Lower δ15N Research Articles

Isotopic signature of N2O produced during sulfur‐ and thiosulfate‐driven chemoautotrophic denitrification in freshwaters

AbstractChemoautotrophic denitrification plays an important role in nitrogen removal and the formation of a greenhouse gas (N2O) in aquatic environments. Natural stable isotopes support the tracing of nitrogen sources and the identification of biogeochemical processes in field research. However, the isotopic characteristics of N2O produced during chemoautotrophic denitrification have not been investigated so far. In this study, we analyzed isotopic signatures of nitrate and N2O in sulfur‐ and thiosulfate‐dependent denitrifying enrichments obtained from freshwater lakes. Chemoautotrophic denitrification exhibited a nitrate isotope pattern similar to heterotrophic denitrification: the 18ε/15ε‐nitrate followed a ratio close to 1. However, chemoautotrophic denitrification produced N2O with lower δ15N, δ18O, and higher site preference (SP = δ15Nα‐δ15Nβ) values, compared to heterotrophic denitrification. The SP value, approximately 5.1‰, was characteristic in detecting chemoautotrophic denitrification driven by different sulfur forms. δ18O varied with specific electron donors, around 20‰ and 40‰ during sulfur‐ and thiosulfate‐dependent denitrification, respectively. The unique N2O isotope characteristics were likely regulated by nitric oxide reductases of Burkholderiaceae populations during sulfur‐dependent denitrification and Sulfurovum during thiosulfate‐dependent denitrification. These findings improve our understanding of N2O production processes and have important implications for predicting N2O emissions at a greater spatial and temporal resolution.

Sources and Sinks of N in Ecosystem Solutions Along the Water Path Through a Tropical Montane Forest in Ecuador Assessed With δ15N Values of Total Dissolved Nitrogen

AbstractThe globally increasing reactive N richness affects even remote ecosystems such as the tropical montane forests in Ecuador. We tested whether the δ15N values of total dissolved N (TDN), measured directly in solution with a TOC‐IRMS, can be used to help elucidate N sources and sinks along the water path and thus might be suitable for ecosystem monitoring. From 2013 to 2016, the δ15N values of TDN in bulk deposition showed the most pronounced temporal variation of all ecosystem solutions (δ15N values: 1.9–5.9‰). In throughfall (TF), TDN was on average 15N‐depleted (−1.8 ± s.d. 0.4‰) relative to rainfall (3.4 ± 0.9‰), resulting from net retention of isotopically heavy N, mainly as NH4+. Simultaneously, N‐isotopically light NO3−‐N and dissolved organic nitrogen (DON) with a δ15N value between NO3−‐N and NH4+‐N were leached from the canopy (leaves: −3.5 ± 0.5‰). The increasing δ15N values in the order, TF < stemflow (SF, 0.1 ± 0.6‰)< litter leachate (LL, 1.3 ± 0.7‰) concurred with an increasing DON contribution to TDN reflecting the δ15N value of the organic layer (1.9 ± 0.9‰). The lower δ15N value of the mineral soil solution at the 0.15 m soil depth (SS15, −1.5 ± 0.3‰) than in LL can be explained by the retention of DON and NH4+ and the addition of NO3− from mineralization and nitrification. The increasing δ15N values in the order, SS15 < SS30 (−0.6 ± 0.2‰) < streamflow (ST, 0.5 ± 0.6‰) suggested gaseous N losses because of increasing denitrification. There was no seasonality of the δ15N values. Our results demonstrate that the δ15N values of TDN in ecosystem solutions help identify N sources and sinks in forest ecosystems.

Manganese mineralization constrained by redox conditions in the Cryogenian Nanhua Basin, South China and its implications for nitrogen and carbon cycling

