Oxygen Isotope Composition Of Phosphate Research Articles

Eocene Shark Teeth From Peninsular Antarctica: Windows to Habitat Use and Paleoceanography

AbstractEocene climate cooling, driven by the falling pCO2 and tectonic changes in the Southern Ocean, impacted marine ecosystems. Sharks in high‐latitude oceans, sensitive to these changes, offer insights into both environmental shifts and biological responses, yet few paleoecological studies exist. The Middle‐to‐Late Eocene units on Seymour Island, Antarctica, provide a rich, diverse fossil record, including sharks. We analyzed the oxygen isotope composition of phosphate from shark tooth bioapatite (δ18Op) and compared our results to co‐occurring bivalves and predictions from an isotope‐enabled global climate model to investigate habitat use and environmental conditions. Bulk δ18Op values (mean 22.0 ± 1.3‰) show no significant changes through the Eocene. Furthermore, the variation in bulk δ18Op values often exceeds that in simulated seasonal and regional values. Pelagic and benthic sharks exhibit similar δ18Op values across units but are offset relative to bivalve and modeled values. Some taxa suggest movements into warmer or more brackish waters (e.g., Striatolamia, Carcharias) or deeper, colder waters (e.g., Pristiophorus). Taxa like Raja and Squalus display no shift, tracking local conditions in Seymour Island. The lack of difference in δ18Op values between pelagic and benthic sharks in the Late Eocene could suggest a poorly stratified water column, inconsistent with a fully opened Drake Passage. Our findings demonstrate that shark tooth bioapatite tracks the preferred habitat conditions for individual taxa rather than recording environmental conditions where they are found. A lack of secular variation in δ18Op values says more about species ecology than the absence of regional or global environmental changes.

Using oxygen isotopes in phosphate to assess biological phosphorus cycling in a small and shallow freshwater lake system

AbstractReducing excess phosphorus (P) loads that cause eutrophication in aquatic systems is essential for meeting water quality standards. The oxygen isotopic composition of phosphate (δ18Op) is a powerful tool for tracking P sources and cycling in diverse natural ecosystems. Here, we use δ18Op distribution in a small freshwater body (a lagoon–lake system) with high biological activity. We report δ18Op values seasonally along the water flow path in lagoon–lake system adjacent to Lake Biwa, Japan. The δ18Op values of inflowing water originating as agricultural runoff were constant throughout the study period at +16.3‰ ± 0.2‰. The δ18Op values in the system were generally offset from temperature‐dependent isotopic equilibrium with the surrounding water, ranging from +11.1‰ to +17.8‰. The δ18Op values of the lake water approached equilibrium values in July and October, when dissolved inorganic P (DIP) retention rates were high, consistent with extensive biologically mediated phosphate cycling. A δ18Op two end‐member mixing model, involving inflowing P and biologically recycled P, suggests that P turnover rates in the lagoon–lake system were high during the productive seasons. In contrast, the longer lake water residence time in the non‐irrigation season (winter) allowed δ18Op values to deviate toward lower values relative to both equilibrium and agricultural source δ18Op values, suggesting that P metabolism was dominated by extracellular/ecto‐enzymatic hydrolysis of dissolved organic P under low DIP concentrations. This work highlighted the utility of δ18Op for understanding P dynamics in shallow lake ecosystems.

Oxygen Isotope Analysis of Nanomole Phosphate Using PO3- Fragment in ESI-Orbitrap-MS.

