Isotope Values Research Articles

Trace metals pollution and trophic position of three sea urchin species in the Gulf of California.

Sea urchin species are ecologically important in the Gulf of California and are becoming popular as a local fishery due to their commercial value. The most abundant species are Echinometra vanbrunti, Eucidaris thouarsii, and Tripneustes depressus. The objective of this study was to evaluate cadmium, lead, copper, zinc, and iron concentrations, as well as stable isotope values in these sea urchin species in the Santa Rosalia mining area (STR), in three sites: Punta Gorda, Punta el Aterrizaje, and Punta Salina. The highest Fe concentration (100.2 mg kg-1) was found in E. vanbrunti, while the highest concentrations of Pb (15.1 mg kg-1), Cu (14.5 mg kg-1), and Zn (347.7 mg kg-1) were recorded in E. thouarsii, and the highest Cd concentration (10.8 mg kg-1) was found in T. depressus. The main health risk of trace metal pollution in STR may be caused by Cd and Pb. δ15N and δ13C values were higher in E. thouarsii and T. depressus, respectively; E. thouarsii has the highest trophic position. Specimen size was not related to metal concentrations, but a positive relationship was observed between specimen size and isotopic values in T. depressus. The three species showed different bioaccumulation patterns for the metals analyzed. Additionally, collection sites and seasons play an important role in the variability of metal concentration.

Effect of agricultural management system (“cash crop”, “livestock” and “climate optimized”) on nitrous oxide and ammonia emissions

AbstractThe study aimed to measure soil-atmosphere N2O fluxes and their controlling factors, as well as NH3 emissions and yields for two soils (silt loam and clay loam) in three management systems over two years under subsequent wheat and maize cultivation. The management systems were characterized as follows: (1) cash crop (C) with mineral fertilizer and conventional tillage; (2) livestock (L) with biogas residue fertilization and its incorporation prior to sowing in maize and reduced tillage; and (3) climate optimized (O) with minimum tillage, 8-year crop rotation, with biogas residue fertilization, in maize without incorporation in clay loam soil or incorporation by strip-tillage prior to seeding in silt loam soil. Stable isotope ratios of N2O and mineral N were determined to identify N2O processes. Within the organically fertilized maize treatments, cumulative N2O fluxes were highest in the O-system treatments of both sites (4.0 to 9.4 kg N ha− 1 a− 1), i.e. more than twice as high as in the L-system (1.5 to 3.1 kg N ha− 1 a− 1). Below root-strip till fertilizer application did not enhance N2O fluxes. Fluxes with mineral fertilization of wheat (1.1 to 3.1 kg N ha− 1 a− 1) were not different from those with organic fertilization. Isotopic values of emitted N2O revealed that bacterial denitrification dominated most of the peak flux events, while the N2O/(N2 + N2O) ratio of denitrification was mostly between 0.1 and 0.5. It can be concluded that, contrary to the intention to lower greenhouse gas fluxes by the O-system management, the highest N2O fluxes occurred in the O-system without biogas digestate incorporation in maize. With respect to NH3 fluxes, we could confirm that the application of digestate application in growing crops without incorporation or late incorporation in fertilization before sowing induces high fluxes. The beneficial aspects of the O-system including more stable soil structure and resource conservation, are thus potentially counteracted by increased N2O and NH3 emissions.

Developing δ15N and δ13C isoscapes using whole blood from Magellanic penguins, Spheniscus magellanicus.

