Bulk δ13C Values Research Articles

Mathematical lipid correction of δ13C and effect of lipid extraction on δ15N of European eel (Anguilla anguilla) muscle: Lipid correction of δ13C in European eels.

Carbon (δ13C) and nitrogen (δ15N) stable isotope analysis is a powerful tool to investigate diverse questions in fish ecology, such as their trophic position or migration strategies. These questions appear particularly important to protect endangered European eel. However, elevated lipid content in eel muscle can bias δ13C values, as lipids are 13C-depleted compared to proteins and carbohydrates. We measured δ13C and δ15N values of bulk and lipid-free samples of eel muscle. Lipid-free samples were obtained after the extraction of lipids with cyclohexane. Lipid-corrected δ13C values, using five different mathematical equations based on bulk δ13C values, were compared to lipid-free δ13C values. We also evaluated the effect of lipid extraction on δ15N values. The analyses were based on linear regression performed on 333 individuals captured in nine lagoons and four rivers. Independently to the capture site or habitat (river or lagoon), the predicted lipid-corrected δ13C values were highly consistent with the measured lipid-free δ13C values (R2 > 0.90). The application of specific equations for each habitat or capture site only slightly increases these R2 (1.5% or less). The lipid extraction treatment significantly decreased by 0.2‰ the δ15N values compared to bulk samples. Given the excellent prediction of mathematical equations and the small decrease of δ15N values after lipids extraction, we propose to use mathematical correction to estimate δ13C values of eel muscle. As the habitats or sites did not strongly influence the results, the coefficients from our study can be applied to other studies on European eel.

Dietary plasticity and broad North Atlantic origins inferred from bulk and amino acid-specific δ15N and δ13C favour killer whale range expansions into Arctic waters.

Killer whales (Orcinus orca) occur seasonally in the eastern Canadian Arctic (ECA), where their range expansion associated with declining sea ice have raised questions about the impacts of increasing killer whale predation pressure on Arctic-endemic prey. We assessed diet and distribution of ECA killer whales using bulk and compound-specific stable isotope analysis (CSIA) of amino acids (AA) of 54 skin biopsies collected from 2009 to 2020 around Baffin Island, Canada. Bulk ECA killer whale skin δ15N and δ13C values did not overlap with potential Arctic prey after adjustment for trophic discrimination, and instead reflected foraging history in the North Atlantic prior to their arrival in the ECA. Adjusted killer whale stable isotope (SI) values primarily overlapped with several species of North Atlantic baleen whales or tuna. Amino acid (AA)-specific δ15N values indicated the ECA killer whales fed primarily on marine mammals, having similar glutamic acid δ15N-phenylalanine δ15N (δ15NGlx-Phe) and threonine δ15N (δ15NThr) as mammal-eating killer whales from the eastern North Pacific (ENP) that served as a comparative framework. However, one ECA whale grouped with the fish-eating ENP ecotype based δ15NThr. Distinctive essential AA δ13C of ECA killer whale groups, along with bulk SI similarity to killer whales from different regions of the North Atlantic, indicates different populations converge in Arctic waters from a broad source area. Generalist diet and long-distance dispersal capacity favour range expansions, and integration of these insights will be critical for assessing ecological impacts of increasing killer whale predation pressure on Arctic-endemic species.

Lipid extraction alters amino acid composition and bulk, but not amino acid, carbon and nitrogen isotope values.

Concerns exist over observed shifts in value and variance of nitrogen isotopes following physicochemical extraction of lipids from organic matter. The mechanisms behind these apparent changes in bulk tissue δ15N values are not fully understood yet have major implications for analytical costs and integrity of data interpretations. Changes in proximate analysis, amino acid composition, C:N ratios, bulk tissue and amino acid δ13C and δ15N values, and resulting isotope-based food web metrics were compared between lipid-intact and lipid-extracted muscle tissue of fishes spanning <1% to >20% muscle fat content to identify mechanisms of nitrogen isotope fractionation associated with physicochemical lipid extraction. Bulk δ13C and δ15N values increased and %N, C:N ratios and crude protein content decreased following lipid extraction. Resulting bulk isotope niche spacing and overlap varied significantly between lipid-intact and lipid-extracted tissues. While amino acid composition significantly changed during lipid extraction, particularly for lipid-associated amino acids (e.g., Glu, Lys, Ser), individual amino acid δ13C and δ15N values, and their associated compound-specific isotope analysis of amino acids (CSIA-AA)-based food web metrics, did not. Physicochemical lipid extraction caused significant tissue composition changes (e.g., leaching of amino acids and 15N-deplete nitrogenous waste) that affected δ13C and δ15N values and tissue %C and %N beyond simply removing lipids. However, lipid extraction did not alter individual amino acid δ13C or δ15N values or their associated CSIA-AA-based food web metrics.