The oxygen isotope composition of phosphate is a useful tool for studying biogeochemical phosphorus cycling. However, the current Ag3PO4 method is not only tedious in PO43- extraction and purification but also requires a large-sized sample at the micromole level, thereby limiting its application. Here, we present an approach to measuring the oxygen isotope composition, δ18O, of dissolved phosphate at the nanomole level using electrospray ionization Orbitrap mass spectrometry (ESI-Orbitrap-MS). We compared the reproducibility of δ18O measurements using the H2PO4- ions (m/z = 97 and 99 for H2P16O4- and H2P18O16O3-, respectively) and using the PO3- fragment ions (m/z = 79 and 81 for P16O3- and P18O16O2-, respectively) generated by source fragmentation and by higher-energy collisional dissociation, respectively. The results demonstrate that phosphate δ18O can be more reliably measured by the PO3- ions than by the H2PO4- ions. PO3- generated by source fragmentation at 40 V achieved the highest reproducibility for δ18O based on precision tests. Furthermore, the mass spectrum for a 50:50 μM mixed solution of phosphate and sulfate revealed that PO3- ions resulting from source fragmentation at 40 V are the predominant species in the Orbitrap analyzer. Notably, P16O3- ions (m/z: 79) are not interfered with by 32S16O3- (m/z: 80) ions. This is in contrast to the case for 1H2P16O4- ions, which share the same m/z value with 1H32S16O4- ions and exhibit much lower signal intensity than HSO4- ions. Using the PO3- fragment method and six phosphate standards with a wide range of δ18O values, we obtained a calibration line with a slope of 0.94 (R2 = 0.98). The overall uncertainty for ESI-Orbitrap-MS phosphate δ18O measurement was 0.8‰ (n = 30; 1 SD). With much room for improvement, the PO3- fragment method presents a better approach to measuring the phosphate oxygen isotope composition, applicable to nanomole sample sizes in a liquid phase.

Geochemical investigation of the mixed Máriahalom vertebrate fauna at the Paleogene–Neogene boundary in the Central Paratethys: environmental conditions and age constrain

The fossil vertebrate fauna of Máriahalom contains remains from a wide range of ecologies including terrestrial and aquatic mammals, crocodiles, sharks, and rays among others. All these were found mixed in mollusc-rich, shallow water, coastal deposits. The aim of the study is to trace the origin of the fossils using their rare earth element (REE) content and their respective ecology with stable oxygen isotopic compositions. In addition, marine vertebrates and calcareous marine fossils were analysed for their Sr isotope composition to provide a new age estimate for the locality. The REE content and their distribution in the fossils indicate similar early diagenetic environments and possible contemporaneous fossilization for the entire vertebrate assemblage. Reworked fossils of significantly different age can be excluded. The enamel/enameloid-derived phosphate oxygen isotope composition of selected fossil taxa fit well with previously inferred habitats that include marine, brackish, and terrestrial environments. Notably, the stem-pinniped Potamotherium valletoni is best interpreted as freshwater dweller instead of marine, consistent with the sedimentology of other occurrences. Our novel 87Sr/86Sr data suggest an Aquitanian age (21.4 ± 0.5 Ma) for the Máriahalom site that is younger than the previously proposed Late Oligocene age based on biostratigraphy (MP28–30 European Mammal Paleogene Reference Levels). An Aquitanian age raises the possibility that the index fossil taxon, the anthracothere mammal Microbunodon minimum, may have vanished earlier in Western Europe than in the Central Paratethys region.

A new phosphate purification method for igneous weathering profiles.

The oxygen isotope composition of phosphate (δ18 OPO4 ) is widely employed for reconstructing paleotemperature and tracing biogeochemical phosphorus cycling. However, existing phosphate purification protocols do not work well for igneous rocks and igneous weathering profiles (IWPs). A reliable purification method is needed for measuring δ18 OPO4 in these materials. Our phosphate purification method includes two steps of cation exchange resin treatment separated by a step of calcium phosphate precipitation (R-Ca-R method). In addition, the silver phosphate precipitation in our procedure is featured by slow evaporation to crystallization until the appearance of ammonium nitrate or silver nitrate crystals. We evaluated our methods on weathered and pristine igneous rocks, phosphorite rocks, KH2 PO4 , and (NH4 )2 HPO4 solutions. Our purification method converted over 99.9% phosphate in solution to calcium phosphate, which can be easily decalcified by cation resin. The improved silver phosphate precipitation method produced high phosphate yields (97.1%-99.5%) and retained original δ18 OPO4 within analytical uncertainty (2σ = 0.6‰). We applied the purification and precipitation method on five igneous rocks and IWPs, and obtained δ18 OPO4 values ranging from 6.4‰ to 8.0‰. Duplicate phosphate extractions yielded δ18 OPO4 values differing by less than 0.3‰. We developed a new phosphate purification method that is applicable to phosphate extraction in igneous rocks and IWPs. We also proposed a reliable indicator for the termination of silver phosphate precipitation. Our method can achieve high phosphate yield and reproducible δ18 OPO4 value.