The Nanhua Basin of South China recorded complete Cryogenian stratigraphic sequence from the Sturtian Glaciation (~717–660 Ma) to the Marinoan Glaciation (~654–635 Ma). The interglacial Datangpo Fm in the Nanhua Basin is divided into two members, and the first member consists of the Mn-carbonate unit and the overlying black shale unit, containing a series of large and superlarge manganese deposits. The metallogenic process of manganese deposits is not clear, and the Mn-carbonates formed through the precursor of Mn-oxide/oxyhydroxide reduction or directly precipitated from an anoxic water column. Moreover, the redox conditions in the deep Nanhua Basin during the precipitation of manganese deposits are also controversial. In this study, the high-resolution nitrogen contents (TN), isotope compositions, carbon isotope compositions of organic and inorganic matter from the first member of the Datangpo Fm are analyzed. The δ15N values of the Mn-carbonate unit (+1.53‰ to +5.26‰, mean +3.36‰) are higher than those of the overlying black shale unit (−3.74‰ to +3.54‰, mean +0.89‰). The Mn contents show a negative relationship with TN but a positive relationship with δ15N in the Mn-carbonate unit, implying that the formation of Mn-carbonates is related to redox variations. The relatively higher δ15N values in the Mn-carbonate unit indicated oxic conditions, and NH4+can be released and partially oxidized during the mineralization of organic matter, resulting in the residual 15N-enriched NH4+ being transferred into clay minerals. Meanwhile, the lower δ15N values in the black shale unit indicated anoxic conditions, which recorded primary N isotope signals. The Mn-carbonate unit is characterized by negative δ13Ccarb values (−11.17‰ to −5.22‰, mean −8.30‰), which show a positive relationship with δ13Corg, but a negative relationship with Mn contents, implying that the negative δ13Ccarb excursions were related to the organic matter degradation during Mn-carbonate formation. The findings of this study indicated that the metallogenesis of manganese deposits in the Cryogenian Nanhua Basin was constrained mainly by the oxic interval in the deep basin. The nitrogen and carbon cycling process can provide new insights into geochemical cycling after the Sturtian Glaciation.

River-estuary continuum highlighted by variabilities in carbon and nitrogen stable isotope ratios of the catadromous eel Anguilla japonica.

Estuaries exhibit high physicochemical variability and the properties of estuaries and the constituent segments are not yet systematically understood. This study aims to reveal the spatial heterogeneity of predominant organic sources using carbon and nitrogen stable isotope ratios (δ13C and δ15N, respectively) of Japanese eels (Anguilla japonica), one of the ideal natural samplers. In the Miyakoda River, Japan, our study site, the effectiveness of eel δ13C and δ15N values as standard indices of predominant organic sources was tested by employing the River Continuum Concept. This study then extended the application of these indices to the estuary, i.e., the Hamana Lake system, into which the Miyakoda River flows. Once in the upper estuary, eel δ13C and δ15N values became high, with the latter peaking in this river-estuary continuum, indicating that artificial labile subsidies (nutrients and organic matter) with high δ15N values were rapidly assimilated into the food web. Eel δ15N values decreased again in the middle estuary. Nevertheless, the influence of terrestrial organic subsidies extended into this segment, as evidenced by the low δ13C values of eels. These results suggest that refractory organic matter with low δ15N values, such as plant-derived ones, is slowly assimilated into the food web in the downstream estuarine segments. The higher δ13C values in the lower estuary suggested that the contribution of eelgrass or macroalgae occurred in addition to benthic microalgae. Thus, our results emphasize the need to consider the multiple energy flows to understand the estuary as a continuum.

Tracking Agulhas Leakage in the South Atlantic Using Modern Planktic Foraminifera Nitrogen Isotopes

AbstractSeawater transported into the South Atlantic from the Indian Ocean via “Agulhas leakage” modulates global ocean circulation and has been linked to glacial‐interglacial climate cycles. However, constraining past Agulhas leakage has been a challenge. We sampled a transect of the Cape Basin in winter 2017 that intersected a mature Agulhas eddy and found that the 15N/14N ratio (δ15N) of mixed‐layer nitrate, zooplankton, and foraminifera (tissue and shells) was 2‰–3‰ lower in the eddy than in the background Atlantic even though the δ15N of the underlying thermocline nitrate was indistinguishable between the two settings. We suggest that the δ15N of foraminifera and other zooplankton in the eddy reflects the original Agulhas Current thermocline nitrate, which is ∼2‰ lower than that of the South Atlantic due to N2 fixation that occurs in the Indian Ocean. Foraminifera δ15N may have been lowered further during eddy migration by in situ N2 fixation and/or recycling of low‐δ15N ammonium. The absence of low‐δ15N Agulhas nitrate in the eddy thermocline can be explained by partial assimilation of the nitrate as it was mixed into the euphotic zone during and after eddy formation, raising its δ15N. The low δ15N of eddy foraminifera, apparent even after several months of eddy migration across the Cape Basin, suggests that fossil foraminifer‐bound δ15N from the region could record variations in past Agulhas leakage.

