during different monsoon seasons. Besides, we also observed the decreased inter-series correlation of both δ18OTR chronologies after 1995, with P. wallichiana experiencing a steeper decrease than P. roxburghii. The weakening correlations between and within the chronologies coincided with a regional drought during 1993-1995 in both sites, highlighting the strong regulation of local climate on the impact of regional extreme climate events. Our findings emphasise the importance of employing climate data with optimal spatial and temporal resolution for improved δ18OTR-climate relationships at the intra-annual scale while considering the influence of site-specific local environmental conditions. Assessing climate data sets with station data is vital for accurately interpreting climate change's impact on forest response and long-term climate reconstructions.

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.

Sources, fate and influencing factors of nitrate in farmland drainage ditches of the irrigation area.

Global irrigation areas face the contradictory challenges of controlling nitrate inputs and ensuring food-safe production. To prevent and control nitrate pollution in irrigation areas, the study using the Yellow River basin (Ningxia section) of China as a case study, employed nitrogen and oxygen dual isotope tracing and extensive field investigations to analyze the sources, fate, and influencing factors of nitrate in agricultural drainage ditches. The results of source tracing of nitrate showed that annual proportions of nitrate sources entering the Yellow River in the ditches are as follows: for manure & sewage, fertilizer, and natural sources, the ratios are 33%, 35%, and 32% overall. The results of nitrate fate showed that nitrates derived from nitrate fertilizer exhibit a lower residual rate in drainage ditches (ecological ditches) compared to ammonium fertilizer, which can undergo self-ecological restoration within one year. The results of influencing factors showed that crops with high water and nutrient requirements, such as vegetables, the nitrate pollution and environmental harm resulting from "exploitative cultivation" are five times more than normal cultivation practices in dryland and paddy fields, especially winter irrigation without crop interception exacerbates the leaching of nitrate from the soil. Therefore, nitrate management in irrigation areas should focus on preventing and controlling "exploitative cultivation" and losses during winter irrigation, while appropriately adjusting the application ratio of ammonium nitrogen fertilizers. The results of the study can guide strategies to mitigate nitrate pollution in irrigated areas such as livestock farming, fertilizer application, irrigation management, ditch optimization, and crop cultivation.

Floating on groundwater: Insight of multi-source remote sensing for Qaidam basin.

Situated in the north of the Qinghai-Tibet Plateau, the Qaidam Basin experiences limited precipitation and significant evaporation. Despite these conditions, it stands out as one of the most densely distributed lakes in China. The formation of these lakes is controversial: whether the lake water primarily originates from local precipitation or external water sources. To address this issue, this paper explores the recharge sources of lakes in the Qaidam Basin and the circulation patterns of groundwater from a remote sensing perspective. Based on deep learning networks, we optimized the soft object regions of the Object-Contextual Representations Network (OCRNet) and proposed the Remote·Sensing Adaptive-Improved OCRNet (RSA-IOCRNet). Compared with seven other networks, RSA-IOCRNet obtained better experimental results and was used to construct an area sequence of 16 major lakes in the Qaidam Basin. Combined with multi-source data, the comprehensive analysis indicates no significant correlation between climatic factors and lake changes, while an obvious correlation between lakes and groundwater changes in the eastern Qaidam, consisting with the results of the field survey. Deep-circulating groundwater recharges numerous Qaidam lakes through upwelling from fault zones, such as Gasikule Lake and Xiaochaidan Lake. Groundwater in the Qaidam Basin is more depleted in hydrogen-oxygen isotope characteristics than surface water in the basin, but similar to some river water in the endorheic Tibetan Plateau. This indicates that Tibetan seepage water, estimated at approximately 540 billion m3/a, is transported through the Qaidam Basin via deep circulation. Moreover, it rises to recharge the groundwater and lakes within this basin through fracture zones, extending to various arid and semi-arid regions such as Taitema Lake. This work provides a new perspective on the impact of deep groundwater on lakes and water circulation in these areas.

Impacts of land use on phosphorus and identification of phosphate sources in groundwater and surface water of karst watersheds.

