Triple Isotope Research Articles

Miniaturized Chemical Tags for Optical Imaging.

Recent advances in optical bioimaging have prompted the need for minimal chemical reporters that can retain the molecular recognition properties and activity profiles of biomolecules. As a result, several methodologies to reduce the size of fluorescent and Raman labels to a few atoms (e.g., single aryl fluorophores, Raman‐active triple bonds and isotopes) and embed them into building blocks (e.g., amino acids, nucleobases, sugars) to construct native‐like supramolecular structures have been described. The integration of small optical reporters into biomolecules has also led to smart molecular entities that were previously inaccessible in an expedite manner. In this article, we review recent chemical approaches to synthesize miniaturized optical tags as well as some of their multiple applications in biological imaging.

Miniaturized Chemical Tags for Optical Imaging

AbstractRecent advances in optical bioimaging have prompted the need for minimal chemical reporters that can retain the molecular recognition properties and activity profiles of biomolecules. As a result, several methodologies to reduce the size of fluorescent and Raman labels to a few atoms (e.g., single aryl fluorophores, Raman‐active triple bonds and isotopes) and embed them into building blocks (e.g., amino acids, nucleobases, sugars) to construct native‐like supramolecular structures have been described. The integration of small optical reporters into biomolecules has also led to smart molecular entities that were previously inaccessible in an expedite manner. In this article, we review recent chemical approaches to synthesize miniaturized optical tags as well as some of their multiple applications in biological imaging.

A triple isotope approach (Sr-O-C) to assess human mobility dynamics in the Lower Germanic limes borderscape (40–470 CE)

The intention of the Roman administration to develop the Lower Germanic limes region into a military zone must have been a catalyst for (long-distance) human and faunal mobility in the course of the 1st century CE. A triple isotope approach (Sr-O-C) has been used on a total of 21 cremations (bone and pars petrosa) and 21 inhumations (dental elements) from the Dutch Lower Germanic limes borderscape region to study the demographicdynamics between 150 and 500 CE. The dental enamel 87Sr/86Sr range from 0.7086 to 0.7158. The variability in Sr within the cremated remains is more limited: 0.7089 to 0.7103. The δ18OPDB data range from −7.6 ‰ to −4.3 ‰. All but one individual dating to the Early and Middle Roman period exhibit Sr ratios that are consistent with the expected local (0.7088–0.7092) or regional (up to ± 0.7110) 87Sr/86Sr signature. The population dynamics drastically change in the subsequent Late Roman period. Fifty percent (6/12) of the investigated Late Roman population (partially) spent part of their childhood away from the Dutch river system or even the Batavian civitas. The cremated long bone 87Sr/86Sr possibly point towards residential stability during the last few years of life: all data are compatible with the expected regional Sr signature. The δ13CPDB data vary between −16.0 ‰ and −8.7 ‰: the latter was indicative of a diet rich in C4 food, which was not a staple in the Roman diet in the Lower Germanic limes region. Although more research is essential to better understand the population dynamics in the limes borderscape, it is clear that the isotope data reflect the political-military status of the Lower Germanic limes region, especially during the transition to a militarized zone in the later Roman period. Identifying possible regions of provenance is a challenge. Another proxy for provenance, namely the cultural artefacts associated with the excavated people, did not show a specific relationship between cultural background and geographical origin.

Towards the Third Millennium Changes in Siberian Triple Tree-Ring Stable Isotopes

Significant air temperature and precipitation changes have occurred since the 2000s in vulnerable Siberian subarctic regions and urged updates of available chronologies towards the third millennium. It is important to better understand recent climatic changes compared to the past decades, centuries and even millennia. In this study, we present the first annually resolved triple tree-ring isotope dataset (δ13C, δ18O and δ2H) for the eastern part of the Taimyr Peninsula (TAY) and northeastern Yakutia (YAK) from 1900 to 2021. We found that the novel and largely unexplored δ2H of larch tree-ring cellulose was linked significantly with δ18O for the YAK site, which was affected by averaged April–June air temperatures and evaporation. Simulated by the Land Surface Processes and Exchanges (LPX-Bern 1.0) model, the water fraction per year for soil depths at 0–20 and 20–30 cm was significantly linked with the new eco-hydrological tree-ring δ2H data. Our results suggest increasing evapotranspiration and response of trees’ water relation to rising thaw water uptake from lower (20–30 cm) soil depth. A positive effect of July air temperature on tree-ring δ18O and a negative impact of July precipitation were found, indicating dry conditions. The δ13C in larch tree-ring cellulose for both sites showed negative correlations with July precipitation and relative humidity, confirming dry environmental conditions towards the third millennium.