Understanding the migration of marine animals is hindered by the limitations of traditional tracking methods. It is therefore crucial to develop alternative methods. Stable isotope-based tracking has proven useful for this task, although it requires detailed isoscapes in the focal area. Here, we present predator-based isoscapes of the coastal zone of the Patagonian Shelf Large Marine Ecosystem (PSLME), which offers a novel tool for geolocation. Whole-blood samples from breeding Magellanic penguins nesting at 11 colonies were used to create δ15N and δ13C isoscapes. Isotopic values were assigned to random positions inside their corresponding foraging area. Spatial analysis and data interpolation resulted in δ15N and δ13C isoscapes for the coastal zone of the PSLME, which were validated through cross-validation. The isoscapes mean standard error ranged from 0.05 to 0.41 for δ15N and from 0.07 to 0.3 for δ13C, similar to the error range of the mass spectrometer used for measuring isotope ratios. Predictive surfaces reflected the latitudinal trends, with δ13C and δ15N values increasing northwards. δ13C values showed a strong latitudinal gradient, while δ15N values had two distinct domains, with higher values in the north. The error surface indicated the highest certainty within 130 km from the shore and within the reported Magellanic penguin foraging areas. Both isoscapes revealed strong spatial variation. The δ13C isoscape showed a latitudinal gradient, consistent with patterns in other oceans. The δ15N isoscape clearly separated northern and southern colonies, likely influenced by nitrogen sources. The error obtained fell within the measurement error ranges, adding credibility to the models.

Total mercury concentrations in Tasman Sea mesopelagic fish: Exploring biotic and abiotic drivers

Understanding mercury (Hg) concentrations in mesopelagic and mid-trophic fishes is important for assessing Hg accumulation in oceanic ecosystems and higher-order predators. This study measured total Hg (THg) concentrations in the whole body of 16 abundant mesopelagic fish species sampled in two distinct sites within the Tasman Sea. Across all species, total Hg concentrations ranged from 0.02 to 0.48 μg g−1 dry weight (0.01 to 0.15 μg g−1 wet weight). Total Hg concentrations varied with vertical migration patterns, with shallower migrators exhibiting higher THg. Females typically had statistically higher THg concentrations than males. Positive correlations between THg concentration and standard length were observed for some but not all species. At the community level, THg concentrations correlated positively with estimated trophic position and foraging habitat, as inferred by stable isotope values. These findings contribute to our understanding of Hg cycling in oceanic ecosystems and the potential for biomagnification in oceanic top-order predators.

Using Stable Isotope Techniques to Analyze the Trophic Relationship between Argentine Hake (Merluccius hubbsi) and Anisakidae.

The Argentine hake (Merluccius hubbsi) is a vital fishery species in the Southwest Atlantic, recognized for its substantial economic importance. Previous studies have identified Anisakidae larvae as common parasites of M. hubbsi. However, the nutritional relationships between these parasites and their host remain poorly understood. This study employs stable isotope techniques to investigate the specific nutritional relationships between Anisakidae larvae and different tissues of M. hubbsi. The findings reveal notable differences in δ13C and δ15N compositions between the parasites and their host. The lower δ13C values in parasites compared to host tissues indicate the utilization of different carbon sources. The δ15N values of the parasites partially overlap with those of the host's stomach, indicating that the parasites primarily derive nutrients from the host's stomach. Nutritional niche indicators show that parasites have a broad carbon range (CR) and nitrogen range (NR), suggesting a high diversity in nutritional sources. The trophic discrimination factor (ΔTDF), which represents the difference in stable isotope values between host tissues and parasites, was analyzed for both δ13C and δ15N. The ΔTDFδ13C between the host liver and the parasites showed the greatest variation, indicating a strong dependence of the parasites on the liver's carbon sources. In contrast, variations in ΔTDFδ15N between host tissues and parasites were minimal. Analyzing ΔTDF across different stages of gonadal maturity in the host fish indicates that, as the gonads of the host fish mature, ΔTDFδ13C between host tissues and parasites significantly decreases (p < 0.01). The Kruskal-Wallis test showed significant differences in ΔTDFδ13C values among different parasite infection levels in muscle, liver, and stomach tissues, while no significant differences were found for ΔTDFδ15N values. These findings offer valuable insights into the nutritional relationships between parasites and hosts, aiding in a better understanding of the growth conditions and habitats of M. hubbsi.