Isotopic study of lipids and collagen in bones from archaeological and modern ungulates for the study of paleodiets in Argentina

In this paper we carried out a sequential extraction of lipids and collagen and obtained carbon and nitrogen stable isotope values of archaeological and modern bone samples of native ungulates from the Argentine Patagonia (Lama guanicoe, Pudu puda, Hippocamelus bisulcus) and Northwest (Lama sp., Vicugna vicugna). Collagen and lipids are biomolecules with exceptional survival rates in archaeological bone matrixes and provide complementary information about diet. We studied 28 ungulate specimens and obtained bulk δ13C values (δ13Clip, δ13Ccoll) and δ15N values to evaluate protein diet, whole diet, and offsets between values from lipids and collagen (Δ13Clip-coll). Results showed greater variability in the offsets of the different ungulate species than previously reported for terrestrial herbivores. This variability could be attributed to differences in body mass, particular niche adaptations, seasonal metabolic stress, diet change, and/ or human-ungulate interactions in each case. This study sheds light on the potential of paired lipid-collagen stable isotope values for interpreting paleodiet dynamics and unraveling individual life histories.

Comparison of Carbon Isotope Ratio Measurement of the Vanillin Methoxy Group by GC-IRMS and 13C-qNMR.

Site-specific carbon isotope ratio measurements by quantitative 13C NMR (13C-qNMR), Orbitrap-MS, and GC-IRMS offer a new dimension to conventional bulk carbon isotope ratio measurements used in food provenance, forensics, and a number of other applications. While the site-specific measurements of carbon isotope ratios in vanillin by 13C-qNMR or Orbitrap-MS are powerful new tools in food analysis, there are a limited number of studies regarding the validity of these measurement results. Here we present carbon site-specific measurements of vanillin by GC-IRMS and 13C-qNMR for methoxy carbon. Carbon isotope delta (δ13C) values obtained by these different measurement approaches demonstrate remarkable agreement; in five vanillin samples whose bulk δ13C values ranged from -31‰ to -26‰, their δ13C values of the methoxy carbon ranged from -62.4‰ to -30.6‰, yet the difference between the results of the two analytical approaches was within ±0.6‰. While the GC-IRMS approach afforded up to 9-fold lower uncertainties and required 100-fold less sample compared to the 13C-qNMR, the 13C-qNMR is able to assign δ13C values to all carbon atoms in the molecule, not just the cleavable methoxy group.

The evolution of the majiang paleoreservoir, west margin of xuefeng uplift: Insights from in situ calcite U–Pb dating and bitumen and shale trace element analysis

The Majiang Reservoir, situated within the Yangtze Block, is the largest paleoreservoir in the region. Employing a comprehensive methodology involving the analysis of trace and rare earth elements in bitumen and shale, in situ U–Pb dating of hydrocarbon-associated calcite, and incorporating previously published data on oil-source correlation and significant stages of reservoir development, we successfully reconstructed the complete evolution of the Majiang Reservoir quantitatively. The bitumen trace elements data show the ratio of V/(V + Ni) ranging from 0.64 to 0.82, Ni/Co exceeding 7.0 and Zr/Cr below 1.0. PAAS-normalized rare earth element distribution patterns of both bitumen and Cambrian shales present zig-zags distributions. In addition, biomarker distribution acquired by catalytic hydropyrolysis and bulk δ13C values of both bitumen and Cambrian shales (−29.1‰ to −34.7‰ vs −30.2‰ to −32.3‰) also show similarity. All the geochemical parameters together indicate that the primary source of bitumen stems from Early Cambrian shales. Integrating fluid inclusion analysis, specifically examining two Th groups with temperatures of 97.2 °C and 142.6 °C, and U–Pb dating on hydrocarbon-bearing calcite (∼300 Ma), referencing prior Re–Os dates on bitumen (∼430 Ma) and pyrobitumen (∼80 Ma) and quartz fluid inclusion Ar–Ar dating (∼225 Ma), we successfully reconstructed the entire hydrocarbon evolution. The findings reveal that initial oil generation occurred during the Caledonian event, followed by secondary continuous oil and gas generation and migration, influenced by the Indosinian event. The combination of fluid inclusion analysis and isotopic geochronology data exemplifies immense potential in precisely determining the progression of petroleum evolution.