Triple oxygen isotope evidence for a hot Archean ocean

Abstract Triple oxygen isotope (δ17O and δ18O) values of high- and low-temperature altered oceanic crust and products of basalt alteration experiments were measured to better constrain ocean isotope compositions in deep time. The data define an array of δ18O and Δ′17O (Δ′17O=δ′17O − λRL × δ′18O + γ) values from mantle values toward 1‰ and −0.01‰, respectively, with a λ of ~0.523. The altered oceanic crust data were used to construct a model for estimating δ18O-Δ′17O values of the ancient oceans if the continental weathering flux (FCW) and/or hydrothermal oceanic crust alteration flux (FHT) changed through time. A maximum lowering of 7‰ and 4‰, respectively, is achieved in the most extreme cases. The δ18O value of the ocean cannot be raised by more than 1.1‰. Eclogites from the Roberts Victor kimberlite (South Africa), with a protolith age of 3.1 Ga, have δ18O-Δ′17O values that precisely overlap with those of the modern altered oceanic crust, suggesting that the Archean oceans had similar isotope values as today. Published triple isotope data for Archean cherts show that all samples have been altered to some degree and suggest an Archean ocean surface temperature of ~70–100 °C. An ocean as light as −2‰ is still consistent with our eclogite data and reduce our temperature estimates by 10 °C.

A new method for the evaluation of measurement uncertainty in strict accordance with measurement model: Determination of total thyroxine in human serum by triple isotope dilution mass spectrometry

The rigorous and reasonable evaluation of uncertainty is crucial for the reliability of the results of a reference measurement procedure. A new uncertainty budget is proposed for uncertainty evaluation of a reference measurement procedure for total thyroxine in human serum based on isotope dilution liquid chromatography-mass spectrometry. In this work, a measurement model for uncertainty evaluation of triple isotope dilution-mass spectrometry was established. The propagation of uncertainties assigned to various input quantities was expressed in strict accordance with the measurement model. A detailed description of the uncertainty evaluation process for the measurement result of a specific serum is given, including the estimate of the input quantities and the determination of the combined standard uncertainty. The expanded uncertainty of the specific human serum (at coverage probability of 95%) was 4.8 nmol/L at the concentration level of 113.6 nmol/L.

New constraints on biological production and mixing processes in the South China Sea from triple isotope composition of dissolved oxygen

Abstract. The South China Sea (SCS) is the world's largest marginal sea, playing an important role in the regional biogeochemical cycling of carbon and oxygen. However, its overall metabolic balance, primary production rates and links to East Asian Monsoon forcing remain poorly constrained. Here, we report seasonal variations in triple oxygen isotope composition (17Δ) of dissolved O2, a tracer for biological O2, gross primary production (GP; inferred from δ17O and δ18O values) and net community production (NP; evaluated from oxygen–argon ratios) from the SouthEast Asian Time-series Study (SEATS) in the SCS. Our results suggest rather stable mixed-layer mean GP rates of ∼ 1500 ± 350 mg C m−2 d−1 and mean NP of ∼ −13 ± 20 mg C m−2 d−1 during the summer southwest monsoon season. These values indicate, within uncertainties and variabilities observed, that the metabolism of the system was in net balance. During months influenced by the stronger northeast monsoon forcing, the system appears to be more dynamic and with variable production rates, which may shift the metabolism to net autotrophy (with NP rates up to ∼ 140 mg C m−2 d−1). Furthermore, our data from the deeper regions show that the SCS circulation is strongly affected by monsoon wind forcing, with a larger part of the water column down to at least 400 m depth fully exchanged during a winter, suggesting the 17Δ of deep O2 as a valuable novel tracer for probing mixing processes. Altogether, our findings underscore the importance of monsoon intensity on shifting the carbon balance in this warm oligotrophic sea and on driving the regional circulation pattern.