Slow recovery in trophic structure of restored wetlands in Northeast China

Restoration measures have been widely implemented in wetland ecosystems globally to bend the curve of biodiversity loss and restore associated ecological functions. However, assessments of the effectiveness of wetland restoration have predominantly focused on the recovery of taxonomic composition, while few studies have assessed the effectiveness of these efforts from a food web perspective. Here, we incorporated stable isotope approach to investigate trophic structure in natural and restored wetlands in Northeast China. The investigated consumers, including zooplankton, macroinvertebrates, and fish, exhibited lower δ15N and higher δ13C values in restored wetlands than in natural wetlands. Natural wetlands exhibited higher trophic positions and a wider range of trophic levels compared to restored wetlands. Primary consumers in natural wetlands relied more on particulate organic matter (POM, 42.9 % ± 24.1 %), while those in restored wetlands were more dependent on substrate organic matter (SOM, 42.3 % ± 23.9 %). Compared to natural wetlands, isotopic richness was significantly lower in restored wetlands, with smaller isotopic variation (SEAs) in basal resources, aquatic invertebrates, and fish. Our findings reveal that the recovery of trophic structures in restored wetlands lags behind that of taxonomic composition. Future restoration efforts should prioritize enhancing habitat heterogeneity and resource availability to support a diverse range of trophic levels. Monitoring trophic dynamics is essential for assessing the progress of wetland restoration and should be integrated into monitoring schemes.

Integrating source tracking tools for marine shellfish tracing: Metataxonomic and isotopic analyses

Shellfish farming is a significant activity in the Northern Adriatic Sea, particularly in Italy, where it plays a crucial role in the European industry of live bivalve mollusks. This study aimed to exploit different analyses, including metataxonomy and isotopic profiling, to address these issues. Isotopic analysis showed differences between habitats, with lower δ15N in sea samples, likely indicating lesser anthropogenic impact compared to lagoon environments. Additionally, seasonal variations in δ15N, δ13C and C/N highlighted differences in primary productivity and organic matter sources across seasons. Metataxonomic analysis revealed significant variability in microbial taxa across harvesting habitats and seasons. While no marked differences were observed in alpha and beta diversity based on habitat, distinct seasonal clustering indicated the influence of environmental factors on microbial community structure. Gammaproteobacteria were prevalent across habitats and seasons, with notable fluctuations in other taxa, such as Alphaproteobacteria, Epsilonproteobacteria, Flavobacteria, and Bacteroidia, particularly in lagoon habitats during winter. Overall, this study highlights the potential of microbial and isotopic characterization for tracing the origin of shellfish products. Metataxonomic analysis identified microbial signatures indicative of habitat and season, with implications for ecological dynamics and consumer safety. Isotopic analysis provided information on habitat characteristics and harvesting seasons, enhancing product traceability.

Establishing the limitations on using archived marine mammal samples for stable isotope analysis: an examination of differing preservation methods on tissues of harbor porpoise (Phocoena phocoena) and gray seal (Halichoerus grypus)

AbstractThe use of biological samples from museum and/or archive collections is common in stable isotope research, particularly for marine mammals. Yet, the temporal stability of isotopic values across various tissue types and the influence of different preservatives on these values are not fully understood, posing significant challenges for accurate data interpretation. Here we examine the impact of three different tissue preservation methods (DMSO, ethanol, freezing), on seven different tissues (blubber, heart, kidney, lung, liver, muscle, and skin) from both a harbor porpoise (Phocoena phocoena) and a gray seal (Halichoerus grypus) for stable isotope analysis in a 1‐year period. Our results demonstrate that storage in DMSO generates greater temporal variability in δ13C and δ15N for all tissue types, particularly in the first six months of storage. Furthermore, tissues stored in DMSO often exhibited lower δ13C and δ15N values compared to those stored frozen or in ethanol. This finding highlights a significant issue for studies utilizing tissues stored in DMSO, regardless of the storage duration. These results underscore the critical need for careful consideration of preservation methods in studies involving stored tissues, providing valuable insights for experimental design and management of tissue archives.