Identification of the sources of different phosphorus fractions in lake sediments by oxygen isotopic composition of phosphate

Phosphorus (P) released from sediment driven by oxidation-reduction potential and enzymes can increase the concentrations of dissolved P in the overlying water, which trigger widespread algal blooms. Therefore, identification sediment P sources is critical for the management of P and restoration of eutrophic aquatic ecosystem. Sediment P fractions have been widely reported, whereas little is known regarding the source and pathway of different P fractions in eutrophic lake sediments. In this study, we applied chemical sequential extraction with oxygen isotopic compositions of phosphate (δ18OP) to identify the inorganic P (Pi) source in the sediments of Lake Dianchi, China. Results show that contents of organic P (Po), HCl-Pi, NaOH-Pi, and NaHCO3-Pi of sediment were the main P fractions compared with that of sediment H2O-Pi, which was attributed to the bioavailable difference of these P fractions. Significant difference on the equilibrium values of δ18OP (δ18OP-eq), δ18OP of sediment P fractions, and δ18OP of external P was observed, which reflected the complex transformation processes of these P fractions in sediments. Further, the values of sediment δ18ONaHCO3-Pi at some sites (17.2–22.5‰) deviated from δ18OP-eq (14.7–19.0‰), and these values fell into the values of δ18OP for external P (7.7–23.8‰), suggesting that sediment NaHCO3-Pi at these sites derived from external P. Comparison the values of sediment δ18ONaOH-Pi (14.5–24.9‰) with δ18OP-eq and δ18O of external P sources suggested that sediment NaOH-Pi was not only from external P, but also from sedimentary Po remineralization. Pi released from sediment NaOH-Pi may be responsible for the higher values of sediment δ18OHCl-Pi (15.2–20.8‰) than that of soils (13.1–15.3‰) and phosphate rock (8.9–12.6‰). Results gained from this study provided critical insights for the source and biogeochemical cycling of P across the sediment-water interface in the eutrophic lake.

Intra-skeletal variability in phosphate oxygen isotope composition reveals regional heterothermies in marine vertebrates

Abstract. Strategies used by marine vertebrates to regulate their body temperature can result in local variations, and the knowledge of these regional heterothermies is crucial for better understanding the thermophysiologies of extant and extinct organisms. In order to investigate regional heterothermies in vertebrates, we analysed the oxygen isotope composition of phosphatic skeletal elements (δ18Op) of two endothermic fishes (Thunnus thynnus and Xiphias gladius) and three dolphins (two Delphinus delphis delphis and one Cephalorhynchus commersonii kerguelensis). We observed a consistent link between δ18Op variations and temperature heterogeneities recorded by classical methods. Our δ18Op data indicate that: (i) bone hydroxylapatite of the axial skeleton of dolphins mineralise at a warmer temperature than that of the appendicular one, (ii) the skull is the warmest body region in X. gladius, and (iii) T. thynnus possesses high body temperature in the skull and visceral mass region. These results demonstrate the possibility of tracking regional heterothermies in extant marine vertebrates using the δ18Op, paving the way to direct assessment of thermophysiological specificities of both living and extinct vertebrates. From a palaeoenvironmental perspective, the significant observed δ18Op variability questions the use of some taxa or random skeletal elements for the reconstruction of palaeoceanographic parameters such as seawater temperature and δ18O.

Phosphate oxygen isotope ratios in vegetated riparian buffer strip soils

AbstractThe oxygen isotopic composition of phosphate (δ18OP) in soils and surface water bodies has been used to trace terrestrial P inputs into aquatic ecosystems. However, enhanced biological activity in vegetated riparian buffer strips (VBSs) may lead to an alteration of δ18OP values. The objective of this study was to assess whether enhanced biological cycling of P in VBS soils can be identified using δ18OP values. For this purpose, we sampled temperate grassland soils at various depths along a VBS to grassland transect. Here, we combined sequential P soil extracts with an analysis of δ18OP values. Soil P pool concentrations tended to decrease significantly along the transect from the VBS to the grassland soils; the strength of this relationship varied with P extract, sample depth, and inorganic or organic bonding form. For the δ18OP values of the 1 M HCl‐extractable P we observed a significant negative trend along the VBS to grassland transect, indicating a tendency for accelerated rates of biological cycling of P within the VBS soil profile compared with the upslope soils. We conclude that oxygen isotope‐based assessments of P source contributions to freshwater bodies should consider the enhanced biological turnover of P in VBS soils.

Pronghorn (Antilocapra americana) enamel phosphate δ18O values reflect climate seasonality: Implications for paleoclimate reconstruction.

