Nitrogen Isotopic Composition Research Articles

Remote sensing estimation of δ15NPN in the Zhanjiang Bay using Sentinel-3 OLCI data based on machine learning algorithm

Remote sensing estimation of δ15NPN in the Zhanjiang Bay using Sentinel-3 OLCI data based on machine learning algorithm

Trophic interactions between common minke whales (Balaenoptera acutorostrata) and their prey during summer in the northern Barents Sea

Global warming is causing rapid change in marine food webs, particularly at northern latitudes where temperatures are increasing most rapidly. In this study, the diet of common minke whales Balaenoptera acutorostrata was assessed both in terms of short-term (morphological analyses of digestive tract contents) and longer-term (tissue chemical markers: fatty acids and stable isotopes) prey use in the northern Barents Sea to see if they are prey shifting. Samples (blubber cores, muscle, and stomach contents) were obtained from 158 common minke whales taken during Norwegian commercial whaling operations during summer over the period 2016–2020. Two prey items, capelin Mallotus villosus and krill (primarily Thysanoessa sp.), dominated the stomach contents in the entire period of investigation, which included sampling both in June and in August, similar to findings from earlier studies. A few gadoids were also observed in the whale stomachs. Lower blubber fatty acid (FA) contents in 2016/2017 as compared with 2018/2019 were observed. This is most likely explained by differences in sampling time (June in 2016/2017 vs August in 2018/2019, i.e., after a longer feeding period during the summer in the latter case). This explanation also fits with the fact that FA profiles of the 2018/2019 whales were more similar to the FA profiles of the potential prey, presumably reflecting the two months longer assimilation time for these whales. Multidimensional mixing models based on carbon and nitrogen isotope composition of the most likely prey groups suggested that the whales ate mostly krill in four of the five sampling years. In 2018 there were indications of a higher proportion of gadoid fish, showing some dietary flexibility. The trophic level of the whales’ feeding, as interpreted from the nitrogen isotope values, was positively correlated with blubber thickness suggesting that fish-eaters tended to assimilate more energy than whales that focused more exclusively on lower trophic prey. The variation suggested by different dietary analyses methods − stomach contents, fatty acids, and stable isotopes – most likely reflects different turnover times, with muscle stable isotopes likely representing several months of dietary integration, while lipid stores are more dynamic and may represent weeks, and stomach contents represent feeding events during the last few hours. The change in diet of minke whales from small pelagic fishes (in the past) to a greater quantity of krill and demersal fish (seen in this study) suggests that the whales are responding to the ongoing borealization of the Barents Sea ecosystem.

Carbon and nitrogen biogeochemistry of a high-altitude Himalayan lake sediment: inferences for the late Holocene climate

A study was conducted to decipher changes in paleoenvironmental conditions of the Kashmir Valley (India) using stable isotopic compositions and elemental concentrations of total organic carbon (TOC) and total nitrogen (TN) in a sediment core from the Wular Lake. The Chronology of the core established through radiocarbon dating estimated the age of the core bottom to be 3752 Cal years BP (Verma et al., 2023), covering the late Holocene. Using carbon isotopic compositions of TOC (δ13C), nitrogen isotopic compositions of TN (δ15N), and TOC - TN contents, the study identified changes in biology and associated biogeochemical processes in the Wular Lake during the late Holocene. Changes in C and N biogeochemistry of the lake through the last 3752 Cal years BP suggested overall drier condition during 3752–1500 Cal years BP that transitioned into a wetter condition at around 1500 Cal years BP until at least 295 Cal years BP. Evidence for relatively intense drier events were observed within the dry and wet phases at around 2500 and 500 Cal years BP. Changes in δ13C and TOC contents in the sediment core revealed that the inorganic C dynamics and productivity (along with organic C contents) in the lake were largely regulated by variations in respired CO2 and HCO3− availability along with terrestrial matter supply through the Jhelum River. Similarly, variations in δ15N and TN contents showed changes in N dynamics of the lake with varying nitrification and decomposition throughout the studied period. Observed dry and wet phases in the region might be due to the weakening and strengthening of the precipitation, which was linked to negative and positive phases of the North Atlantic Oscillation, respectively.

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.