Response of stable isotopes (δ2H, δ13C, δ15N, δ18O) of lake water, dissolved organic matter, seston, and zooplankton to an extreme precipitation event

Lake ecosystems process and cycle organic substrates, thus serving as important bioreactors in the global carbon cycle. Climate change is predicted to increase extreme weather and precipitation events that can flush nutrients and organic matter from soils to streams and lakes. Here we report changes in stable isotopes (δ2H, δ13C, δ15N, or δ18O) of water, dissolved organic matter (DOM), seston, and zooplankton in a subalpine lake at short time resolution following an extreme precipitation event between early July to mid-August 2021. Water from excess precipitation and runoff remained in the lake epilimnion and coincided with increasing δ13C values of seston (−30 ‰ to −20 ‰), due to the input of carbonates and terrestrial organic matter. Particles settled into deeper lake layers after two days and contributed to the uncoupling of C and N cycling as the lake responded to this extreme precipitation event. Following the event, there was an increase in bulk δ13C values of zooplankton (from −35 ‰ to −32 ‰). Throughout this study, δ13C values of DOM remained stable throughout the water column (−29 ‰ to −28 ‰), while large isotopic fluctuations in DOM δ2H (−140 ‰ to −115 ‰) and δ18O (+9 ‰ to +15 ‰) values suggested DOM relocation and turnover. Integrating isotope hydrology, ecosystem ecology, and organic geochemistry offers an element-specific, detailed approach to investigating the impact of extreme precipitation events on freshwater ecosystems and particularly aquatic food webs.

Preservation of stable isotope signatures of amino acids in diagenetically altered Middle to Late Holocene archaeological mollusc shells

Stable isotope proxies measured in the proteinaceous fraction of archaeological mollusc shell represents an increasingly important archive for reconstructing past ecological and biogeochemical conditions of nearshore environments. A major issue, however, is understanding the impact of diagenetic alteration in sub-fossil shell isotope values. “Bulk” stable isotope values of nitrogen (δ15N), and especially carbon (δ13C) often shift strongly with increasing C/N ratios in degraded shell, resulting in unreliable data. Here, we examine preservation of an entirely new set of shell paleo-proxies, compound-specific isotopes of amino acids (CSI-AA). We examine carbon (δ13CAA) and nitrogen (δ15NAA) patterns and values from the organic fraction of California mussel (Mytilus californianus) shells from the California Channel Islands. Archaeological shell samples ranging in age from ca. 6,100 to 250 cal BP exhibiting a wide range of degradation states were collected from varied depositional environments (e.g., exposed coastal bluff, buried strata, etc.), and were directly compared to modern shells of the same species and region.Our results indicate organic matter C/N ratios as the best bulk diagnostic indicator of the relative degradation state of shell organic fraction, including changes at the molecular level. Modern shell organic C/N ratios ranged from 2.8 to 3.5, while those in archaeological shell were substantially elevated (3.4–9.5), exhibiting strong and significant negative correlations with bulk δ13C values, weight %C, and weight %N, and a significant but weaker correlation with δ15 N values. An additional “cleaning” step using weak NaOH helped to remove possible exogenous contaminants and improved bulk values of some samples. However, relative molar AA abundances revealed that some AAs, especially the two most abundant, Glycine and Alanine, progressively decreased with increasing C/N ratio. The loss of these amino acids permanently alters bulk isotope values regardless of removal of contaminants. Modeling the bulk isotope change expected due to amino acid molar composition showed major and predictable shifts in bulk δ13C values from selected AA loss, and similarly large but far more variable impacts from exogenous contaminants.In contrast to bulk data, key CSI-AA values and patterns remained almost entirely unaltered, even in the most degraded shell samples, closely matching expected biosynthetic isotope patterns in modern mussel shell. AA isotope proxies for “baseline” (δ15N-Phenylalanine and average δ13C-Essential AAs) and planktonic trophic structure (δ15N-Glutamic Acid and δ15N-Phenylalanine) were not statistically altered with degradation in any sample. Overall, we conclude that while bulk isotopes, particularly δ13C, are very likely to be unreliable in archaeological or subfossil shell with C/N ratios higher than ∼4.0, CSI-AA proxies can still be used to reconstruct past climatic and ecological conditions of the nearshore marine environment.