Stable oxygen isotope (δ18O) compositions from vertebrate tooth enamel are widely used as biogeochemical proxies for paleoclimate. However, the utility of enamel oxygen isotope values for environmental reconstruction varies among species. Herein, we evaluate the use of stable oxygen isotope compositions from pronghorn (Antilocapra americana Gray, 1866) enamel for reconstructing paleoclimate seasonality, an elusive but important parameter for understanding past ecosystems. We serially sampled the lower third molars of recent adult pronghorn from Wyoming for δ18O in phosphate (δ18OPO4) and compared patterns to interpolated and measured yearly variation in environmental waters as well as from sagebrush leaves, lakes, and rivers (δ18Ow). As expected, the oxygen isotope compositions of phosphate from pronghorn enamel are enriched in 18O relative to environmental waters. For a more direct comparison, we converted δ18Ow values into expected δ18OPO4* values (δ18OW‐PO4*). Pronghorn δ18OPO4 values from tooth enamel record nearly the full amplitude of seasonal variation from Wyoming δ18OW‐PO4* values. Furthermore, pronghorn enamel δ18OPO4 values are more similar to modeled δ18OW‐PO4* values from plant leaf waters than meteoric waters, suggesting that they obtain much of their water from evaporated plant waters. Collectively, our findings establish that seasonality in source water is reliably reflected in pronghorn enamel, providing the basis for exploring changes in the amplitude of seasonality of ancient climates. As a preliminary test, we sampled historical pronghorn specimens (1720 ± 100 AD), which show a mean decrease (a shift to lower values) of 1–2‰ in δ18OPO4 compared to the modern specimens. They also exhibit an increase in the δ18O amplitude, representing an increase in seasonality. We suggest that the cooler mean annual and summer temperatures typical of the 18th century, as well as enhanced periods of drought, drove differences among the modern and historical pronghorn, further establishing pronghorn enamel as excellent sources of paleoclimate proxy data.

Oxygen isotope exchange rates between phosphate and water catalyzed by inorganic pyrophosphatase: Implications for the biogeochemical cycle of phosphorus

The oxygen isotope composition of phosphate (δ18OPO4) has been widely used as (paleo)temperature and bio-signature proxies and a tracer of biogeochemical cycling of phosphorus (P). In natural aqueous systems, reactive inorganic phosphorus is dominantly present as dissolved inorganic phosphate (DIP), and reactions involving DIP are primarily carried out by microorganisms and catalyzed by enzymes. One enzyme suggested to dominate P-cycling in nature is inorganic pyrophosphatase (PPase), a ubiquitous intracellular enzyme that catalyzes oxygen (O) isotope exchange between DIP and water. Herein, we determined PPase-catalyzed O-isotope exchange rates between DIP and water over the range of typical Earth surface temperatures (3 - 37°C) using isotope ratio mass spectrometry (IRMS). Exchange rates determined at pH 7.4 and between 3 and 37°C, were described by first-order reaction kinetics (rate constant k = 1.51E-05 to 3.13E-04 sec−1; half-life of reaction t1/2 = 37 to 765 minutes), and strongly dependent on temperature. The temperature dependence of the exchange reaction was fitted by the Arrhenius equation, with an activation energy of 61.8 kJ/mole. The rate of PPase-catalyzed O-isotope exchange is ca. 7 - 8 orders of magnitude faster than the rate of abiotic reactions (pH 5) at 37°C calculated by the extrapolation of high-temperature rate data. The results of this study can be used to improve the interpretation of measured δ18O values of phosphate preserved in the rock record or during biogeochemical reactions (e.g., deconvolution of simultaneous abiotic and enzymatic/microbial processes).

Oxygen isotopic fingerprints on the phosphorus cycle within the deep subseafloor biosphere