Stable isotope variations of dew under three different climates

As a supplementary or the only water source in dry regions, dew plays a critical role in the survival of organisms. The new hydrological tracer 17O-excess, with almost sole dependence on relative humidity, provides a new way to distinguish the evaporation processes and reconstruct the paleoclimate. Up to now, there is no published daily dew isotope record on δ2H, δ18O, δ17O, d-excess, and 17O-excess. Here, we collected daily dew between July 2014 and April 2018 from three distinct climatic regions (i.e., Gobabeb in the central Namib Desert with desert climate, Nice in France with Mediterranean climate, and Indianapolis in the central United States with humid continental climate). The δ2H, δ18O, and δ17O of dew were simultaneously analyzed using a Triple Water Vapor Isotope Analyzer based on Off-Axis Integrated Cavity Output Spectroscopy technique, and then d-excess and 17O-excess were calculated. This report presents daily dew isotope dataset under three climatic regions. It is useful for researchers to use it as a reference when studying global dew dynamics and dew formation mechanisms.

Comparison of GC-ICP-MS, GC-EI-MS and GC-EI-MS/MS for the determination of methylmercury, ethylmercury and inorganic mercury in biological samples by triple spike species-specific isotope dilution mass spectrometry

We present here the comparison of three mass spectrometric techniques coupled to gas chromatography for the speciation of Hg in complex matrices in order to evaluate the limiting factors for providing accurate and precise quantification results.

A 187Re-187Os, 87Rb-87Sr, highly siderophile and incompatible trace element study of some carbonaceous, ordinary and enstatite chondrite meteorites

New 187Re-187Os, 87Rb-87Sr, triple O-isotope isotope, bulk rock highly siderophile- (HSE: Os, Ir, Ru, Pt, Pd, Re), major- and trace-element abundance data are reported for a variety of carbonaceous, ordinary and enstatite chondrite meteorites. In addition, new mineral chemical data are reported for the Chelyabinsk LL5 ordinary chondrite fall for comparison with existing chondrite data and to investigate element sequestration into metal and mineral phases within some chondrites. The focus of the study is to link the variations observed in the HSE abundances and Re-Os isotopes with other isotopic and elemental data to explore the relative roles of sample sizes, terrestrial alteration and parent body processes more fully on chondrite meteorite compositions. Trace element variations in Chelyabinsk silicate, oxide and metal grains highlight the importance of geochemical heterogeneity imparted by mineralogical variations and mode effects, as well as sample size. Using a range of sample powder aliquot sizes, it is possible to show that this becomes significant for the HSE at <0.1 g. Variations in high field strength elements relative abundances (HFSE: Ti, Zr, Nb, Ta, Hf) are also identified within individual aliquots of carbonaceous chondrite Ivuna, emphasizing the importance of complete dissolution of refractory phases. The range of fall and find meteorites examined here demonstrates that terrestrial alteration effects revealed for trace elements (e.g., Ba, U, Sr) do not correlate particularly well with Re/Os variations. Instead, the Re/Os ratios of carbonaceous chondrites are susceptible to disturbance, more so than indicated by incompatible trace element systematics, with the Murchison CM2 carbonaceous chondrite showing significant Re/Os fractionation between sample aliquots. For sample aliquots measured that do not show significant mode or terrestrial alteration effects, parent body processes appear to be largely restricted to thermal metamorphism and dehydration. Including data for this study, the combined published dataset for Re-Os isotope and HSE abundances now extends to 33 ordinary, 39 carbonaceous, 27 enstatite and 6 Rumuruti chondrites. The range in absolute HSE abundances among these meteorite groups is ∼30%, with all chondrites having, within uncertainties, the same average Os, Ir, Ru, Pt and Pd abundances. Notably, carbonaceous chondrites have long-term Re/Os ∼ 8% lower than for the other chondrite groups. If chondrite groups are representative of early planetary feedstocks, then the measured 187Os/188Os of ordinary chondrites make them a close match to the composition of the bulk silicate Earth. Assuming ∼0.5% late accretion of ordinary chondrites to Earth, this would result in a long-term Rb/Sr ratio ∼0.6% higher than from late accretion of carbonaceous chondrites, indicating that ordinary chondrites are a potentially attractive source for moderately volatile enrichment.