Sources of NH4+ in PM2.5 and Their Seasonal Variations in Urban Tianjin China: New Insights From the Seasonal δ15N Values of NH3 Source

AbstractThe stable nitrogen isotopic composition (δ15N) has been widely used to quantify sources of ammonium (NH4+) in PM2.5. However, the overlap and uncertainty in δ15N values from different NH3 sources, coupled with their seasonal variability, hinder accurate identification of NH4+ source. Here, the δ15N values of various NH3 source samples collected by the active sampler were determined. Subsequently, we measured the δ15N values of NH4+ in PM2.5, which were collected seasonally in Tianjin. We found that the combustion‐related NH3 (c‐NH3) exhibiting higher δ15N values compared to volatile NH3 (v‐NH3), but all δ15N values was fell within the range reported by previous studies. Furthermore, inconsistent seasonal variations were observed in the δ15N‐NH3 values originating from emissions of agricultural soil and human excreta. The application of the Bayesian isotope mixing model (MixSIAR model) revealed a significant increase in the contribution of v‐NH3 to NH4+ when incorporating current source data, as opposed to previous data, for δ15N of NH3 source. Notably, the contribution of v‐NH3 (53.1%) to NH4+ was almost equivalent to that of c‐NH3 (46.9%) when considering the seasonal δ15N signatures of NH3 source. Additionally, the estimated contribution of v‐NH3 to NH4+ exhibited significant seasonal variability, which is more reasonable than in the non‐seasonal scenario. This study demonstrated that v‐NH3 and c‐NH3 contributed to NH4+ in PM2.5 in Tianjin almost equally, and it is highlighted that the seasonal δ15N values of NH3 sources should be considered when estimating the contributions of different NH3 sources to NH4+ in PM2.5 by the MixSIAR model.

Quantification of NOx sources contribution to ambient nitrate aerosol, uncertainty analysis and sensitivity analysis in a megacity

Dual isotopes of nitrogen and oxygen of NO3− are crucial tools for quantifying the formation pathways and precursor NOx sources contributing to atmospheric nitrate. However, further research is needed to reduce the uncertainty associated with NOx proportional contributions. The acquisition of nitrogen isotopic composition from NOx emission sources lacks regulation, and its impact on the accuracy of contribution results remains unexplored. This study identifies key influencing factors of source isotopic composition through statistical methods, based on a detailed summary of δ15N-NOx values from various sources. NOx emission sources are classified considering these factors, and representative means, standard deviations, and 95 % confidence intervals are determined using the bootstrap method. During the sampling period in Tianjin in 2022, the proportional nitrate formation pathways varied between sites. For suburban and coastal sites, the ranking was fP1(NO2 + OH radical) >fP2(N2O5 + H2O) >fP3(NO3 + DMS/HC), while the rural site exhibited similar fractional contributions from all three formation pathways. Fossil fuel NOx sources consistently contributed more than non-fossil NOx sources in each season among three sites. The uncertainties in proportional contributions varied among different sources, with coal combustion and biogenic soil emission showing lower uncertainties, suggesting more stable proportional contributions than other sources. The sensitivity analysis clearly identifies that the isotopic composition of 15N-enriched and 15N-reduced sources significantly influences source contribution results, emphasizing the importance of accurately characterizing the localized and time-efficient nitrogen isotopic composition of NOx emission sources. In conclusion, this research sheds light on the importance of addressing uncertainties in NOx proportional contributions and emphasizes the need for further exploration of nitrogen isotopic composition from NOx emission sources for accurate atmospheric nitrate studies.

Experimental simulation of thermal evolution of nitrogen content and isotopes in source rocks: Implications for nitrogen cycling characterization and oil-source correlation