Large nitrogen cycle perturbations during the Early Triassic hyperthermal

Ocean temperature, redox state, circulation, and nutrient levels regulate the marine nitrogen (N) cycle, yet their specific impacts during greenhouse intervals remain poorly understood. Here, we examined the Smithian–Spathian hyperthermal event (∼250.5 Ma) during the Early Triassic greenhouse using stable N isotopes (δ15N) from sedimentary records in the Nanpanjiang Basin and Northern Yangtze Basin of South China. The δ15N profiles in both basins reveal consistent trends that correspond to fluctuations in temperature across the Smithian–Spathian transition. The Smithian hyperthermal interval exhibited low δ15N values (mostly <+2‰), indicating N deficiency and enhanced biological N2 fixation. Bacterial blooms and the release of the potent greenhouse gas N2O, enhanced by high temperatures, may have triggered positive feedback mechanisms that sustained the warming and contributed to the late Smithian extinction. During subsequent cooling across the Smithian–Spathian transition, δ15N increased to a range of +3‰ to +7‰, likely reflecting signals of partial denitrification based on reconstruction of the NO3− inventory associated with oceanic cooling and oxygenation. The prevailing increases in sedimentary TOC/TN ratios signify heightened deamination (removal of amino groups) and N recycling across the Smithian–Spathian boundary. This transition is likely attributed to cooling-driven amelioration of seawater stratification and anoxia from the Smithian to the Spathian, which resulted in increased nitrate availability in the photic zone. Eukaryotic algae thrived while prokaryotes declined during the Spathian, evidenced by elevated δ15N and Δ13Ccarb-org (the difference between carbonate and organic carbon isotopes). The proliferation of eukaryotic algae had a positive impact on environmental conditions and facilitated biotic recovery due to more efficient burial of organic particles. A notable latitudinal gradient in the N cycle response was observed, with low-latitude regions showing a more pronounced response to cooling compared to mid-latitude areas. This significant gradient may suggest that the rapid recovery of nutrient cycles, despite relatively small decline in high temperature, was a key factor in the amelioration of climate and recovery of life in low latitudes. These findings highlight that the marine N cycle is highly sensitive to temperature changes, particularly in low-latitude regions, and that changes in N cycle under high-temperature conditions may be a critical life-limiting factor.

A nitrogen isotopic shift in fish otolith–bound organic matter during the Late Cretaceous

The nitrogen isotopes of the organic matter preserved in fossil fish otoliths (ear stones) are a promising tool for reconstructing past environmental changes. We analyzed the 15N/14N ratio (δ15N) of fossil otolith-bound organic matter in Late Cretaceous fish otoliths (of Eutawichthys maastrichtiensis, Eutawichthys zideki and Pterothrissus sp.) from three deposits along the US east coast, with two of Campanian (83.6 to 77.9 Ma) and one Maastrichtian (72.1 to 66 Ma) age. δ15N and N content were insensitive to cleaning protocol and the preservation state of otolith morphological features, and N content differences among taxa were consistent across deposits, pointing to a fossil-native origin for the organic matter. All three species showed an increase in otolith-bound organic matter δ15N of ~4‰ from Campanian to Maastrichtian. As to its cause, the similar change in distinct genera argues against changing trophic level, and modern field data argue against the different locations of the sedimentary deposits. Rather, the lower δ15N in the Campanian is best interpreted as an environmental signal at the regional scale or greater, and it may be a consequence of the warmer global climate. A similar decrease has been observed in foraminifera-bound δ15N during warm periods of the Cenozoic, reflecting decreased water column denitrification and thus contraction of the ocean's oxygen deficient zones (ODZs) under warm conditions. The same δ15N-climate correlation in Cretaceous otoliths raises the prospect of an ODZ-to-climate relationship that has been consistent over the last ~80 My, applying before and after the end-Cretaceous mass extinction and spanning changes in continental configuration.