Assessing the impacts of trace element contamination on the physiology and health of seabirds breeding along the western and southern coasts of Portugal

Coastal seabirds serve as sentinels of ecosystem health due to their vulnerability to contamination from human activities. However, our understanding on how contaminant burdens affect the physiological and health condition of seabirds is still scarce, raising the uncertainty on the species' vulnerability vs tolerance to environmental contamination. Here, we quantified 15 Trace Elements (TE) in the blood of gull (yellow-legged gull Larus michahellis and Audouin's gull Ichthyaetus audouinii) and shearwater (Cory's shearwater Calonectris borealis) adults, breeding in five colonies along the Portuguese coastline. Additionally, stable isotopes of carbon (δ13C) and nitrogen (δ15N) were quantified to elucidate foraging habitat and trophic ecology of adults, to identify potential patterns of TE contamination among colonies. We used immuno-haematological parameters as response variables to assess the influence of TE concentrations, stable isotope values, and breeding colony on adults' physiological and health condition. Remarkably, we found blood mercury (Hg) and lead (Pb) concentrations to exceed reported toxicity thresholds in 25% and 13% of individuals, respectively, raising ecotoxicological concerns for these populations. The breeding colony was the primary factor explaining variation in five out of six models, underlining the influence of inherent species needs on immuno-haematological parameters. Model selection indicated a negative relationship between erythrocyte sedimentation rate and both Hg and selenium (Se) concentrations, but a positive relationship with δ13C. The number of immature erythrocyte counts was positively related to Hg and Se, particularly in yellow-legged gulls from one colony, highlighting the colony-site context's influence on haematological parameters. Further research is needed to determine whether essential TE concentrations, particularly copper (Cu) and Se, are falling outside the normal range for seabirds or meet species-specific requirements. Continuous monitoring of non-essential TE concentrations like aluminium (Al), Hg, and Pb, is crucial due to their potential hazardous concentrations, as observed in our study colonies.

Dual isotopic (33P and 18O) tracing and solution 31P NMR spectroscopy to reveal organic phosphorus synthesis in organic soil horizons

Soil microorganisms can do both, mineralize and synthesize organic and condensed phosphate (P) species. Whereas P mineralization has been extensively studied, few studies have assessed the biological synthesis of organic P species, which can potentially accumulate in soil. The goal of this study was to investigate biotic and abiotic P transformations, particularly the synthesis of organic P species, upon water-soluble P addition in the organic (O) horizons of two beech forest sites with contrasting P availability.The two O horizons (low-P and high-P) were subjected to four different nutrient addition treatments (Control without addition, CN, P, and CNP additions) in an incubation experiment of up to 104 days. We combined isotopic tracing (33P-labelled P addition and 18O-enriched soil water) into sequentially extracted P pools with the characterization of organic P species (solution 31P nuclear magnetic resonance (NMR) spectroscopy) and soil respiration measurements.The P availability of the two O horizons shaped the microbial response to the nutrient additions. In the low-P O horizon, P addition stimulated microbial activity together with the increase of organic (phosphodiesters and phosphonates) and condensed (polyphosphates) P species, most likely from microbial origin. In the high-P O horizon, microbes were unaffected by the added P and abiotic processes controlled its fate. CN addition had no effect on P fate in the high-P O horizon but reduced the transformation of added P into organic P and increased soil-derived P in the resin P pool in the low-P O horizon. The 18O isotopic values in phosphate of the resin P pool suggest that the released P was biologically cycled.Our study confirms with a unique multi-analytical approach the microbial synthesis of phosphodiesters, phosphonates, and polyphosphates upon inorganic P addition under low P availability.

Discrimination of different forms and oceanic regions of purpleback flying squid (Sthenoteuthis oualaniensis) based on stable isotopes and fatty acid composition