Sedimentary nitrogen isotopes have been widely used to reconstruct the nitrogen cycling and redox characteristics of ancient oceans, but they also have important value in the study of oil genesis, such as oil classification. However, the thermal evolution of nitrogen isotopes in the source rock and associated oil is currently unclear. In this study, the thermal evolution (from the oil generation to the dry gas stage) of three types of low-maturity source rock was simulated. And the content and isotope composition of total organic carbon (TOC) and total nitrogen (TN) of the pyrolyzed source rock, expelled oil and retained oil were measured. In combination with weight-quantitative analyses, the following conclusions can be drawn: (1) During the main oil and gas generation stage, the pyrolyzed source rocks lost 15.1–28.3% of TN, which is much lower than the loss of TOC (26.2–46.1%). This difference may be related to the fact that the TOC content of the generated oil and gas is two orders of magnitude higher than the TN. In addition, TOC loss occurred mainly within the oil generation-expulsion stage, whereas TN loss occurred mainly in the dry gas stage and higher maturity stage. (2) The nitrogen isotope compositions of three types of source rocks and associated kerogens became heavier by 0.5–1.5‰ as thermal maturity increased, which is similar to the change of organic carbon isotope compositions. The δ15N values of pyrolyzed source rocks generally have poor relationships with either the amount of expelled oil and gas or the TN loss, which is different from the δ13Corg values. The δ15N fluctuations may be attributed to three processes: oil generation-expulsion, N2 gas generation-expulsion, and inorganic N (like NH4+) expulsion. The bulk nitrogen isotope composition of source rocks is only slightly affected by thermal maturity and can be used to indicate the nitrogen biogeochemical cycle and water redox conditions during the deposition. (3) Similar to δ13Corg values, δ15N values of both expelled oil and retained oil increased gradually with enhanced thermal maturity, implying a control of kinetic isotope effect. Among the three types of source rock, two of them having relatively light nitrogen isotope compositions (δ15N value of ∼2.5‰) generated and expelled oils with similar nitrogen isotope compositions, while the third type, which has heavy nitrogen isotope composition (δ15N value of ∼13.0‰), generated and expelled oils with much lighter nitrogen isotope compositions (by 3–6‰). This finding shows that there may be significant nitrogen isotope fractionation during the generation and primary migration of oil from source rocks. The nitrogen isotopes should be used in oil-source correlation with caution, even though related mechanisms need to be further studied. Nevertheless, using a combination of organic carbon and nitrogen isotopes, the oil generated and expelled by the three types of source rocks could be distinguished. Therefore, the use of nitrogen isotopes for oil-source correlation under geological conditions should be combined with other isotope and molecular indicators.

Nitrogen isotope gradient on continental margins during the late Paleoproterozoic

The late Paleoproterozoic was a key period in the evolution of Earth’s surface environments and life. It is generally accepted that during the 2.43–2.06 Ga Great Oxidation Episode, the atmospheric oxygen level rose to an intermediate state (0.1% to 10% of the present atmospheric level) and the chemical composition of the oceans changed significantly. The paleontological record indicates that eukaryotes appeared during the late Paleoproterozoic. Nitrogen, an essential nutrient for life, is thought to have been one of the key factors in eukaryote evolution. However, nitrogen bioavailability and spatial heterogeneity in nitrogen cycle in the late Paleoproterozoic oceans remain controversial. Here, we examine carbon and nitrogen cycling in the late Paleoproterozoic ocean, via analysis of redox-sensitive element contents and organic carbon and nitrogen isotope compositions of black shales of the ca. 1.9 Ga Nuvilic Formation of the Povungnituk Group, Cape Smith Belt, Canada. Two diamond drill-holes (DDHs) 718–3333 (∼50 m-long) and 4G8069 (∼90 m-long) investigated in this study contain turbiditic greywackes and black shales deposited on the northern margin of the Archean Superior craton below the storm wave-base. Sedimentary rocks of DDH 4G8069 might have been deposited closer to the continental source area, as indicated by sandstone abundance, than those of DDH 718–3333. Redox-sensitive element (V, U, and Mo) contents in black shales of DDH 4G8069 are low and show positive correlation with Al contents, whereas those of DDH 718–3333 are irregularly elevated. Fe/Al ratios of DDH 718–3333 are low, which likely reflect Fe loss from sediments under anoxic water-column conditions. Depositional environment is inferred to be above and below the redoxcline for DDHs 4G8069 and 718–3333, respectively. Organic carbon isotope values of DDH 718–3333 are approximately 1.7‰ lighter than those of DDH 4G8069, which might reflect methane cycling at the redoxcline. Nitrogen isotope values are positive (> +3‰) for all the black shale samples, corresponding to aerobic nitrogen cycling and presence of bioavailable nitrate on the northern margin of the Superior craton during the late Paleoproterozoic. Furthermore, nitrogen isotope values for DDH 718–3333 are approximately 2‰ heavier than those for DDH 4G8069. The observed isotopic heterogeneity is similar to that in modern oxygen-minimum zones and could represent intense denitrification at the redoxcline. Although no ca. 1.9 Ga microfossils reported to date are considered unambiguously eukaryotic, the aerobic nitrogen cycling inferred for the Nuvilic Formation, as well as for the previously studied Rove, Virginia, and Menihek formations, suggests that nitrogen limitation was unlikely to have inhibited biological evolution during the late Paleoproterozoic, a finding that is consistent with molecular clock studies suggesting that the emergence of eukaryotes occurred during the Paleoproterozoic.