Tracing Nitrate Source and Transformation in Glacier Runoffs on the Tibetan Plateau Using Triple Nitrate Isotopes

Glaciers are the largest reservoir of fresh water on earth. Global warming accelerates glacier retreat and enhances glacier runoff, which heavily impacts the geochemical cycling in downstream ecosystems. Nitrate is the main form of nitrogen in glacier runoff, while little is known about its source in high-altitude regions. Here, we measured triple nitrate isotopes (δ 15 N, δ 18 O, and Δ 17 O) in ten geographically separated glacier runoffs on the Tibetan Plateau with the altitudes ranged from 2,409 to 5,564 m. The isotope results were combined with hydrogeochemical indicators to assess the primary sources and transformation processes of nitrate. Results showed that all the glacier runoffs exhibited low nitrate concentration, which ranged from 0.3 ± 0.0 to 1.5 ± 0.8 mg·L -1 . The SIAR model results indicated that soil organic nitrogen and atmospherically oxidized nitrate accounted for 67% of nitrate in the runoffs, whereas human-related source (i.e., chemical fertilizers) contributed 33% on average. Significant geospatial differences in the contribution of chemical fertilizers were identified, with their contributions being significantly higher in the monsoon domain (43% ± 3%) than that in the westerlies domain (22% ± 8%). Furthermore, δ 18 O of nitrate ranged from -15‰ to 15‰, this suggested that the nitrification process is responsible for the nitrogen transformation in Tibetan glacier ecosystems. Our study reveals the source of nitrogen in Tibetan glaciers and highlights the substantial impact of human activity on glacier nutrient cycling. Our work may shed light on the understanding of nitrogen cycling in downstream ecosystems.

Isotopic modelling of Archean crustal evolution from comagmatic zircon–apatite pairs

The composition of Earth's early crust is challenging to assess as only a fragmented record remains. As a consequence, deciphering the composition of early crust as a means to understand early processes on our planet often relies on the isotopic composition of resistive minerals. Here we present a new tool for investigating igneous petrogenesis and crustal evolution by combining 87Sr/86Sr measurements of apatite inclusions with U–Pb and Hf isotope analysis of their host zircon crystals. This approach takes advantage of the complementary inverse fractionation behaviour of Rb/Sr and Lu/Hf, and the cogenetic host/inclusion relationship, to link the three isotopic systems and construct an evolution model in triple isotope space. By applying this triple isotope system modelling to Mesoarchean igneous rocks from the Akia terrane in SW Greenland, we reconstruct a bulk SiO2 composition of 63-68 wt% for the precursor source crust and infer an average crustal residence time of 300–350 Ma. Our modelling implicates involvement of intermediate to felsic Paleo-Eoarchean crust in the genesis of voluminous 3.0 Ga magmatic rocks of the Akia terrane, one of the largest components of the Archean North Atlantic Craton. A further outcome of this approach is the ability to place more robust empirical constraints on the Lu/Hf ratio of the precursor crust by comparison of the modelling output to a global whole-rock dataset. The approach in this work provides a template for further application to ancient rocks in order to better understand the evolution of early Earth.