IntroductionPelagic cephalopods play a key role in the Chinese food supply. The market value of seafood frequently fluctuates based on its geographical origin and species, making it imperative to trace the origin and distinguish forms to guarantee food quality and accurate information.MethodsIn this study, we used biochemical tracers, including stable isotope analysis and fatty acid composition profiling, to trace the origin of purpleback flying squid (Sthenoteuthis oualaniensis) from the Indian Ocean and South China Sea. We measured the δ13C and δ15N values and fatty acid (FA) contents in samples from different forms of S. oualaniensis obtained from these two oceanic regions. We analyzed the feeding and nutritional differences among these populations and conducted discriminant analysis.Results and discussionSignificant regional and form differences were observed in both isotopic values and FA profiles in the muscle tissues of S. oualaniensis. Forms with larger sizes exhibited higher δ13C and δ15N values, potentially resulting from different feeding preferences and geographical environments. The discriminant analysis revealed that isotopic composition could effectively distinguish individuals from different oceanic regions, whereas FA composition was more effective in distinguishing different forms within the same oceanic region. The combination of isotopes and FAs could accurately discriminate S. oualaniensis of different forms and from different oceanic regions, achieving a discrimination accuracy of 100%. This study provides a reference for tracing the origin of pelagic cephalopods with complex form structures.

Mytilus galloprovincialis shell growth – Insights from shell geochemistry

Despite the wide geographic distribution of mussels and their importance in fisheries and aquaculture, understanding of temporal and spatial variations of their growth is still limited. This can be, at least partly, attributed to the lack of distinct growth lines in their shells. Our study uses geochemical properties of shells, particularly oxygen (δ18Oshell) and carbon (δ13Cshell) stable isotope values, to reconstruct mussel growth. Mytilus galloprovincialis specimens were collected from two of the most important bivalve aquaculture sites in the eastern Adriatic - Krka River estuary and Mali Ston Bay. The first site has variable environmental conditions, influenced mainly by the Krka River, resulting in a strong temperature and salinity gradient along the estuary. In contrast, Mali Ston Bay is a relatively shallow enclosed bay with more stable conditions. Samples for δ18Oshell and δ13Cshell analysis were acquired by manual microdrilling cross-sectioned shells from three similar sized shells from each site. In addition, analysis of elemental profiles (Mg/Ca, Sr/Ca, and Ba/Ca) in shells from the Krka River estuary was conducted using laser ablation ICPMS. Temperature and salinity values were obtained for each site through research and monitoring projects and used to calculate predicted δ18Oshell values. By aligning the measured δ18Oshell data along the predicted δ18Oshell curve, it was possible to reconstruct the timing and rate of seasonal shell growth. Results show that M. galloprovincialis shell deposition slows down and/or ceases during high temperature and low salinity periods. Specimens from the Krka River estuary had faster shell growth rates and were characterised by higher δ13Cshell values. Mg/Ca profiles of M. galloprovincialis specimens from the Krka River estuary, confirm growth periodicity data obtained by δ18O analysis. Ba/Ca peaks were also discussed by comparison with δ13C time-series and environmental data. Results have potential applications in fisheries studies as well as in palaeoecology and palaeoceanography research.

An unusual occurrence of carbonatites derived from the crust in the UHT granulite facies metamorphic terrain of Sri Lanka

The special calcite bodies (CBs) exposed within the ultrahigh temperature (UHT) granulite facies terrain in the Balangoda area of Sri Lanka preserve shreds of evidence for the generation of crust-derived carbonatite in the crust. The CBs are exclusively made up of massive calcites and appear as concordant bands extending tens of meters or as meso-scale isolated pockets hosting the massive dolomitic marble band. Various sizes of mafic and calc-silicate enclaves occur as rotated or tilted structures within the CBs. The contact between the CBs and the host marble is texturally and mineralogically gradational, while the contact between the enclaves and the CBs is sharp. The large-ion lithophile elements and rare earth element contents of the CBs show enrichment compared to the host marble, while depletion compared to typical carbonatites. Furthermore, the Sr content and C-O isotope values in CBs differ from those found in known carbonatites, hydrothermal carbonates, or metasomatic carbonates. We suggested that the crustal anatexis of marble should be hypothesized as the possible mechanism for the origin of the CBs. Microtexural evidence of the calcite grains shows indications of the melting of the host marble. The release of CO2-rich fluids from the collision and thrusting of HC over VC, or related metamorphic events, likely lowered the solidus of carbonates, triggering crustal anatexis of marble during UHT granulite facies metamorphism. The generated low viscous carbonate melt may have moved rapidly, resulting in a low degree of mixing of silicates and fragmentation and dislocation of enclaves. The results of the present study reflect the existence of anatexis of carbonates under extreme crustal conditions and provide a better understanding of the sources, migration paths and reservoirs of the carbon recycling processes.