Quantifying the δ15N trophic offset in a cold-water scleractinian coral (CWC): implications for the CWC diet and coral δ15N as a marine N cycle proxy

Abstract. The nitrogen (N) isotope composition (δ15N) of cold-water corals is a promising proxy for reconstructing past ocean N cycling, as a strong correlation was found between the δ15N of the organic nitrogen preserved in coral skeletons and the δ15N of particulate organic matter exported from the surface ocean. However, a large offset of 8 ‰–9 ‰ between the δ15N recorded by the coral and that of exported particulate organic matter remains unexplained. The 8 ‰–9 ‰ offset may signal a higher trophic level of coral dietary sources, an unusually large trophic isotope effect or a biosynthetic δ15N offset between the coral's soft tissue and skeletal organic matter, or some combinations of these factors. To understand the origin of the offset and further validate the proxy, we investigated the trophic ecology of the asymbiotic scleractinian cold-water coral Balanophyllia elegans, both in a laboratory setting and in its natural habitat. A long-term incubation experiment of B. elegans fed on an isotopically controlled diet yielded a canonical trophic isotope effect of 3.0 ± 0.1 ‰ between coral soft tissue and the Artemia prey. The trophic isotope effect was not detectably influenced by sustained food limitation. A long N turnover of coral soft tissue, expressed as an e-folding time, of 291 ± 15 d in the well-fed incubations indicates that coral skeleton δ15N is not likely to track subannual (e.g., seasonal) variability in diet δ15N. Specimens of B. elegans from the subtidal zone near San Juan Channel (WA, USA) revealed a modest difference of 1.2 ± 0.6 ‰ between soft tissue and skeletal δ15N. The δ15N of the coral soft tissue was 12.0 ± 0.6 ‰, which was ∼6 ‰ higher than that of suspended organic material that was comprised dominantly of phytoplankton – suggesting that phytoplankton is not the primary component of B. elegans' diet. An analysis of size-fractionated net tow material suggests that B. elegans fed predominantly on a size class of zooplankton ≥500 µm, implicating a two-level trophic transfer between phytoplankton material and coral tissue. These results point to a feeding strategy that may result in an influence of the regional food web structure on the cold-water coral δ15N. This factor should be taken into consideration when applying the proxy to paleo-oceanographic studies of ocean N cycling.

Low blank sampling method for measurement of the nitrogen isotopic composition of atmospheric NOx.

The nitrogen isotopic composition of nitrogen oxide (NOx) is useful for estimating its sources and sinks. Several methods have been developed to convert atmospheric nitric oxide (NO) and/or nitrogen dioxide (NO2) to nitrites and/or nitrates for collection. However, the collection efficiency and blanks are poorly evaluated for many collection methods. Here, we present a method for collecting ambient NOx (NO and NO2 simultaneously) with over 90% efficiency collection of NOx and low blank (approximately 0.5 μM) using a 3 wt% hydrogen peroxide (H2O2) and 0.5 M sodium hydride (NaOH) solution. The 1σ uncertainty of the nitrogen isotopic composition was ± 1.2 ‰. The advantages of this method include its portability, simplicity, and the ability to collect the required amount of sample to analyze the nitrogen isotopic composition of ambient NOx in a short period of time. Using this method, we observed the nitrogen isotopic compositions of NOx at the Tsukuba and Yoyogi sites in Japan. The averaged δ15N(NOx) value and standard deviation (1σ) in the Yoyogi site was (-2.7 ± 1.8) ‰ and in the Tsukuba site was (-1.7 ± 0.9) ‰ during the sampling period. The main NOx source appears to be the vehicle exhaust in the two sites.