Seasonal variability in the feeding ecology of an oceanic predator

Complementary approaches (stomach contents, DNA barcoding, and stable isotopes) were used to examine seasonal shifts in the feeding ecology of an oceanic predator, yellowfin tuna (Thunnus albacares, n = 577), in the northern Gulf of Mexico. DNA barcoding greatly enhanced dietary resolution and seasonally distinct prey assemblages were observed for both sub-adults and adults. In general, diet was characterized by ommastrephid squids and exocoetids in spring, juvenile fishes (i.e., carangids and scombrids) in summer, migratory coastal fishes during fall, and an increased consumption of planktonic prey (e.g., amphipods) in winter. Seasonal variability in bulk stable isotope values (δ13C, δ15N, and δ34S) was also observed, with low δ15N values and high δ34S values during late summer/early fall and high δ15N values (low δ34S) during late winter/early spring. Bayesian stable isotope mixing models corroborated seasonal diet shifts, highlighting the importance of oceanic nekton in spring/summer, coastal nekton during fall, and oceanic plankton during winter. Seasonal shifts in diet appeared to be influenced by prey reproductive cycles, habitat associations, and environmental conditions. Findings highlight the complex food web dynamics supporting an opportunistic oceanic predator and the importance of seasonal cycles in prey availability to predator resource utilization in open-ocean ecosystems.

Heterogeneous marine response during the Toarcian Oceanic Anoxic Event (TOAE): The potential role of storminess

The Toarcian Oceanic Anoxic Event (TOAE; ∼183 Ma) represents an important hyperthermal and deoxygenation event in the Early Jurassic. However, TOAE marine records are spatially heterogeneous with regard to nutrient levels, primary productivity, redox conditions and organic enrichment. This non-uniform response to global hyperwarming is not readily accounted for by local variations in paleogeography, climate, or water depth. Largely overlooked to date is the intensified storm activity that characterized the TOAE, and the role that this may have played in controlling marine responses to that event. A review of TOAE studies from multiple marine environments suggests that storm intensity covaried with paleoceanographic conditions, such as nutrient availability, primary productivity, redox conditions, and organic-rich sedimentation. At mid-paleolatitude sites, relatively weak storm activity during the TOAE induced short-term watermass oxygenation, and marine settings were mainly characterized by enhanced anoxia (even euxinia), water-column stratification, increased primary productivity (fueled by terrestrial runoff and P regeneration in euxinic settings), and organic-rich sedimentation. At low-paleolatitude sites, TOAE storm activity was relatively strong, and contributed to marine environments characterized by oxic to suboxic conditions, reduced water-column stratification, decreased primary productivity (possibly due to limited P regeneration and upwelling), low sedimentary organic content, and locally high oolite abundance. TOAE marine sites at all paleolatitudes exhibit: i) sea-level rise and enhanced continental weathering fluxes linked to an intensified hydrological cycle; ii) reduced dinoflagellate and increased cyanobacterial activity; and iii) low δ15N values (mainly −1‰ to +3‰) linked to enhanced diazotrophic nitrogen fixation. The spatial heterogeneity of the response of TOAE marine systems is difficult to reconcile with scenarios linking increased terrestrial flux to marine eutrophication, primary productivity increase and organic-rich sedimentation. Consequently, we hypothesize that the intensity of storm activity influenced TOAE marine systems, and that this factor can, at least partially, account for heterogeneous patterns of environmental changes at middle versus low paleolatitudes and open versus restricted marine settings. Importantly, increased storm activity can induce pycnocline deepening via vertical water-column mixing, thereby promoting: i) enhanced aerobic degradation of organic matter (low sediment organic matter content) due to a reduced oxygen-minimum zone; ii) less nutrient upwelling from deep waters into the photic zone (nutrient-depleted upper ocean), and iii) blooms of nitrogen-fixing cyanobacteria (low δ15N) and calcification (ooid formation). Thus, the interaction between storminess and pycnocline depth is a potentially important factor affecting marine environmental changes during TOAE. These findings have implications for modern oceans now experiencing climatic warming and intensified tropical storm activity.

Stable isotope and fatty acid variation of a planktivorous fish among and within large lakes.