Resource utilisation and trophic niche overlap of coralline intertidal benthic amphipods: an isotopic perspective.

Benthic amphipod feeding groups are a well-established trophic classification that is mostly based on field observations and laboratory tests and are used in ecological studies to monitor the ecological state of benthic ecosystems. Globally, carbon and nitrogen stable isotope ratio investigations have provided confirmation of, and novel insights into, the trophic ecology of benthic animals, such as polychaetes. However, stable isotopic examinations of benthic amphipods have been limited. Here, we used microgram samples to compare the species-specific dietary sources, trophic positions, and isotopic niche overlap of selected benthic amphipods from the Gulf of Kachchh, Marine National Park, using elemental analyser-isotopic ratio mass spectrometry (EA-IRMS) of carbon and nitrogen. Overall, all primary carbon sources presented wide variation in the isotopic values of δ13C (6.3‰) and δ15N (greater than 13‰). Conversely, the amphipod taxa displayed relatively narrow range for δ13C (3.9‰) and wider range for δ15N (more than 10‰). The results of the Bayesian mixing model revealed that the benthic amphipods had species-specific feeding preferences. However, the predominant carbon source was organic matter in sediment which reinforced benthic pathways for energy flow for most species. According to the estimated trophic level values (1.62-3.39), these species play a significant role as primary and secondary consumers serving as crucial trophic intermediaries in the food chain, connecting the base to the top consumers. High overlapping ecological niche amongst species was detected by SIBER analysis which indicated co-existence of the benthic amphipods in their respective microhabitats. This signifies wider utilisation of resources and inter-specific feeding preferences with minimal competition amongst amphipod species.

Identification of processes in Cu-ore heap leaching using Cu isotopes and leachate chemistry at Tschudi mine, northern Namibia

Copper isotopic fractionation (in δ65Cu) and leachate characterization were studied in the context of heap leaching at the Tschudi copper mine in northern Namibia. The leached solution is of Mg-SO4 type with high Al and Fe concentrations. The source of Mg and Al in the leachate can be from the alteration of micas such as Mg-bearing muscovite confirmed by X-ray diffraction and scanning electron microscopy; however, the source of Mg cannot be determined with certainty. The principal secondary minerals identified in the leached ore are gypsum and jarosite. The value of pH in leachate is ∼1.21 and the concentration of dissolved Cu, occurring mostly as CuSO40 and Cu2+, is about 2 g/L. In comparison with unleached ore (avg. δ65Cu −1.47 ‰), leached ore exhibits lighter isotopic values (avg. δ65Cu −6.01 ‰) with apparent isotopic fractionation Δ65Culeached ore-unleached ore of about −4.54 ‰. In contrast, there is isotopic enrichment of leachate in heavier 65Cu isotope (leachate δ65Cu 0.34 ‰) with apparent isotopic fractionation Δ65Culeachate-unleached ore value of +1.81 ‰. These results are in good agreement with Cu isotopic fractionation and depletion in heavier 65Cu isotope reported for dissolution experiments in laboratory and groundwater linked to the porphyry copper ore deposits around the world. The leaching of heaps can be considered an analogy of upper part of gossans, but here the supergene enrichment zone is missing due to extremely low pH and oxidizing conditions.

Optimization of separation and MC-ICP-MS methods for determining Eu isotopic ratios in Si- and Ba-rich fractionated igneous rocks and other natural materials