Phosphorus (P) is essential for all known forms of life. The oxygen isotopic composition of phosphate can carry a strong imprint from the metabolic processes in Earth’s surface environments, including the deep subseafloor biosphere extending to > 1 km beneath the seafloor. Here, we report the 18O/16O ratios (δ18O) of dissolved inorganic phosphate (DIP) to identify different pathways of P cycling in deep-sea sediments sampled up to 200 meters below the seafloor during Ocean Drilling Program (ODP) Leg 201. Our results, along with a diagenetic model, indicate that the δ18O of DIP (δ18ODIP) is mainly controlled by three pathways of P cycling at Site 1230: (1) release of DIP by extracellular enzymatic degradation of organic matter (i.e., organophosphate), (2) precipitation of authigenic apatite, (3) enzyme-catalyzed oxygen isotopic exchange between phosphate and water. Our diagenetic model quantitatively deconvolves the rates of the three P cycling pathways. In particular, a shift of δ18ODIP towards equilibrium around 140 m below the seafloor corresponds well with a shift in microbial communities, suggesting that δ18ODIP has potential as a proxy for microbial activities in the deep subseafloor biosphere. We also find that the rate of oxygen isotopic exchange can be scaled with the rate of organic matter degradation, suggesting microbially controlled oxygen isotopic exchange. Further, the pattern of variation between authigenic phosphate in sediments and DIP in porewaters bolsters the case that authigenic phosphate (authigenic apatite and Fe-bound phosphate) should reflect the oxygen isotopic composition of contemporaneous porewater DIP and thus can be used to track biogeochemical cycling of P.

Phosphate distribution and sources in the waters of Huangbai River, China: using oxygen isotope composition of phosphate as a tracer.

We investigated the distributions of phosphate (PO4-P) and used the oxygen isotope composition of phosphate (δ18OP) to quantify PO4-P sources in the waters of Huangbai River. According to the environmental characteristics of Huangbai River basin, the sampling stations in the Huangbai River were divided into three groups: sampling stations in the phosphate mining area, in the outcrop area of phosphate rock, and in the residential/agricultural area. The average PO4-P concentration was highest (2.34 ± 1.00 μmol/L) in the outcrop area of phosphate ore, intermediate in the residential/agricultural area (1.06 ± 1.21 μmol/L), and lowest in the phosphate mining area (0.58 ± 0.31 μmol/L). The δ18OP measured in the Huangbai River waters ranged from 6.0 to 20.9‰, with the highest average value in the outcrop area of phosphate rock (average: 14.6‰ ± 3.1‰). The majority of the measured δ18OP values in the Huangbai River deviated greatly from the expected equilibrium values, indicating that δ18OP in this area could be used to trace PO4-P sources. We used two end-member mixing models to quantify the contribution of PO4-P from different sources. In the phosphate mining area, the average fractions of PO4-P from phosphate ore and sewage were 49.5% ± 23.8% and 50.5% ± 23.8%, respectively. In the outcrop area of phosphate rock, the average fractions of PO4-P from phosphate ore and sewage were 60.1% ± 21.7% and 39.9% ± 21.7%, respectively. In the residential/agricultural area, the average fractions of PO4-P from fertilizer and sewage were 49.2% ± 23.2% and 50.8% ± 23.2%, respectively. These results indicate that phosphate mining activities was not an important source for PO4-P in the waters of Huangbai River. The natural weathering of phosphate rock, fertilization, and domestic sewage contributed more to the high PO4-P concentrations in the Huangbai River waters.

In or Out of Equilibrium? How Microbial Activity Controls the Oxygen Isotopic Composition of Phosphate in Forest Organic Horizons With Low and High Phosphorus Availability

While there are estimates of the abiotic processes contribution to soil phosphorus (P) availability, less is known about the contribution of biological processes. Two main enzymatic processes involved in soil P cycling are known to alter the oxygen isotopic composition of phosphate (δ18O-P), each in a different way, through the cleavage of the P–O bond: the intracellular P turnover and the organic P hydrolysis. The former induces isotopic equilibration between phosphate and water and is considered the major process affecting soil available P via microbial P release. The latter induces depleted δ18O-P in the phosphate released from the mineralization of organic P. We studied P dynamics in organic horizons of two contrasting soils (low- and high-P availability) from temperate beech forests. We labelled the soil with 18O-enriched water and followed changes in the δ18O-P of different soil P pools in the presence or absence of added leaf litter during three months of incubation. δ18O-P values of almost all P pools progressively increased indicating oxygen incorporation from the enriched soil water into phosphate via the above-mentioned enzymatic processes. δ18O-P of available P increased more in the P-rich soil than in the P-poor soil and approached the isotopic equilibrium between phosphate and water, revealing the impact of microbial P release into the available P. However, in the P-poor soil, the available P brought the signature induced by phosphatase enzymes, indicating that it was mostly originated from the hydrolysis of organic P. Therefore, a below-equilibrium signature can be still an indicator of control of microbial P on the available P via Po hydrolysis reactions. Finally, two independent isotopic approaches with 33P and δ18O-P provided very similar estimates of P exchanged between the available P and other inorganic soil pools. This suggests that δ18O-P can be successfully used to trace P fluxes, provided that the underlying processes do not break the P – O bonds of the phosphate molecule.