Persistently high efficiencies of terrestrial organic carbon burial in Chinese marginal sea sediments over the last 200 years

Constraining the origins, transport history, and burial efficiency of terrestrial organic carbon (OCterr) accumulating in marine sediments is of fundamental importance for understanding the carbon cycle on a range of spatial and temporal scales. While there is abundant evidence that OC composition and age influences the sequestration of OCterr in surface sediments, little is known about longer-term controls on OCterr sources and burial efficiencies in response to natural and anthropogenic processes that influence marginal sea sediments. Here, we use bulk and molecular-level carbon isotopic (δ13C and Δ14C) measurements to examine depth-related variations in the sources, ages and burial efficiency of OCterr in a sediment core that captures deposition over the last 200 years in the central Yellow Sea mud area, the largest mud deposit in eastern Chinese marginal seas. The similar 14C ages of terrestrial higher plant long-chain fatty acid biomarkers (1830–2700 yr) to those of sedimentary OC (1890–3360 yr) suggest the continuous and dominant supply of pre-aged OC (OCpre-aged). Two carbon isotopic mixing models are used to apportion contributions from different terrestrially-derived OC pools. A dual carbon mixing model based on bulk OC and molecular δ13C and Δ14C values showed OCpre-aged and fossil OC (OCfossil) accounted for 52 ± 3% and 13 ± 2% of sedimentary OC, respectively; while a binary mixing model based on bulk δ13C values showed OCterr accounted for 45 ± 3% of sedimentary OC. Estimates of high burial efficiency for OC (~60%) and especially for the different terrestrial OC pools (>80%) over the last 200 years highlight that refractory millennial-aged terrestrial OC inputs from the Yellow River combined with stable depositional conditions promote OC preservation in the Yellow Sea. Notably, OCpre-aged and OCfossil exhibited contrasting fates, with higher burial efficiency for the former. These observations are attributed to differences in mineral associations, transport pathways as well as changes in sediment provenance and hydrodynamic regime. Furthermore, our results suggest that initial sequestration of OCterr in surface sediments presages long-term burial in deeper sediments despite the existence of temporal variability. Although not directly influenced by riverine discharge, persistent and efficient sequestration of millennial-aged terrestrial OC renders the distal marginal sea mud area a long-term carbon sink on (at least) centennial to millennial timescales.

Fluid flow and water/rock interaction during the Early Triassic evolution of the western Canada sedimentary basin as revealed by carbonate diagenesis

Diagenetic evolution of sedimentary basins, which is crucial to resource exploration and development, and carbon capture, utilization, and storage (CCUS), is mainly controlled by fluid influx associated with the regional tectonic and hydrogeologic setting of these basins. Therefore, petrographic and isotope geochemical studies integrated with geodynamics of sedimentary basins, fluid flow and transport hydrodynamics are insightful tools to reconstruct the regional history of paleofluid flow and their driving mechanisms. This study investigates carbonate diagenesis in the Lower Triassic Montney Formation of the Western Canadian Sedimentary Basin (WCSB) to constrain the origin of diagenetic fluids, their major flow systems, and their association with the tectonics and hydrogeology of the WCSB. Petrographic analysis shows various generations of early-to late-stage non-ferroan to ferroan calcite (C1–C3) and dolomite (D1-D4) cement. Bulk δ13C and δ18O values of carbonate cements range from −7.1 to +0.4‰ and −9.5 to −2.8‰ (VPDB), respectively, noticeably more depleted than those estimated for Early Triassic seawater. Their 87Sr/86Sr isotope ratio, 0.7108 to 0.7128, is significantly more radiogenic than Early Triassic seawater. These isotopic values confirm the extensive interaction of the Montney Formation pore water with hot basinal brines of Precambrian metasediments and siliciclastic strata, the influx of hydrothermal fluids, and high burial temperature in the basin. The 13C-depleted signature of these cements supports the contribution of organic carbon, from the breakdown and oxidation of organic matter and hydrocarbons via microbial and thermochemical sulfate reduction processes. The results of this study suggest that Montney Formation diagenesis was influenced by evolved Montney pore water interacting with fluids sourced from metasediments of the Cordillera thrust belt and topography-driven fluids from Columbian and Laramide tectonism. This study highlights the importance of an integrated approach to better understand changes in fluid compositions during diagenesis and reconstruction of basin-scale paleofluid flow systems in sedimentary basins.