Aquatic food webs are spatially complex, potentially contributing to intraspecific variability in production pathway reliance of intermediate trophic level consumers. Variation in trophic reliance may be described by well-established trophic indicators, like stable isotope ratios (δ13C, δ15N), along with emerging trophic indicators, such as fatty acid composition. We evaluated stable isotope ratios and fatty acid profiles of European smelt (Osmerus eperlanus) among and within distinct regions of three large Swedish lakes (Hjälmaren, Mälaren, Vättern) which differed in trophic status. We expected that smelts in more oligotrophic lakes and regions would be characterized by distinct stable isotope signatures and fatty acid profiles, with particularly high polyunsaturated fatty acid (PUFA) relative levels. However, we acknowledge that frequent movement of smelts among regions may serve to spatially integrate their diet and lead to limited within-lake variation in stable isotope ratios and fatty acid composition. As expected, in comparison with more productive lakes (i.e., Hjälmaren and Mälaren), smelts from ultra-oligotrophic Vättern were characterized by low δ15N, high δ13C and high percent of a dominant PUFA, docosahexaenoic acid (DHA). Smelts from different regions of the morphometrically complex Mälaren displayed differential stable isotope ratios and fatty acid relative concentrations, which were consistent with within-lake differences in productivity and water residence times, suggesting that smelts in this lake forage locally within distinct regions. Finally, at the individual smelt level there were particularly strong and consistent associations between a well-established trophic indicator (δ13C) and percent DHA, suggesting that the relative concentration of this fatty acid may be a useful additional trophic indicator for smelt.

Mercury bioaccumulation and trophic transfer in Pacific Saury from the North Pacific Ocean

This study investigates mercury (Hg) dynamics in Pacific Saury (Cololabis saira) across the North Pacific Ocean, specifically off East Japan in 2018. Saury traits vary with total mercury (THg) concentrations in muscle tissues ranging from 0.017 to 0.082 μg g−1 w. w., averaging of 0.042 (n = 46). A positive correlation between THg and saury length (Knob length, 270–319 mm) indicates increased Hg concentration with size. Stable isotopic tracers suggest Pacific Euphausiids (Krill) are significant contributors to the saury diet (>70% of total). Significant correlations between logarithm THg concentration (Log THg) and δ15N (‰) (R2 = 0.70) demonstrate Hg trophic biomagnification, with regional variations. Comparative analysis between the eastern (ENPO) and western North Pacific Ocean (WNPO) indicates differences, with WNPO saury exhibiting lower δ15N values and higher THg levels than ENPO saury. This suggests that the WNPO, located near East Asia, the world's largest Hg emitter, experiences elevated Hg levels in seawater due to anthropogenic release. Overall, this study advances understanding of Pacific Saury's ecological interactions and Hg bioaccumulations, emphasizing the importance of species-specific behaviors and regional influences in ecological studies.

Camelids in the hyperarid core of the Atacama desert 12,000–11,000 years ago? A stable isotope study and its consequences for early human settlement

How did hunter-gatherers initially settle and move across extreme environments? We conducted a multi-disciplinary study to tackle this question, focusing on how Paleoindigenous populations inhabited the hyperarid core of the Atacama Desert. Particularly, we examined the stable isotopic values of ∼12,000–11,200-year-old camelid and rodent bones and hair samples retrieved from low-elevation archaeological sites (Pampa del Tamarugal basin - PdT, 800–1200 masl). By integrating novel and existing data into a regional stable isotope ecology, we offer a baseline for interpreting our results. δ13C and δ15N values on archaeological remains show animals with different geographical origins. A first group includes camelids and rodents with lower δ15N values and δ13C values indicating a dominantly C3 diet, corresponding to animals either local to the PdT or from the Andean Steppe, at least ∼80 km away and between 4000 and 4500 masl. Most of these remains, however, come from residential sites and belong to young camelids, indicating a local origin. A second group presents a higher δ15N signal and δ13C values indicative of a mixed C3–C4 based diet. These animals were not local but source to the Puna at least ∼60 km away between 3200 - 4000 masl. We hypothesize that the first would correspond to animals associated with hunter-gatherer bands settled around a wetland and grove environment in the PdT. The second group could correspond to remains brought by humans from the Puna to the PdT. Our results demonstrate that during the Late Pleistocene/Early Holocene the Atacama was very different than today, supporting life that included large and mid-size game. These results also show that the core of the Atacama attracted animals and people and counters the notion of this ecosystem as a barren passageway from the Andes to the coast.