Quantification of a North American greenhouse hydrological cycle: using oxygen isotopic composition of phosphate from Early Cretaceous (Aptian–Albian) turtles

Abstract The oxygen isotopic composition of turtle phosphate from Early (Aptian–Albian) Cretaceous turtles from several North American palaeolatitudes was measured to estimate the isotopic compositions of groundwater δ 18 O w . In Earth's history, under greenhouse conditions, researchers have recorded an intensification of the hydrological cycle as global heat was distributed from the equator to the poles via latent heat transport. Previous studies, using pedogenic carbonate nodules, show an increased rainout effect, causing intense depletion in δ 18 O w at high latitudes due to this phenomenon. This study shows the utility of another palaeo- δ 18 O w proxy, turtle phosphate oxygen from turtle carapace and plastron. Turtle δ 18 O p was sampled from several Early Cretaceous sites. We find that turtle-derived δ 18 O w values range from −3.1 ± 0.9‰ at a palaeolatitude of 29.5° N to −7.2‰ at 40° N. Turtles at the lowest latitude (Arkansas) plot off the carbonate-derived δ 18 O w gradient; however, turtles at 34° N and 40° N plot within the range of carbonate-derived δ 18 O w . Turtles from Arkansas (29.5° N) were likely to have been influenced by marine water and/or enriched Gulf of Mexico water vapour resulting in a deviation from the expected δ 18 O w gradient. These data are encouraging steps towards using turtles to estimate palaeohydrological dynamics; however, additional analysis of lower- and higher-latitude specimens is necessary to confirm this trend.

San José 520: An Unusual Teotihuacan Settlement System

San José 520 is a Classic period hamlet of single-family residences in the urban periphery of Teotihuacan, just beyond the southeast edge of the city. Three burial features were associated with one of the residences, AF2. One of the features contained the burial of a single adult, another the successive burials of eight adults and one neonate, and the third held a neonate. We analyzed 29 bone and enamel samples from the adults for bioapatite phosphate oxygen-isotope composition; we also considered isotopic data for another five bone samples analyzed in a separate project. The isotopic results suggest a pattern of birth in the Teotihuacan region and then movement in early childhood to a “relocation” region, the geographic location of which is unknown. Later, probably in adolescence, the individuals returned to live, and eventually die, in San José 520. Without knowing more about the occupation of the relocation region, it is difficult to say what concerns or beliefs underlay this unusual but long-established settlement system.

Quantification of a North American greenhouse hydrological cycle: using oxygen isotopic composition of phosphate from Early Cretaceous (Aptian–Albian) turtles

Quantification of a North American greenhouse hydrological cycle: using oxygen isotopic composition of phosphate from Early Cretaceous (Aptian–Albian) turtles

Oxygen isotopes and ecological inferences of Permian (Guadalupian) tetrapods from the main Karoo Basin of South Africa

The Abrahamskraal Formation of South Africa has a diverse middle Permian (Guadalupian) fossil tetrapod fauna comprising largely basal therapsids and pareiasaurian parareptiles. Knowledge on the paleoecology of these animals is limited because inferences of many ecological traits in mid-Permian tetrapods are based on deductions from morphology. While it is widely accepted that the rhinesuchid amphibians were aquatic, the ecological lifestyle of pareiasaurs and dinocephalian therapsids remains uncertain. To investigate the ecological roles of different middle Permian tetrapod taxa we studied stable oxygen isotope compositions of phosphate from teeth and bones as a proxy for water dependence. Our results reveal similar δ18Op values for pareiasaurs, the dinocephalian Anteosaurus, and therocephalians, with a range of values similar to those of extant terrestrial species. The consistent δ18Op values for pareiasaurs strengthen our interpretation of a terrestrial lifestyle for these parareptiles, but the lower Anteosaurus δ18Op values might question the interpretation and a larger sample size may result in a more conclusive outcome. These results conclude the debate on the ecology of middle Permian pareiasaurs. A terrestrial lifestyle is applicable only to the middle Permian species and a different lifestyle is possible for pareiasaurs species that lived after the end Capitanian extinction.