Carbon isotope stratigraphy of Precambrian iron formations and possible significance for the early biological pump

The origin of Precambrian iron-formations (IF) remains contentious, particularly with respect to the mineralogy of primary precipitates and the exact processes and conditions leading to their formation. Despite the uncertainties, prevailing hypotheses range from biological precipitation of ferrihydrite to abiotic water-column formation of greenalite. By contrast, iron carbonate minerals (siderite, ankerite) in IF have traditionally been attributed to diagenetic origins based on textural and isotopic relationships. Recent studies on IF from the Neoarchaean-Paleoproterozoic Transvaal Supergroup of South Africa have revealed evidence for apparently primary, low-δ13C, Fe/Mn-bearing Mg calcite as precursor to iron carbonate formation and as a potentially underestimated pathway of isotopically light carbon burial during IF deposition. Here, we present whole-rock δ13C data and carbonate-specific geochemical analyses for samples from five drill cores that capture the entire stratigraphic extent of the Kuruman and Griquatown IF of the Transvaal Supergroup. Our results demonstrate remarkable consistency in stratigraphic profiles among the locations for the trends and magnitudes of bulk δ13C values that are independent of paragenetic association, modal mineralogy, and chemical composition of the bulk carbonate fraction of each sample. We interpret these records as resulting from water-column abiotic carbonate formation that was accompanied by kinetic isotopic effects associated with fluctuating conditions (pH, alkalinity) controlling carbonate supersaturation in ambient seawater. Although our interpretation provides strong support for abiotic, anoxic models for IF genesis prior to the Great Oxidation Event (GOE), it does not entirely preclude additional biological mechanisms of primary ferric oxyhydroxide formation and its possible role in an early biological pump.

Middle Jurassic–Lower Cretaceous glendonites from the eastern Barents Shelf as a tool for paleoenvironmental and paleoclimatic reconstructions

Glendonites are carbonate pseudomorphs after ikaite which use as indicators of near-freezing temperatures. We describe the first glendonites of Middle–Late Jurassic to Early Cretaceous age from the Barents Shelf, including the first glendonites of Late Barremian–Early Aptian age ever discovered on Earth and provide the detailed mineralogical-geochemical and isotopic studies. Mesozoic glendonites are well-known across the Arctic realm, however the ikaite-calcite transformation and implication of glendonite findings are still debatable. Pseudomorphs are mainly composed of calcite. Cathodoluminescence and scanning electron microscopy studies reveal three types (I-III) of calcite: type I - elongated, rounded and irregular calcite; type II - blocky, fibrous and needle-like calcite/siderite; type III - blocky calcite in pores. Elemental analyses distinguish geochemical differences between the calcite types: type I comprises pure CaCO3; type II calcite contains Mg and P (in all studied samples), Fe (Bajocian–Callovian), S (Middle Volgian) or Sr (Upper Barremian–Lower Aptian); type III calcite is depleted in Mg, P and Fe. Concentrations of Mn, Fe, Sr and calculated Mn/Ca, Fe/Ca and Sr/Ca ratios are suggestive of diagenetic alteration. Bulk δ18O values range from −5.39 to −1.71‰ VPDB, supporting overprinting of primary values during burial diagenesis, while bulk δ13C values range from −33.3 to −22.6‰ VPDB, providing the influence of organic matter on ikaite-glendonite formation. However, 87Sr/86Sr values range from 0.7070 to 0.7110, mainly corresponding to Jurassic–Cretaceous seawater. Rare-earth elements characterize porewater REE-patterns, with slight middle REE-enrichment and depletion in light and heavy REE. Weak positive and negative Ce anomalies indicate fluctiating from anoxic to oxic conditions during ikaite-glendonite formation. Our new biostratigraphic data refine the ages of glendonite-bearing horizons in the Barents Shelf region, allowing a more definitive correlation with coeval glendonite occurrences across the Arctic realm and with global climatic changes during the Jurassic–Cretaceous.