The triple argon isotope composition of groundwater on ten-thousand-year timescales

Understanding the age and movement of groundwater is important for predicting the vulnerability of wells to contamination, constraining flow models that inform sustainable groundwater management, and interpreting geochemical signals that reflect past climate. Due to both the ubiquity of groundwater with order ten-thousand-year residence times and its importance for climate reconstruction of the last glacial period, there is a strong need for improving geochemical dating tools on this timescale. Whereas 14C of dissolved inorganic carbon and dissolved 4He are common age tracers for Late Pleistocene groundwater, each is limited by systematic uncertainties related to aquifer composition and lithology, and the extent of water-rock interaction. In principle, radiogenic 40Ar in groundwater acquired from decay of 40K in aquifer minerals should be insensitive to some processes that impact 14C and 4He and thus represent a useful, complementary age tracer. In practice, however, detection of significant radiogenic 40Ar signals in groundwater has been limited to a small number of studies of extremely old groundwater (>100 ka). Here we present the first high-precision (<1‰) measurements of triple Ar isotopes (40Ar, 38Ar, 36Ar) in groundwater. We introduce a model that distinguishes radiogenic 40Ar from atmospheric 40Ar by using the non-radiogenic Ar isotopes (36Ar, 38Ar) to correct for mass-dependent fractionation. Using this model, we investigate variability in radiogenic 40Ar excess (Δ40Ar) across 58 groundwater samples collected from 36 wells throughout California (USA). We find that Δ40Ar ranges from ~0‰ (the expected minimum value) to +4.2‰ across three study areas near Fresno, San Diego, and the western Mojave Desert. Based on measurements from a network of 23 scientific monitoring wells in San Diego, we find evidence for a strong dependence of Δ40Ar on aquifer lithology. We suggest that Δ40Ar is fundamentally controlled by the weathering of old K-bearing minerals and thus reflects both the degree of groundwater-rock interaction, which is related to groundwater age, and the integrated flow through different geological formations. Future studies of Late Pleistocene groundwater may benefit from high-precision triple Ar isotope measurements as a new tool to better interpret 14C- and 4He-based constraints on groundwater age and flow.

Triple sulfur-oxygen-strontium isotopes probabilistic geographic assignment of archaeological remains using a novel sulfur isoscape of western Europe.

Sulfur isotope composition of organic tissues is a commonly used tool for gathering information about provenance and diet in archaeology and paleoecology. However, the lack of maps predicting sulfur isotope variations on the landscape limits the possibility to use this isotopic system in quantitative geographic assignments. We compiled a database of 2,680 sulfur isotope analyses in the collagen of archaeological human and animal teeth from 221 individual locations across Western Europe. We used this isotopic compilation and remote sensing data to apply a multivariate machine-learning regression, and to predict sulfur isotope variations across Western Europe. The resulting model shows that sulfur isotope patterns are highly predictable, with 65% of sulfur isotope variations explained using only 4 variables representing marine sulfate deposition and local geological conditions. We used this novel sulfur isoscape and existing strontium and oxygen isoscapes of Western Europe to apply triple isotopes continuous-surface probabilistic geographic assignments to assess the origin of a series of teeth from local animals and humans from Brittany. We accurately and precisely constrained the origin of these individuals to limited regions of Brittany. This approach is broadly transferable to studies in archaeology and paleoecology as illustrated in a companion paper (Colleter et al. 2021).

The last battle of Anne of Brittany: Solving mass grave through an interdisciplinary approach (paleopathology, biological anthropology, history, multiple isotopes and radiocarbon dating).

Mass graves are usually key historical markers with strong incentive for archeological investigations. The identification of individuals buried in mass graves has long benefitted from traditional historical, archaeological, anthropological and paleopathological techniques. The addition of novel methods including genetic, genomic and isotopic geochemistry have renewed interest in solving unidentified mass graves. In this study, we demonstrate that the combined use of these techniques allows the identification of the individuals found in two Breton historical mass graves, where one method alone would not have revealed the importance of this discovery. The skeletons likely belong to soldiers from the two enemy armies who fought during a major event of Breton history: the siege of Rennes in 1491, which ended by the wedding of the Duchess of Brittany with the King of France and signaled the end of the independence of the region. Our study highlights the value of interdisciplinary approaches with a particular emphasis on increasingly accurate isotopic markers. The development of the sulfur isoscape and testing of the triple isotope geographic assignment are detailed in a companion paper [13].