Uptake patterns for nitrogen and sulfur source by aquatic plants and various nitrogen acquisition strategies: Affected by mining activities

Understanding the nitrogen and sulfur uptake strategies of mine plants, including sources and preferences for nitrogen forms (ammonium nitrogen (NH4+) vs nitrate nitrogen (NO3−)), is critical to improving understanding of the role of plants in participating in the biogeochemical cycles of nitrogen and sulfur in mining areas. In this study, the stable N and S isotopic compositions of two species of aquatic plants (calamus and reed) in Linhuan mining area were analyzed to determine their absorption strategies for different nitrogen and sulfur sources. The results showed that river water was the largest source of nitrogen and sulfur, contributing 54.6% and 53.9% respectively. NO3− is the main form of nitrogen uptake by reed and calamus, followed by NH4+. In order to adapt to the change of nitrogen form in the environment, reed and calamus tend to absorb and utilize NO3− to maintain their absorption of nitrogen. Mine effluents from mining activities provide at least 12.9% and 16.8% sulfate to reed and calamus respectively, and the effect of mine effluents on reed and calamus sulfur has been underestimated. This study reveals the key factors controlling plant isotope composition, and the use of nitrogen and sulfur isotope composition of aquatic plants can help quantify the level of influence of mining activities, and understand the biogeochemical cycle of nitrogen and sulfur in mining areas.

Ecophysiological traits of seedlings from different accessions of Stipa tenacissima along a climatic gradient

Predicting the future impact of climate change on Stipa tenacissima steppes is of paramount importance to prevent desertification. From this perspective, we selected seven populations, covering a rainfall range from 100 to 600 mm/year at the sites of seed collection, and we grew the seedlings at the same site. Gas exchange measurements of CO2, light response curves, chlorophyll content and isotopic analysis were investigated. Thala and Valencia populations displayed a contrasted gas exchange response. Both populations were subjected to A-Ci curve analysis. No significant difference was detected between these two different populations in the maximum rate of carboxylation (Vcmax) and the maximum rate of electron transport (Jmax). Stipa tenacissima exhibited a variable response in relation to different light intensities. Photosynthesis and chlorophyll fluorescence parameters proved to be significantly different among populations in response to light intensities. All populations exhibited similar chlorophyll content. The isotopic analysis highlighted a different carbon and nitrogen isotopic composition (δ13C and δ15N) and carbon content © among populations. Mesic populations presented a higher gas exchange activity and light response. The xeric populations performed a photosynthesis adjustment along with minimizing chlorophyll content. Under climate change, S. tenacissima limits productivity, which may lead to desertification.

Potential impacts of coal mining activities on nitrate sources and transport in a karst river basin in southwest China.

Typical sources of nitrate pollution in the fragile ecological environment of karst areas, such as agricultural production activities and domestic sewage, have long attracted serious concern. However, coal development can play an equally significant role in releasing the nitrogen fixed in coal into surface watersheds in the form of nitrate, nitrite, or ammonia, consequently threatening the water quality of surface water systems in mining areas. In this study, a typical karst surface watershed system affected by coal mining activities was selected for an in-depth investigation with the aim of realistically assessing the potential contribution of coal mining to nitrogen pollution. The results reveal increasingly concerning nitrate pollution from August 2020 to November 2021 in the Huatan River watershed under the influence of anthropogenic activities, especially mining development and agricultural production. Given that the nitrogen and oxygen isotope compositions of nitrate do not support the presence of denitrification, the variation in the NO3-/Cl- ratio and the relatively stable Cl- concentration may be a reflection of nitrification. Although the leaching of atmospheric precipitation on the strata in the basin promoted the release of nitrogen associated with coal mining, the higher rate of nitrogen cycling in the oligotrophic mine water environment limited the contribution of coal mining to nitrogen pollution in the surface watershed. Specifically, the contribution of coal mining activities to nitrogen pollution in surface karst river is mainly NH4+-N, which contributes 10% or less to the nitrate input to the waters of the Huatan River. The findings thus highlight the necessity of further uncovering the geochemical cycling process of nitrogen during the transport of mine water in the coal mining environment.