Palaeopathology and amino acid δ13C analysis: Investigating pre-Columbian individuals with tuberculosis at Pica 8, northern Chile (1050-500 BP)

Bulk δ15N and δ13C values of proteinaceous tissues are being increasingly used in bioarchaeological studies to elucidate the physio-pathological status of ancient individuals. This method has not always been successful.The present study aims to explore the novel use of single amino acid carbon isotope analysis in palaeopathology by investigating the effect of a serious infectious disease, tuberculosis (TB), on the isotope composition of two collagenous tissues (tendon, rib). This is achieved by comparing the bulk and amino acid stable isotope compositions of collagenous tissues collected from human remains with and without TB-like bone lesions. The sample set comprises twelve adult individuals (males = 6, females = 6), who were buried at Pica 8, an inland oasis situated on the mid-elevation plains of northern Chile (Late Intermediate Period, ~1050-500 BP). Similarity and consistency in the diet of these individuals are explored using amino acid carbon isotope analysis of 1-cm hair segments longitudinally cut along a single hair fibre.The results show that there is a difference between collagen δ13C serine values measured in the rib collagen of five individuals presenting TB-like bone lesions (3 males and 2 females) and in those five without lesions (3 males and 2 females; control individuals). The rib collagen δ13C serine values of pathological individuals are lower (more negative) than those of the control individuals. Within the group of pathological individuals, lower δ13C serine values in rib collagen are correlated with higher (more positive) δ15N values. Since only individuals (N = 10) with similar dietary intakes were included in the statistical analyses, it appears that the δ13C serine values could be linked to altered carbon metabolism, rather than induced by dietary factors. Serine accounts for less than 3% of the total carbon in bone collagen, and thus an altered serine metabolism would be masked within the averaged bulk carbon isotope value. In future studies, it is advised to undertake stable carbon isotope analysis of non-essential amino acids as a means of characterising pathologically altered body tissues.

Stable isotope signatures in historic harbor seal bone link food web-assimilated carbon and nitrogen resources to a century of environmental change.

Anthropogenic climate change will impact nutrient cycles, primary production, and ecosystem structure in the world's oceans, although considerable uncertainty exists regarding the magnitude and spatial variability of these changes. Understanding how regional-scale ocean conditions control nutrient availability and ultimately nutrient assimilation into food webs will inform how marine resources will change in response to climate. To evaluate how ocean conditions influence the assimilation of nitrogen and carbon into coastal marine food webs, we applied a novel dimension reduction analysis to a century of newly acquired molecular isotope data derived from historic harbor seal bone specimens. By measuring bulk δ13 C and δ15 N values of source amino acids of these top predators from 1928 to 2014, we derive indices of primary production and nitrogen resources that are assimilated into food webs. We determined coastal food webs responded to climate regimes, coastal upwelling, and freshwater discharge, yet the strength of responses to individual drivers varied across the northeast Pacific. Indices of primary production and nitrogen availability in the Gulf of Alaska were dependent on regional climate indices (i.e., North Pacific Gyre Oscillation) and upwelling. In contrast, the coastal Washington and Salish Sea food webs were associated with local indices of freshwater discharge. For some regions (eastern Bering Sea, northern Gulf of Alaska) food web-assimilated production was coupled with nitrogen sources; however, other regions demonstrated no production-nitrogen coupling (Salish Sea). Temporal patterns of environmental indices and isotopic data from Washington state varied about the long-term mean with no directional trend. Data from the Gulf of Alaska, however, showed below average harbor seal δ13 C values and above average ocean conditions since 1975, indicating a change in primary production in recent decades. Altogether, these findings demonstrate stable isotope data can provide useful indices of nitrogen resources and phytoplankton dynamics specific to what is assimilated by food webs.

Amino acid δ13C and δ15N patterns from sediment trap time series and deep-sea corals: Implications for biogeochemical and ecological reconstructions in paleoarchives