The thin soil layer with uneven distribution in karst areas facilitates the migration of phosphorus (P) to groundwater, threatening the safety of water sources seriously. To offer a scientific guidance for water pollution control and land use planning in karst areas, this study examined the relationships between land use and P in groundwater and surface water, and quantified the phosphate sources in Gaoping river basin, a small typical watershed in karst areas. Spatial distribution analysis revealed that the highest mean P concentrations in groundwater and surface water were in farmland and construction-farmland zones, respectively. Land use impact analysis showed that the concentration of P in groundwater was influenced positively by farmland but negatively by forest land. In contrast, the concentration of P in surface water was influenced positively by both farmland and construction land. The mixed end-element and Bayesian-based Stable Isotope Analysis in R (SIAR) model results showed that agricultural fertilizers were the main phosphate source for groundwater in farmland and forest-farmland zones, while urban sewage was the main source in the construction-farmland zone. For surface water, the main phosphate source was agricultural fertilizers in both farmland and construction-farmland zones. This study indicates that controlling P pollution in local water bodies should pay close attention to the management of land use related to human activities, including regulating sewage discharge from construction land and agricultural fertilizer usage.

Covariation between oxygen and hydrogen stable isotopes declines along the path from xylem water to wood cellulose across an aridity gradient.

Oxygen and hydrogen isotopes of cellulose in plant biology are commonly used to infer environmental conditions, often from time series measurements of tree rings. However, the covariation (or the lack thereof) between δ18 O and δ2 H in plant cellulose is still poorly understood. We compared plant water, and leaf and branch cellulose from dominant tree species across an aridity gradient in Northern Australia, to examine how δ18 O and δ2 H relate to each other and to mean annual precipitation (MAP). We identified a decline in covariation from xylem to leaf water, and onwards from leaf to branch wood cellulose. Covariation in leaf water isotopic enrichment (Δ) was partially preserved in leaf cellulose but not branch wood cellulose. Furthermore, whilst δ2 H was well-correlated between leaf and branch, there was an offset in δ18 O between organs that increased with decreasing MAP. Our findings strongly suggest that postphotosynthetic isotope exchange with water is more apparent for oxygen isotopes, whereas variable kinetic and nonequilibrium isotope effects add complexity to interpreting metabolic-induced δ2 H patterns. Varying oxygen isotope exchange in wood and leaf cellulose must be accounted for when δ18 O is used to reconstruct climatic scenarios. Conversely, comparing δ2 H and δ18 O patterns may reveal environmentally induced shifts in metabolism.

Unenriched xylem water contribution during cellulose synthesis influenced by atmospheric demand governs the intra-annual tree-ring δ18 O signature.

The oxygen isotope composition (δ18 O) of tree-ring cellulose is used to evaluate tree physiological responses to climate, but their interpretation is still limited due to the complexity of the isotope fractionation pathways. We assessed the relative contribution of seasonal needle and xylem water δ18 O variations to the intra-annual tree-ring cellulose δ18 O signature of larch trees at two sites with contrasting soil water availability in the Swiss Alps. We combined biweekly δ18 O measurements of soil water, needle water, and twig xylem water with intra-annual δ18 O measurements of tree-ring cellulose, xylogenesis analysis, and mechanistic and structural equation modeling. Intra-annual cellulose δ18 O values resembled source water δ18 O mean levels better than needle water δ18 O. Large parts of the rings were formed under high proportional exchange with unenriched xylem water (pex ). Maximum pex values were achieved in August and imprinted on sections at 50-75% of the ring. High pex values were associated with periods of high atmospheric evaporative demand (VPD). While VPD governed needle water δ18 O variability, we estimated a limited Péclet effect at both sites. Due to a variable pex , source water has a strong influence over large parts of the intra-annual tree-ring cellulose δ18 O variations, potentially masking signals coming from needle-level processes.

Determination of water balance maintenance in Orcinus orca and Tursiops truncatus using oxygen isotopes.

The secondary adaptation of Cetacea to a fully marine lifestyle raises the question of their ability to maintain their water balance in a hyperosmotic environment. Cetacea have access to four potential sources of water: surrounding salt oceanic water, dietary free water, metabolic water and inhaled water vapour to a lesser degree. Here, we measured the 18O/16O oxygen isotope ratio of blood plasma from 13 specimens belonging to two species of Cetacea raised under human care (four killer whales Orcinus orca, nine common bottlenose dolphins Tursiops truncatus) to investigate and quantify the contribution of preformed water (dietary free water, surrounding salt oceanic water) and metabolic water to Cetacea body water using a box-modelling approach. The oxygen isotope composition of Cetacea blood plasma indicates that dietary free water and metabolic water contribute to more than 90% of the total water input in weight for cetaceans, with the remaining 10% consisting of inhaled water vapour and surrounding water accidentally ingested or absorbed through the skin. Moreover, the contribution of metabolic water appears to be more important in organisms with a more lipid-rich diet. Beyond these physiological and conservation biology implications, this study opens up questions that need to be addressed, such as the applicability of the oxygen isotope composition of cetacean body fluids and skeletal elements as an environmental proxy of the oxygen isotope composition of present and past marine waters.