Proof of Principle of the Lunar Soil Volatile Measuring Instrument on Chang’ e-7: In Situ N Isotopic Analysis of Lunar Soil

The nitrogen isotopic compositions of lunar soil have important implications for the sources of lunar volatiles and even the evolution of the moon. At present, the research on the lunar nitrogen isotopic compositions is mainly based on the lunar meteorites and the samples brought back by the Apollo and Luna missions. However, volatiles adsorbed on the surface of the lunar soil may be lost due to changes in temperature and pressure, as well as vibration and shock effects when the sample is returned. At the same time, in the case of low N content in the sample, since N is the main component of the earth’s atmosphere, it is easily affected by the atmosphere during the analysis process. Therefore, in situ nitrogen isotopic analysis of lunar soil on orbit is necessary to avoid the problems mentioned above and is one of the primary science goals for the Lunar Soil Volatile Measuring instrument on Chang’e-7 spacecraft. After the nitrogen purification procedure, the volatiles in lunar soil that are released through single-step or stepped heating techniques diffuse to the quadrupole mass spectrometer to obtain the N contents and isotopic compositions of the lunar soil. This paper introduces the ground test for N isotopic analysis of lunar soil in orbit according to the Lunar Soil Volatile Measuring Instrument. After long-term repeated measurements, the background and CO-corrected Air-STD 14N/15N ratio is 268.986 ± 4.310 (1SD, n = 35), and the overall reproducibility of measurements is 1.6%. The accuracy of N isotopic compositions is calculated to be better than 5%, which can distinguish different sources of N components in lunar soil.

Amino acid nitrogen isotopic compositions show seep copepods gain nutrition from host animals

Deep-sea chemosynthetic ecosystems harbour high biomass centred around animals with chemoautotrophic symbionts. Despite being intensively studied over the last 4 decades, microscopic animals associated with and/or parasitic on dominating holobionts remain understudied. Here, we combine bulk tissue isotope analysis for carbon and nitrogen and compound-specific isotope analysis of amino acids (CSIA-AA) for nitrogen to elucidate the relationship between 2 copepod-host pairs from the Off Hatsushima hydrothermal seep in Sagami Bay, Japan: the vesicomyid clam Phreagena okutanii and Hyphalion sagamiense living on its mantle, and the tubeworm Lamellibrachia columna and Dirivultus kaiko found on its plume. Bulk tissue isotope analyses found overall large variations in δ13C and δ15N values across both associations, and did not allow conclusions on the trophic relationship between each pair. In contrast, CSIA-AA for Phreagena-Hyphalion clearly showed trophic positions (TPGlu/Phe) increasing from gill (symbiont) to adductor muscle (host tissue) to H. sagamiense. In the case of Lamellibrachia-Dirivultus, a similar increase in TPGlu/Phe was found from the plume to D. kaiko. These results show that both H. sagamiense and D. kaiko are nutritionally dependent on their respective hosts and therefore should be considered parasites despite being from copepod families that are typically not recognised as parasitic. Our CSIA-AA results represent the first use of this technique to document host-parasite relationships in chemosynthetic ecosystems. Understanding the role of parasites is of great importance in reconstructing energy flow in ecosystems, and our results underscore the promising nature of CSIA-AA in revealing their otherwise hidden relationships.

A nitrogen isoscape of phytoplankton in the western North Pacific created with a marine nitrogen isotope model

The nitrogen isotopic composition (δ15N) of phytoplankton varies substantially in the ocean reflecting biogeochemical processes such as N2 fixation, denitrification, and nitrate assimilation by phytoplankton. The δ15N values of zooplankton or fish inherit the values of the phytoplankton on which they feed. Combining δ15N values of marine organisms with a map of δ15N values (i.e., a nitrogen isoscape) of phytoplankton can reveal the habitat of marine organisms. Remarkable progress has been made in reconstructing time-series of δ15N values of migratory fish from various tissues, such as otoliths, fish scales, vertebrae, and eye lenses. However, there are no accurate nitrogen isoscapes of phytoplankton due to observational heterogeneity, preventing improvement in the accuracy of estimating migratory routes using the fish δ15N values. Here we present a nitrogen isoscape of phytoplankton in the western North Pacific created with a nitrogen isotope model. The simulated phytoplankton is relatively depleted in 15N at the subtropical site (annual average δ15N value of phytoplankton of 0.6‰), where N2 fixation occurs, and at the subarctic site (2.1‰), where nitrate assimilation by phytoplankton is low due to iron limitation. The simulated phytoplankton is enriched in 15N at the Kuroshio–Oyashio transition site (3.9‰), where nitrate utilization is high, and in the region around the Bering Strait site (6.7‰), where partial nitrification and benthic denitrification occur. The simulated δ15N distributions of nitrate, phytoplankton, and particulate organic nitrogen are consistent with δ15N observations in the western North Pacific. The seamless nitrogen isoscapes created in this study can be used to improve our understanding of the habitat of marine organisms or fish migration in the western North Pacific.