Recent work using compound-specific stable isotopes of amino acids (CSI-AA) in proteinaceous deep-sea corals opens a new realm of high-fidelity reconstruction for biogeochemical and ecological changes in the ocean. However, underlying these CSI-AA paleoceanographic applications are a series of fundamental assumptions, which hold first that baseline-proxy AA isotope values fixed at the base of food webs represent integrated δ13C and δ15N values of primary production, and second they are unaltered during subsequent export and incorporation from particles into corals. We explored long-term δ13C and δ15N CSI-AA data on a sediment trap time series together with contemporaneous, geographically close deep-sea bamboo corals (Isidella sp.) in the California margin, directly testing these assumptions for the first time. Our data show that isotope values of essential (δ13CEAA) and source AAs (δ15NPhe) in sinking particles quantitatively track bulk δ13C and δ15N values of export production. These CSI-AA baseline proxies varied independently of carbon flux, trophic position (TPCSI-AA) and microbial alteration, suggesting that they were well preserved in the sinking particles consumed by corals. Paired comparisons between sinking particles and corals revealed minor elevations of δ13CEAA (by ∼2‰) and δ15NPhe (by ∼1‰) in available coral specimens. We hypothesize that the difference in δ13CEAA is due to the geographic offset in δ13C values of primary production expected between the (more offshore) sediment trap site and (more onshore) coral specimens, whereas the δ15NPhe offset is likely related to expected minor trophic fractionation. Using empirical models derived from the sediment trap time series, we demonstrate for the first time that CSI-AA in proteinaceous deep-sea corals can reconstruct known bulk δ15N values of export production, source nitrogen δ15N values, and exported TPCSI-AA values with very good fidelity. Together, these findings represent a major advance in our understanding of AA isotope behavior in modern and paleoarchives, and can be used to underpin the rapidly evolving use of CSI-AA-based tools in multiple paleoceanographic studies and archives.

Organic Carbon and Nitrogen Isoscapes of Reef Corals and Algal Symbionts: Relative Influences of Environmental Gradients and Heterotrophy.

The elemental (C/N) and stable isotopic (δ13C, δ15N) compositions and compound-specific δ15N values of amino acids (δ15NAA) were evaluated for coral holobionts as diagnostic tools to detect spatiotemporal environmental heterogeneity and its effects on coral health. Hermatypic coral samples of eight species were collected at 12 reef sites with differing levels of pollution stress. The C/N ratios, δ13C values, and δ15N values of coral tissues and endosymbiotic algae were determined for 193 coral holobionts, and the amino acid composition and δ15NAA values of selected samples were analyzed. δ15N values were influenced most by pollution stress, while C/N ratios and δ13C values depended most strongly on species. The results imply that δ13C and δ15N values are useful indicators for distinguishing the ecological niches of sympatric coral species based on microhabitat preference and resource selectivity. Using δ15NAA values, the trophic level (TL) of the examined coral samples was estimated to be 0.71 to 1.53, i.e., purely autotrophic to partially heterotrophic. Significant portions of the variation in bulk δ15N and δ13C values could be explained by the influence of heterotrophy. The TL of symbionts covaried with that of their hosts, implying that amino acids acquired through host heterotrophy are translocated to symbionts. Dependence on heterotrophy was stronger at polluted sites, indicating that the ecological role of corals changes in response to eutrophication.

The stable carbon isotope signature of methane produced by saprotrophic fungi

Abstract. Methane (CH4) is the most abundant organic compound in the atmosphere and is emitted from many biotic and abiotic sources. Recent studies have shown that CH4 production occurs under aerobic conditions in eukaryotes, such as plants, animals, algae, and saprotrophic fungi. Saprotrophic fungi play an important role in nutrient recycling in terrestrial ecosystems via the decomposition of plant litter. Although CH4 production by saprotrophic fungi has been reported, no data on the stable carbon isotope values of the emitted CH4 (δ13C-CH4 values) are currently available. In this study, we measured the δ13C values of CH4 and carbon dioxide (δ13C-CO2 values) emitted by two saprotrophic fungi, Pleurotus sapidus (oyster mushroom) and Laetiporus sulphureus (sulphur shelf), cultivated on three different substrates, pine wood (Pinus sylvestris), grass (mixture of Lolium perenne, Poa pratensis, and Festuca rubra), and corn (Zea mays), which reflect both C3 and C4 plants with distinguished bulk δ13C values. Applying Keeling plots, we found that the δ13C source values of CH4 emitted from fungi cover a wide range from −40 to −69 mUr depending on the growth substrate and fungal species. Whilst little apparent carbon isotopic fractionation (in the range from −0.3 to 4.6 mUr) was calculated for the δ13C values of CO2 released from P. sapidus and L. sulphureus relative to the bulk δ13C values of the growth substrates, much larger carbon isotopic fractionations (ranging from −22 to −42 mUr) were observed for the formation of CH4. Although the two fungal species showed similar δ13CH4 source values when grown on pine wood, δ13CH4 source values differed substantially between the two fungal species when they were grown on grass or corn. We found that the source values of δ13CH4 emitted by saprotrophic fungi are highly dependent on the fungal species and the metabolized substrate. The source values of δ13CH4 cover a broad range and overlap with values reported for methanogenic archaea, the thermogenic degradation of organic matter, and other eukaryotes.