Eu isotope ratio can be precisely measured by MC-ICP-MS using a Sm isotope pair as spike for normalization. The standard chemical reagent NIST3117a exhibits almost no Eu isotope fractionation regardless of the kind of Sm isotope pairs used in normalization. However, Eu isotope fractionation can appear even in high purity Eu chemical reagents due to Gd and Ba impurities, interference with Sm isotope pair or use of different sample introduction methods. The Eu isotope fractionation in highly fractionated igneous rocks or feldspar minerals can arise from Gd and Ba impurities left by incomplete chemical separation. This study describes a modified, optimal method for accurately and precisely determining the degree of Eu isotope fractionation in highly fractionated Si-rich igneous rocks and Ba-rich feldspar. Ba oxide effects on Sm, Eu and Gd isotopes were monitored by MC-ICP-MS using different wet and dry plasma conditions for sample introduction. The Gd impurities exerts more influence than Ba impurities on Eu isotope ratios. The highly fractionated igneous rocks and feldspar materials showed consistent enrichment in the lighter Eu isotope (151Eu) which becomes a negative Eu isotopic value relative to NIST3117a. Results showed that highly purified Eu solutions from reagents containing no detectable Gd and Ba gave consistent Eu isotopic values regardless of Sm isotope pair (e.g., 147Sm149Sm, 147Sm152Sm, 147Sm154Sm, 149Sm154Sm, 150Sm154Sm) used in normalization. In order to obtain the best estimates of Eu isotope fractionation in different kinds of geological materials (including Si- and Ba-rich materials), Ba and Gd matrix must be completely removed and the Eu isotopic values calculated using four or more Sm spike isotope pairs.

Adsorption rate of uranium and thorium isotopes in soil and plants grown in a high background radiation area

ABSTRACT An important method for measuring radionuclide activity is alpha spectrometry. Ten soil samples were collected from the studied area. The activity concentrations of 238U and 234U in the collected soil samples ranged between 135 and 218 Bq kg–1 and between 117 and 183 Bq kg–1, respectively. 232Th, 230Th and 228Th activity concentrations ranged between 101 and 339, between 122 and 234 and between 106 and 385 Bq kg–1, respectively. When calculating the amount of radionuclide transport across the food chain, assessment models usually employ a transfer factor. Through root uptake, U and Th are transferred from the soil to food plants. To monitor the movement of radionuclides from the uranium series in diverse environments, it may be possible to use the ratios of uranium and thorium isotopes. Uranium mobility in soil depends on different physicochemical, organic and enzymatic factors and mechanisms. The high mobility of uranium is the main reason for the accumulation of uranium in the soil at root level and the possibility of its transfer to plants. A group of plants were selected that are grown in this area and the population relies on them mainly to meet their food needs. The concentration and transfer factor values of uranium isotopes were the highest in roots as compared with leaves and stems. Uranium in plants accumulates in roots and is then transferred to leaves. The mobility of uranium in plant tissues is constrained because it frequently adsorbs cell wall components. As a result, concentrations are frequently higher in tissues located in lower parts of the plant, with root surfaces having the highest concentrations.

Deep learning insights into spatial patterns of stable isotopes in Iran’s precipitation: a novel approach to climatological mapping

ABSTRACT Stable isotope techniques are precise methods for studying various aspects of hydrology, such as precipitation characteristics. However, understanding the variations in the stable isotope content in precipitation is challenging in Iran due to numerous climatic and geographic factors. To address this, forty-two precipitation sampling stations were selected across Iran to assess the fractional importance of these climatic and geographic parameters influencing stable isotopes. Additionally, deep learning models were employed to simulate the stable isotope content, with missing data initially addressed using the predictive mean matching (PMM) method. Subsequently, the recursive feature elimination (RFE) technique was applied to identify influential parameters impacting Iran’s precipitation stable isotope content. Following this, long short-term memory (LSTM) and deep neural network (DNN) models were utilized to predict stable isotope values in precipitation. Interpolated maps of these values across Iran were developed using inverse distance weighting (IDW), while an interpolated reconstruction error (RE) map was generated to quantify deviations between observed and predicted values at study stations, offering insights into model precision. Validation using evaluation metrics demonstrated that the model based on DNN exhibited higher accuracy. Furthermore, RE maps confirmed acceptable accuracy in simulating the stable isotope content, albeit with minor weaknesses observed in simulation maps. The methodology outlined in this study holds promise for application in regions worldwide characterized by diverse climatic conditions.