Multiple sulfur isotopes in post-Archean deposits as a potential tracer for fluid mixing processes: An example from an iron oxide–copper–gold (IOCG) deposit in southern Peru

Sulfur has multiple stable isotopes (32S, 33S, 34S, and 36S), but little research has been conducted to investigate the information that low abundance sulfur isotope ratios (i.e., 33S/32S and 36S/32S) may carry on ore-forming processes in post-Archean deposits. In this study, the Cretaceous Mina Justa iron oxide–copper–gold deposit, was selected to examine the capability of multiple sulfur isotopes to trace ore-forming processes in post-Archean mineral deposits. In situ secondary ion mass spectrometry was applied to the pyrite of the magnetite–pyrite stage in the deposit to characterize the spatial variation of multiple sulfur isotopes at the microscale. This revealed a clear co-variation trend between δ34S (= 1000 × [(34S/32S)sample/(34S/32S)V-CDT − 1]) and Δ33S (= δ33S − 1000 × [(1 + δ34S/1000)0.515 – 1]). Simple modeling suggests that the triple sulfur isotope data recorded is best explained by mixing magmatic and externally derived (e.g., basinal brine) fluids. The contribution of external fluids is also supported by the trace element distribution patterns in pyrite, as revealed by laser ablation-inductively coupled plasma-mass spectrometry. This study is the first attempt to use multiple sulfur isotopes to trace ore-forming processes in post-Archean deposits and demonstrates that multiple sulfur isotopes are a faithful recorder of ore-forming processes at the microscale, especially when multiple fluids mix.

Sulfur isotope signatures of sulfides from the Khibina and Lovozero massifs (Kola Alkaline Province, Fennoscandian Shield)

The sulfur isotope geochemistry of the Khibina and Lovozero agpaitic massifs provides an opportunity to understand the role of plume-lithosphere interaction processes responsible for the Paleozoic alkaline igneous activity in the north-eastern part of the Fennoscandian Shield. The stable sulfur isotope δS analysis using triple collector isotope ratio mass spectrometer (IRMS) has been carried out on the pentlandite, chalcopyrite and pyrite from nepheline syenites. The δS values for pentlandite from Khibina rocks range from +0.69 to +2.06 ‰ relative to the Vienna Canyon Diablo Troillite standard (VCDT), and the pyrite has significantly higher δS values up to +4.92 ‰ VCDT. The pentlandite from the Lovozero samples has value +1.48 ‰ VCDT, δS values of chalcopyrite is +2.85 ‰ VCDT. The maximum positive δS values are obtained for Lovozero pyrite, which vary from +5.41 to +6.30 ‰ VCDT. Comparison of sulfur-geochemical features of Khibina and Lovozero nepheline syenite with δS data for the carbonatites from the Khibina, Sallanlatvi, Seblyavr, Vuoriyarvi, Salmagora and Kovdor massifs show later carbonatite formation relatively to associated alkaline rocks. Geochemical sulfur isotope δS investigations emphasizes that parental magmas of the Khibina and Lovozero alkaline massifs were derived from a metasomatized subcontinental lithospheric mantle (SCLM). We suggest that high-δS signature on the SCLM (δS of +1 to +6 ‰ VCDT) can be explained by subduction of the high-δS Archaean crust.

Sources of atmospheric lead (Pb) after quarter century of phasing out of leaded gasoline in Bangkok, Thailand