Shifts in carbon and nitrogen stable isotope composition and epicuticular lipids in leaves reflect early water-stress in vineyards

Changes in leaf carbon and nitrogen isotope composition (δ13C and δ15N values) and the accumulation of epicuticular lipids have been associated with plant responses to water stress. We investigated their potential use as indicators of early plant water deficit in two grapevine (Vitis vinifera L.) cultivars, Chasselas and Pinot noir, that were field-grown under well-watered and water-deficient conditions. We tested the hypothesis that the bulk δ13C and δ15N values and the concentrations of epicuticular fatty acids may change in leaves of similar age with the soil water availability. For this purpose, leaves were sampled at the same position in the canopy at different times (phenological stages) during the 2014 growing season. Bulk dry matter of young leaves from flowering to veraison had higher δ13C values, higher total nitrogen content, and lower δ15N values than old leaves. In both cultivars, δ15N values were strongly correlated with plant water deficiency, demonstrating their integration of the plant water stress response. δ13C values recorded the water deficiency only in those plants that had not received foliar organic fertilization. The soil water deficiency triggered the accumulation of C>26 fatty acids in the cuticular waxes. The compound-specific isotope analysis (CSIA) of fatty acids from old leaves showed an increase in δ13C among the C16-C22 chains, including stress signaling linoleic and linolenic acids. Our results provide evidence for leaf 13C-enrichment, 15N-depletion, and enhanced FA-chain elongation and epicuticular accumulation in the grapevine response to water stress. The leaf δ13C and δ15N values, and the concentration of epicuticular fatty acids can be used as reliable and sensitive indicators of plant water deficit even when the level of water stress is low to moderate. They could also be used, particularly the more cost-efficient δ13C and δ15N measurements, for periodic biogeochemical mapping of the plant water availability at the vineyard and regional scale.

Occurrence and fate studies (sunlight exposure and stable carbon isotope analysis) of the halogenated natural product MHC-1 and its producer Plocamium cartilagineum

MHC-1 is a halogenated natural product (HNP) produced by the red seaweed Plocamium cartilagineum. MHC-1 concentrations of 550–2700 μg/g dry weight were found in Plocamium collected by divers at Heligoland (Germany). Compared to that MHC-1 concentrations were much lower in samples collected on beaches in Ireland and Portugal. Exposure of leaves of Plocamium to sunlight showed that MHC-1 was readily transformed by hydrodebromination. At Heligoland in March, MHC-1 (δ13C value −45.2‰) was lighter in carbon by ~15‰ compared to the bulk δ13C value (‰) of Plocamium (−30.7‰). Collected at the same time and location at Heligoland, samples of Halichondria and Mastocarpus sp. were richer in carbon (by ~10‰) as Plocamium. However, the δ13C value of MHC-1 in Halichondria (−44.6‰) and Mastocarpus sp. (−42.1‰) was as negative as in Plocamium. This was indirect proof that MHC-1 was produced by Plocamium and then released into the water phase from where it then was bioconcentrated by Halichondria and Mastocarpus sp. In agreement with that, concentrations of MHC-1 in Halichondria and Mastocarpus sp. were much lower than in Plocamium. In addition, a potential isomer of MHC-1 (compound X) was detected in all samples from Heligoland at ~2% of the MHC-1 level.

Multivariate geostatistical analysis of stable isotopes in Portuguese varietal extra virgin olive oils

Stable isotope contents of carbon, hydrogen and oxygen are known to reflect the geo-climatic conditions under which olives grown. This study aims to unravel the correlation between some of the main geographic variables and the isotopic composition of different Portuguese varietal extra virgin olive oil (EVOO) samples. Thus, the isotopic composition (δ13C, δ18O and δ2H) of 38 EVOO samples from 11 olive varieties from 2 Portuguese regions (Alentejo and Trás-os-Montes) was studied using an elemental analyzer coupled to an isotope ratio mass spectrometry. Multivariate analysis indicated that bulk δ13C, δ2H and δ18O values were enough to significantly (P < 0.05) predict altitude, latitude, longitude, temperature, rainfall, and sea distance. This work showed that the assessment of EVOO isotopic composition give information not only on the geographic origin, but also on the environmental conditions. To the best of our knowledge, this is the first report on bulk isotopic composition of Portuguese EVOOs.