Invertebrate trophic structure on marine ferromanganese and phosphorite hardgrounds

AbstractThe Southern California Borderland hosts a variety of geologic and oceanographic features that allow for diverse habitats to occur in a restricted region with a strong oxygen minimum zone (OMZ) and hard substrates. These include ferromanganese (FeMn) crusts and phosphorites targeted for deep‐seabed mining in other regions. Baseline studies regarding hardground macro‐ (&gt; 0.3 mm) and megafaunal (&gt; 2 cm) invertebrates are lacking, although they contribute to understanding nutrient cycling and resilience of deep‐sea communities to ocean deoxygenation, fishing, or mineral extraction. With the goal of understanding how substrate type, depth, and dissolved oxygen concentration influence invertebrate trophic structure, we surveyed δ13C and δ15N values of invertebrates on hard substrates on the Southern California Borderland margin along a depth gradient (120–2400 m) through the OMZ at inshore (&lt; 100 km from shore) and offshore (100–250 km from shore) sites, using generalized additive models and community‐level metrics. Macrofaunal isotopic values correlate with substrate type, exhibiting higher trophic diversity on FeMn crusts and specialized communities on phosphorites. Megafaunal isotopic values correlate with proximity to shore; animals offshore seem to depend more on phytoplanktonic production than animals inshore. In general, δ15N increased with decreasing dissolved oxygen and increasing depth, possibly due to remineralization processes within the OMZ and with depth. We discuss how feeding modes and community composition might influence the observed patterns. This study elucidates the importance of the environmental context in shaping invertebrate trophic structure on continental margins and provides baseline knowledge that may be useful in regions where these minerals are targeted for extraction.

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.

Primary to post-depositional microbial controls on the stable and clumped isotope record of shoreline sediments at Fayetteville Green Lake.

Lacustrine carbonates are a powerful archive of paleoenvironmental information but are susceptible to post-depositional alteration. Microbial metabolisms can drive such alteration by changing carbonate saturation insitu, thereby driving dissolution or precipitation. The net impact these microbial processes have on the primary δ18O, δ13C, and Δ47 values of lacustrine carbonate is not fully known. We studied the evolution of microbial community structure and the porewater and sediment geochemistry in the upper ~30 cm of sediment from two shoreline sites at Green Lake, Fayetteville, NY over 2 years of seasonal sampling. We linked seasonal and depth-based changes of porewater carbonate chemistry to microbial community composition, insitu carbon cycling (using δ13C values of carbonate, dissolved inorganic carbon (DIC), and organic matter), and dominant allochems and facies. We interpret that microbial processes are a dominant control on carbon cycling within the sediment, affecting porewater DIC, aqueous carbon chemistry, and carbonate carbon and clumped isotope geochemistry. Across all seasons and sites, microbial organic matter remineralization lowers the δ13C of the porewater DIC. Elevated carbonate saturation states in the sediment porewaters (Ω > 3) were attributed to microbes from groups capable of sulfate reduction, which were abundant in the sediment below 5 cm depth. The nearshore carbonate sediments at Green Lake are mainly composed of microbialite intraclasts/oncoids, charophytes, larger calcite crystals, and authigenic micrite-each with a different origin. Authigenic micrite is interpreted to have precipitated insitu from the supersaturated porewaters from microbial metabolism. The stable carbon isotope values (δ13Ccarb) and clumped isotope values (Δ47) of bulk carbonate sediments from the same depth horizons and site varied depending on both the sampling season and the specific location within a site, indicating localized (μm to mm) controls on carbon and clumped isotope values. Our results suggest that biological processes are a dominant control on carbon chemistry within the sedimentary subsurface of the shorelines of Green Lake, from actively forming microbialites to pore space organic matter remineralization and micrite authigenesis. A combination of biological activity, hydrologic balance, and allochem composition of the sediments set the stable carbon, oxygen, and clumped isotope signals preserved by the Green Lake carbonate sediments.