Isotopic Evidence for Microbial Nitrogen Cycling in a Glacier Interior of High-Mountain Asia.

Glaciers are now acknowledged as an important biome globally, but biological processes in the interior of the glacier (englacial) are thought to be slow and to play only a minor role in biogeochemical cycles. In this study, we demonstrate extensive, microbially driven englacial nitrogen cycling in an Asian glacier using the stable isotopes (δ15N, δ18O, and Δ17O values) of nitrate. Apparent decreases in Δ17O values of nitrate in an 8 m shallow firn core from the accumulation area indicate that nitrifiers gradually replaced ∼80% of atmospheric nitrate with nitrate from microbial nitrification on a decadal scale. Nitrate concentrations did not increase with depth in this core, suggesting the presence of nitrate sinks by microbial assimilation and denitrification within the firn layers. The estimated englacial metabolic rate using isotopic mass balance was classified as growth metabolism, which is approximately 2 orders of magnitude more active than previously known cold-environment metabolisms. In a 56 m ice core from the interior of the ablation area, we found less nitrification but continued microbial nitrate consumption, implying that organic matter is microbially accumulated over centuries before appearing on the ablating surface. Such englacial microbial products may support supraglacial microbes, potentially promoting glacial darkening and melting. With predicted global warming and higher nitrogen loads, englacial nutrient cycling and its roles may become increasingly important in the future.

Hydrogen Peroxide Formation during Ozonation of Olefins and Phenol: Mechanistic Insights from Oxygen Isotope Signatures.

Mitigation of undesired byproducts from ozonation of dissolved organic matter (DOM) such as aldehydes and ketones is currently hampered by limited knowledge of their precursors and formation pathways. Here, the stable oxygen isotope composition of H2O2 formed simultaneously with these byproducts was studied to determine if it can reveal this missing information. A newly developed procedure, which quantitatively transforms H2O2 to O2 for subsequent 18O/16O ratio analysis, was used to determine the δ18O of H2O2 generated from ozonated model compounds (olefins and phenol, pH 3-8). A constant enrichment of 18O in H2O2 with a δ18O value of ∼59‰ implies that 16O-16O bonds are cleaved preferentially in the intermediate Criegee ozonide, which is commonly formed from olefins. H2O2 from the ozonation of acrylic acid and phenol at pH 7 resulted in lower 18O enrichment (δ18O = 47-49‰). For acrylic acid, enhancement of one of the two pathways followed by a carbonyl-H2O2 equilibrium was responsible for the smaller δ18O of H2O2. During phenol ozonation at pH 7, various competing reactions leading to H2O2 via an intermediate ozone adduct are hypothesized to cause lower δ18O in H2O2. These insights provide a first step toward supporting pH-dependent H2O2 precursor elucidation in DOM.

Using a Multi-isotope Approach and Isotope Mixing Models to Trace and Quantify Phosphorus Sources in the Tuojiang River, Southwest China.

Identifying phosphorus (P) sources is critical for solving eutrophication and controlling P in aquatic environments. Phosphate oxygen isotopes (δ18Op) have been used to trace P sources. However, the application of this method has been greatly restricted due to δ18OP values from the potential source having wide and overlapping ranges. In this research, P sources were traced by combining δ18Op with multiple stable isotopes of nitrogen (δ15N), hydrogen (δD), and dissolved inorganic carbon (δ13C). Then, a Bayesian-based Stable Isotope Analysis in R (SIAR) model and IsoSource model were used to estimate the proportional contributions of the potential sources in the Tuojiang River. δ18Op was not in equilibrium with ambient water, and statistically significant differences in the δ18Op values were found between the potential sources, indicating that δ18Op can be used to trace the P sources. δ15N, δD, and δ13C could assist δ18Op in identifying the main sources of P. The SIAR and IsoSource models suggested that industrial and domestic sewage was the largest contributor, followed by phosphate rock and phosphogypsum and agricultural sewage. The uncertainty of the calculation results of the SIAR model was lower than that of the IsoSource model. These findings provide new insights into tracing P sources using multiple stable isotopes in watersheds.