After global phasing out of leaded gasoline, anthropogenic sources of atmospheric lead (Pb) are dominated by coal combustion emissions, high-temperature metallurgical processes, and vehicle exhausts. Thailand was one of the first countries in Southeast Asia to completely phase out leaded gasoline by the year 1994. This study investigates the sources of atmospheric Pb in Thai aerosols, a quarter-century after phasing out of leaded gasoline using a multiproxy approach, Pb isotopes in conjunction with trace metal composition of PM2.5. Aerosol samples were collected for 1 year from January 2018 to April 2019 from Bangkok and Chonburi to understand the influence of seasonal variation on aerosol chemistry. Bangkok is the only megacity in Thailand and notorious for traffic congestion and Chonburi is a coastal town, 80 km southeast of Bangkok where the inter monsoon winds make landfall. Aerosol Pb concentrations significantly decreased in 25 years from 74 ± 5 ng/m3 in 1994–1995 to 14 ± 13 ng/m3 measured in Bangkok during Northeast (NE) monsoon winds. Concentrations of all the metals are higher in Chonburi compared to Bangkok in the NE monsoon wind, owing to the addition of local emissions from the megacity over the long-range transported metals before the winds reach the coastal town. The Pb isotope ratios have a wide range (206Pb/207Pb range 1.1343–1.1685 and 208Pb/207Pb range 2.4138–2.4450) but the average ratios are not significantly different in Bangkok and Chonburi for all three seasons. However, present day 206Pb/207Pb ratios are more radiogenic than those measured 25 years ago in Bangkok. The Pb isotopes from both locations in all seasons have considerable overlap with unleaded gasoline and diesel used in Southeast Asia indicating automobile exhaust as an important source. Additionally, the NE monsoon winds are influenced by mixing of crustal dust (Al/Pb ratios correlates well with 206Pb/207Pb, r2 = 0.63) with coal combustion emission (strong inter-correlation of Pb, Zn, As and Cd, r2 from 0.72 to 0.94) from China and Vietnam. Pb isotopes of the Southwest (SW) monsoon winds are also influenced by crustal dust and falls on the mixing line between coal combustion and ore processing emission from India in a Pb triple isotope plot. Chemical composition of aerosols in the inter-monsoon winds are similar to SW monsoon winds. After a quarter-century of leaded gasoline banning in Thailand, the atmospheric Pb sources have changed from less radiogenic leaded gasoline exhaust and Chinese ore processing to more radiogenic unleaded gasoline and diesel exhaust and coal combustion.

I‐Type Cosmic Spherules as Proxy for the Δ′17O of the Atmosphere—A Calibration With Quaternary Air

AbstractRemnants of shooting stars are preserved in form of cosmic spherules in ice and sediments. The extraterrestrial material is heated and melted upon atmospheric entry and is collected at the Earth's surface as cosmic spherules. A fraction of cosmic spherules (I‐type cosmic spherules) sources from extraterrestrial Fe,Ni metal. These metal particles melt and become oxidized in the atmosphere. The oxygen in the resulting oxides (magnetite, wüstite) sources entirely from the atmosphere. Here, we demonstrate that I‐type cosmic spherules can be used to reconstruct the triple oxygen isotope anomaly of the past atmosphere, which provides information on the gross primary productivity and/or paleo‐CO2 levels. We present a calibration of the proxy using Antarctic cosmic spherules. We further introduce Δ′56Fe and demonstrate that triple iron isotopes can be used to obtain information about the underlying fractionation mechanism (e.g., kinetic vs. equilibrium fractionation).

Global Estimates of Marine Gross Primary Production Based on Machine Learning Upscaling of Field Observations

AbstractApproximately half of global primary production occurs in the ocean. While the large‐scale variability in net primary production (NPP) has been extensively studied, ocean gross primary production (GPP) has thus far received less attention. In this study, we derived two satellite‐based GPP models by training machine learning algorithms (Random Forest) with light‐dark bottle incubations (GPPLD) and the triple isotopes of dissolved oxygen (GPP17Δ). The two algorithms predict global GPPs of 9.2 ± 1.3 × 1015 and 15.1 ± 1.05 × 1015 mol O2 yr−1 for GPPLD and GPP17Δ, respectively. The projected GPP distributions agree with our understanding of the mechanisms regulating primary production. Global GPP17Δ was higher than GPPLD by an average factor of 1.6 which varied meridionally. The discrepancy between GPP17Δ and GPPLD simulations can be partly explained by the known biases of each methodology. After accounting for some of these biases, the GPP17Δ and GPPLD converge to 9.5 ∼ 12.6 × 1015 mol O2 yr−1, equivalent to 103 ∼ 150 Pg C yr−1. Our results suggest that global oceanic GPP is 1.5–2.2 fold larger than oceanic NPP and comparable to GPP on land.