‘Co-evolution’ of uranium concentration and oxygen stable isotope in phosphate rocks

Phosphate rocks (PRs) used in fertilizer production contain uranium (U), which enters agricultural soils through phosphorus fertilization. However, our knowledge is still limited and cannot explain the different levels of U contamination found in agricultural systems. The paper reviewed the spatial and temporal U variations in PRs to obtain a comprehensive overview of U levels in various PRs worldwide and to investigate why U concentrations in igneous PRs are significantly lower compared to sedimentary PRs, and why less U is present in old sedimentary PRs (Precambrian-Cambrian) than in younger PRs (Ordovician-Neogene). In addition, the natural oxygen isotope compositions of phosphate (δ18Op) in various PRs were determined to identify their origins in relation to their U concentration. The δ18Op values differed among igneous PRs, old sedimentary PRs, and younger sedimentary PRs. Generally, the PRs with low δ18Op values had low U concentrations. In igneous PRs, low U concentrations were due to the lack of secondary U enrichment processes after rock formation, with low δ18Op values resulting from limited isotope fractionation at high temperature. Conversely, in sedimentary PRs, both U concentrations and δ18Op values were influenced by paleoclimate and paleogeographic features. Overall, there is a time-dependent coincidence of processes altering U concentration and δ18Op signatures of sedimentary PRs in a similar direction.

A New Technique to Determine the Phosphate Oxygen Isotope Composition of Freshwater Samples at Low Ambient Phosphate Concentration.

The oxygen isotope composition of dissolved inorganic phosphate (δ18Op) offers new opportunities to understand the sources and the fate of phosphorus (P) in freshwater ecosystems. However, current analytical protocols for determining δ18Op are unable to generate reliable data for samples in which ambient P concentrations are extremely low, precisely the systems in which δ18Op may provide new and important insights into the biogeochemistry of P. In this Article, we report the development, testing and initial application of a new technique that enables δ18Op analysis to be extended into such ecosystems. The twist spinning mode (TSM) protocol described here enables >1000 L of sample with a P concentration <0.016 mg P L-1 to be initially processed within the field in approximately 24 h. Combined with a new freeze-drying method to maximize the yield and minimize the contamination of silver phosphate generated for isotope ratio mass spectrometry, the TSM protocol is able to generate accurate and precise δ18Op data. We evaluated the TSM protocol using synthetic test solutions and subsequently applied the protocol to samples from locations around the Saint Lawrence River in Montreal, Canada. We believe that the novel technique reported here offers the methodological basis for researchers to extend the application of δ18Op into a much wider range of freshwater ecosystems than has been possible to date.

The relationship between the phosphate and structural carbonate fractionation of fallow deer bioapatite in tooth enamel.

RationaleThe species‐specific relationship between phosphate (δ18OP values) and structural carbonate (δ18OC values) oxygen isotope ratios has been established for several modern and fossil animal species but until now it has not been investigated in European fallow deer (Dama dama dama). This study describes the relationship between phosphate and structural carbonate bioapatite in tooth enamel of extant fallow deer, which will help us further understand the species' unique environmental and cultural history.MethodsThe oxygen isotope composition of phosphate (δ18OP value) and structural carbonate (δ18OC value) of hydroxylapatite was determined in 51 modern fallow deer tooth enamel samples from across Europe and West Asia. The δ18OC values were measured on a GV IsoPrime dual‐inlet mass spectrometer and the δ18OP values on a temperature‐controlled elemental analyser (TC/EA) coupled to a DeltaPlus XL isotope ratio mass spectrometer via a ConFlo III interface.ResultsThis study establishes a direct and linear relationship between the δ18OC and δ18OP values from fallow deer tooth enamel (δ18OC = +9.244(±0.216) + 0.958 * δ18OP (±0.013)). Despite the successful regression, the variation in δ18O values from samples collected in the same geographical area is greater than expected, although the results cluster in broad climatic groupings when Koppen‐Geiger classifications are taken into account for the individuals' locations.ConclusionsThis is the first comprehensive study of the relationship between ionic forms of oxygen (phosphate oxygen and structural carbonate) in fallow deer dental enamel. The new equation will allow direct comparison with other herbivore data. Variable δ18O values within populations of fallow deer broadly reflect the ecological zones they are found in which may explain this pattern of results in other euryphagic species.