Geochronology, geochemistry, and isotope signatures of porphyries from the dabate Mo—Cu deposit, Western Tianshan, China: Implications for petrogenesis and geodynamic setting

The Dabate deposit in the West Tianshan Orogenic Belt is a large porphyry Mo-Cu deposit with obvious zoning feature. The Dabate pluton is closely related to mineralization associated with the rhyolite and granite porphyries. Copper (Cu) mineralization occurs on the margin of the rhyolite porphyry, and molybdenum (Mo) mineralization occurs in the interior of the rhyolite porphyry. Petrology, zircon U-Pb isotopic data, whole-rock geochemistry, and Sr-Nb-Hf-Pb isotopic data of the rhyolite and granite porphyries in the Dabate Mo-Cu mining zone and to discuss the properties, sources, evolution, and tectonic environment of the magma. Zircon U-Pb age dating shows that the rhyolite porphyry and granite porphyry were formed in 300.1 ± 1.3 Ma and 290.4 ± 5.2 Ma, respectively, and they are geochemically similar. Both are characterized by negative Eu anomalies (δEu = 0.09–0.15 and 0.10–0.11, respectively) and are slightly rich in light rare earth elements (LREE) but depleted in high-field-strength elements (HFSE), which indicates that they are both A2 type granites that underwent high differentiation. The Sr isotope (ISr) values for the rhyolite and granite porphyries range from 0.70564 to 0.70658 and 0.70833–0.70954, respectively. The Nd isotopic composition [εNd(t)] values for both are negative but close to zero (−0.25 to −0.46 and −0.65 to −1.10, respectively), and the two-stage depleted mantle Nd model ages (TDM2(Nd)) are 1.07–1.10 Ga and 1.11–1.14 Ga, respectively. Zircon εHf(t) values are 7.29–11.97 and 6.26–11.08 for rhyolite porphyry and granite porphyry, respectively, and the two-stage Hf model ages (TDM2(Hf)) are 550–848 Ma and 605–916 Ma, respectively. The initial Pb isotope ratios for the rhyolite and granite porphyry are close at (206Pb/204Pb)i = 18.26–18.65, (207Pb/204Pb)i = 15.54–15.64, and (208Pb/204Pb)i = 38.19–38.57. These results indicate that the two porphyries have a mixed source, likely originating from the partial melting of mantle blended with some recently formed lower crust material. The geochronology, geochemistry, and Sr-Nd-Hf-Pb isotope data of existing intrusions in the West Tianshan imply that the Late Carboniferous to Early Permian Dabate area was underplated in a post-collisional extensional setting, and A2-type granite intrusions with related Mo-Cu mineralization were formed.

Challenging trophic position assessments in complex ecosystems: Calculation method, choice of baseline, trophic enrichment factors, season and feeding guild do matter: A case study from Marquesas Islands coral reefs.

Assessments of ecosystem functioning are a fundamental ecological challenge and an essential foundation for ecosystem-based management. Species trophic position (TP) is essential to characterize food web architecture. However, despite the intuitive nature of the concept, empirically estimating TP is a challenging task due to the complexity of trophic interaction networks. Various methods are proposed to assess TPs, including using different sources of organic matter at the base of the food web (the 'baseline'). However, it is often not clear which methodological approach and which baseline choices are the most reliable. Using an ecosystem-wide assessment of a tropical reef (Marquesas Islands, with available data for 70 coral reef invertebrate and fish species), we tested whether different commonly used TP estimation methods yield similar results and, if not, whether it is possible to identify the most reliable method. We found significant differences in TP estimates of up to 1.7 TPs for the same species, depending on the method and the baseline used. When using bulk stable isotope data, the choice of the baseline significantly impacted TP values. Indeed, while nitrogen stable isotope (δ15N) values of macroalgae led to consistent TP estimates, those using phytoplankton generated unrealistically low TP estimates. The use of a conventional enrichment factor (i.e. 3.4‰) or a 'variable' enrichment factor (i.e. according to feeding guilds) also produced clear discrepancies between TP estimates. TPs obtained with δ15N values of source amino acids (compound-specific isotope analysis) were close to those assessed with macroalgae. An opposite seasonal pattern was found, with significantly lower TPs in winter than in summer for most species, with particularly pronounced differences for lower TP species. We use the observed differences to discuss possible drivers of the diverging TP estimates and the potential ecological implications.