Drivers of organic carbon distribution and accumulation in the northern Barents Sea

Sedimentary properties and accumulation rates on the continental shelf and in the deep sea reflect temporal oceanographic, biological and chemical processes occurring in the water column and the sediment surface. We used the radionuclides 210Pb, 226Ra, and 137Cs activities to estimate sedimentation rates during the last century at nine stations in the northern Barents Sea region. Elemental (C, N) and stable isotopic composition (δ13C, δ15N) were also analysed from the nine stations sampled in August 2018, and, for five other stations sampled in August and December 2019, and in March and May 2021. Sediment accumulation rates varied between 130 and 1 410 g m−2 y−1. The < 63 μm normalized total organic carbon (TOC63) and the total nitrogen from the sediment surface varied between 0.90–2.56 % and 0.13–0.33 %, respectively. Ice-free shelf stations had higher TOC63 and possibly fresher organic matter (high δ13C, low δ15N) than ice-covered more northern stations. The opposite trend was observed for total inorganic carbon. We found that these trends in biogeochemical parameters were spatially structured by the winter sea ice concentration and biological production differences, and exhibited a south-north separation of the Polar Front region. The low and stable organic carbon accumulation rate (1.7–13.4 g Corg m-2 y−1; ARtoc) is a function of slow sedimentation rates, and high degradation and residence time in the water column and at the sediment–water interface. Overall, the ARtoc has been stable for the past 100 years, with a slight increase from the early 1970s to the present at the shelf and slope stations. Our results highlight that spatial scales of variability of the studied sedimentary parameters are linked to spatial patterns of important environmental variables (e.g., chlorophyll-a, sea ice concentration) in the region. In contrast, no seasonal differences were observed in the sediment parameters of revisited stations, and the dated sediment geochemical profiles did not exhibit substantial longer-term variation. This means that climate-induced changes in variables that modify the sedimentary geochemistry of the environment may affect benthic community activity and structure before leaving a record in ARtoc.

An Updated Isotopic Database of Fertilizers Used in Intensive Organic Farming: A Case Study on Protein Hydrolyzed Derivatives and Chelated Nutrients

The global demand for organic food products has rapidly increased over the last years, becoming an emerging niche market targeting the high-income segment. The higher retailing price for organic food products may increase the risk of fraudulent practices at the different stages of the food supply chain, and consequently, substantial control is needed. Currently, the authentication of organic food products, such as those of plant origin, remains a key challenge in analytical chemistry. While stable isotopes have emerged as a powerful tool for this purpose, most studies have focused on crops, missing the agricultural inputs used for fertilization that influence the isotopic values of the crops. In this study, we aimed to isotopically characterize commonly used fertilizers, soil conditioners, and micronutrient fertilizers in intensive organic agriculture in the largest organic production region in the world (Almería, Spain). Our goal was to clarify the limitations that nitrogen isotopic fingerprinting presents for the fertilizer input industry and to characterize the organic inputs. The conventional fertilizers analyzed in this study showed low δ15N values compared to their organic counterparts, except for some plant-based fertilizers, protein hydrolyzed fertilizers, and chelated nutrients. Both protein hydrolyzed fertilizers and micronutrient fertilizers presented a wide range of variability in their δ15N values, including some very low or even negative values, more similar to those of conventional fertilizers. The results of this study highlight the challenges of authenticating organic foods in agriculture when using nitrogen isotope analysis.

Acropora tenuis energy acquisition along a natural turbidity gradient

Predicted future increases in both local and global stressors are expected to lead to elevated turbidity levels and an expansion of the geographical range of turbid coral reefs. Corals typically respond to elevated turbidity by increasing their rates of heterotrophy as means of compensating for low energy levels from reduced light and photosynthesis. We analysed Acropora tenuis energy acquisition along a natural turbidity gradient over two time points in Exmouth Gulf, Western Australia, using in-situ environmental data with coral physiology attributes and stable isotopes to assess trophic strategy. Our hypothesis was that as turbidity levels increased, so too would heterotrophy rates. Both δ13C and δ15N values decreased from the clear-water to the turbid sites, which along with Bayesian analysis revealed that all A. tenuis communities along the turbidity gradient are on a mixotrophic-heterotrophic feeding strategy scale. We propose that the low δ15N levels at the most turbid site may result from a combination of Acropora physiological limitations (e.g., reduced feeding capacity) and highly variable turbidity levels. In contrast, the higher δ15N at the clear-water site likely results from increased nutrient availability from additional sources such as upwelling. Our findings suggest that increased heterotrophy by coral hosts in turbid coral reef areas is not a universal pattern. Importantly, the loss of carbon in the turbid sites is not supplemented by nitrogen intake, which might suggest that Exmouth Gulfs Acropora communities are more vulnerable to future climate stressors and bleaching.

Long-term effects of biochar application on biological nitrogen fixation of acacia species and soil carbon and nitrogen pools in an Australian subtropical native forest

PurposeBiological nitrogen (N) fixation (BNF) of understory acacia species presents a potential way for effectively restoring N in forest systems. This study aimed to quantify the impact of acacia species and biochar application rates on BNF and soil mineral N in a suburban native forest of subtropical Australia in the first 4–5 years after prescribed burning.MethodPlant growth values and BNF were measured to assess the impact of biochar rates at 0, 5, and 10 t ha−1 on different acacia species. Soil NH4+-N and NO3−-N along with their N isotope composition (δ15N) were determined to investigate soil–plant interactions in response to acacia species and biochar application.ResultsThe application of 10 t ha−1 biochar significantly enhanced the growth of acacia species, and concurrently reduced the loss of NO3−-N at soil depths of 0–5 and 5–10 cm. Compared with Acacia disparimma (percentage of N derived from the atmosphere or %Ndfa: 78.2%), A. leiocalyx demonstrated significant higher BNF ability (%Ndfa: 91.3%). Similarly, A. leiocalyx had better growth, in terms of height (269.1 cm versus 179.6 cm), diameter at ground level (2.62 cm versus 1.94 cm), basal area (6.49 cm2 versus 3.43 cm2) and volume (692.2 cm3 versus 258.0 cm3). This was associated with its ability to promote organic matter mineralization, resulting in the accumulation of 15N-depleted NH4+-N. NH4+-N, acting as a substrate, was transformed into NO3−-N through nitrification. From regression analysis, the efficient absorption of NH4+-N by A. leiocalyx significantly mitigated NH4+-N leaching with increasing soil moisture concentration (SMC), resulting in lower δ15N of NH4+-N, which was more negatively related to SMC (R2 = 0.401), compared to that of A. disparimma (R2 = 0.250) at soil depth of 0–5 cm. The production of NO3−-N was reduced, leading to lower NO3−-N concentrations of A. leiocalyx than A. disparimma at soil depth of 0–5 cm (8.06 µg N g−1 versus 9.61 µg N g−1) and that of 5–10 cm (8.24 µg N g−1 versus 9.21 µg N g−1) respectively.ConclusionsAs an effective soil amendment, biochar exhibited promise in reducing mineral N loss and stimulating plant growth in long-term applications of exceeding three years. Higher BNF capacity and greater plant growth were observed with A. leiocalyx, compared with those of A. disparimma. The retention and utilisation of mineral N by A. leiocalyx can be considered as strategy to restore forest soils.

The Earth atmosphere‐like bulk nitrogen isotope composition obtained by stepwise combustion analyses of Ryugu return samples

AbstractThe nitrogen isotope compositions of two samples returned from the asteroid Ryugu were determined using a stepwise combustion method, along with Ivuna (CI) and Y‐980115, a CI‐like Antarctic meteorite, as references. The two Ryugu samples A0105‐07 and C0106‐07 showed bulk δ15N values of +1.7 ± 0.5‰ and +0.2 ± 0.6‰, respectively, significantly lower than Ivuna with +36.4 ± 0.4‰, but close to Y‐980115 with +4.0 ± 0.3‰. The Ryugu samples are further characterized by C/N and 36Ar/N ratios up to 3.4× and 4.9× the value of Ivuna, respectively. Among all Ryugu samples and CI chondrites, a positive correlation was observed between nitrogen concentrations and δ15N values, with samples with lower nitrogen concentrations exhibiting lower δ15N. This trend is explained by a two‐component mixing model. One component is present at a constant abundance among all CI‐related samples, with a δ15N value around 0‰ or lower. The other varies in abundance between different samples, and exhibits a δ15N value of +56 ± 4‰. The first 15N‐poor endmember is seemingly tightly incorporated into a carbonaceous host phase, whereas the 15N‐rich endmember can be mobilized and decoupled from carbon, potentially because it is in the form of ammonia. Asteroid materials with volatile compositions that are similar to those reported here for the Ryugu samples are attractive candidates for the volatile sources among Earth's building blocks.