Modern analogs for ammonia flux from terrestrial hydrothermal features to the Archean atmosphere

The isotopic composition of nitrogen in the rock record provides valuable evidence of reactive nitrogen sources and processing on early Earth, but the wide range of δ15N values (− 10.2 to + 50.4‰) leads to ambiguity in defining the early Precambrian nitrogen cycle. The high δ15N values have been explained by large fractionation associated with the onset of nitrification and/or fractionation produced by ammonia-ammonium equilibrium and water–air flux in alkaline paleolakes. Previous flux sensitivity studies in modern water bodies report alkaline pH is not a prerequisite and temperature can be the dominate parameter driving water–air flux. Here, I use the chemical and physical components of 1022 modern hydrothermal features to provide evidence that water–air NH3 flux produced a significant source of fixed nitrogen to early Earth’s atmosphere and biosphere. With regard to the modeled average NH3 flux (2.1 kg N m−2 year−1) and outlier removed average flux (1.2 kg N m−2 year−1), the Archean Earth’s surface would need to be 0.0092, and 0.017% terrestrial hydrothermal features, respectively, for the flux to match the annual amount of N produced by biogenic fixation on modern Earth. Water–air NH3 flux from terrestrial hydrothermal features may have played a significant role in supplying bioavailable nitrogen to early life.

A novel ontogeny-related sampling of dental tissues for stable isotopes interpretation of the paleobiology of the cave bear

In cave bear studies, stable isotope analysis of carbon and nitrogen is typically conducted on bone collagen. However, challenges arise due to biases in the classification of bones into age groups, which can be influenced by various factors that affect bone size. To overcome such issues, we present and evaluate a novel approach that involves sampling dental collagen from different ontogenetic stages of 45 fossil teeth, where only a portion of each tooth formed during the periods of interest was sampled. This approach enabled us to obtain a carbon and nitrogen fingerprint specific to a particular period in a cave bear’s life without interference from earlier stages. Stable isotopic analysis revealed a rapid decrease in δ15N values from 3 to 15 months of age. After that, the δ15N values remain stable. Based on the nitrogen isotope composition (15N/14N), cubs aged 0–3 months exclusively consumed milk, while the gradual introduction of solid plant food occurs at 5–10 months, resulting in a shift in δ15N values. Based on similar δ15N values in older age groups, it can be assumed that juveniles did not resume milk suckling after the first hibernation. The δ13C values increase until 15 months, followed by a gradual decrease until adulthood, potentially attributable to hibernation. The δ13C values also seems to indicate isotopic differences between yearlings with low δ13C values that successfully established hibernation and those with high δ13C values that failed to hibernate and starved. This novel observation, i.e., decreasing δ13C values from the second year of life onward, agrees with predicted isotopic skeletal collagen δ13C values calculated from modern brown bear blood plasma. In summary, the ontogenetic sampling strategy facilitated the acquisition of further paleobiological insights into the distinct life periods of cave bears.

Large Seasonal Variation in Nitrogen Isotopic Abundances of Ammonia Volatilized from a Cropland Ecosystem and Implications for Regional NH3 Source Partitioning.

Ammonia (NH3) volatilization from agricultural lands is a main source of atmospheric reduced nitrogen species (NHx). Accurately quantifying its contribution to regional atmospheric NHx deposition is critical for controlling regional air nitrogen pollution. The stable nitrogen isotope composition (expressed by δ15N) is a promising indicator to trace atmospheric NHx sources, presupposing a reliable nitrogen isotopic signature of NH3 emission sources. To obtain more specific seasonal δ15N values of soil NH3 volatilization for reliable regional seasonal NH3 source partitioning, we utilized an active dynamic sampling technique to measure the δ15N-NH3 values volatilized from maize cropping land in northeast China. These values varied from -38.0 to -0.2‰, with a significantly lower rate-weighted value observed in the early period (May-June, -30.5 ± 6.7‰) as compared with the late period (July-October, -8.5 ± 4.3‰). Seasonal δ15N-NH3 variations were related to the main NH3 production pathway, degree of soil ammonium consumption, and soil environment. Bayesian isotope mixing model analysis revealed that without considering the seasonal δ15N variation in soil-volatilized NH3 could result in an overestimate by up to absolute 38% for agricultural volatile NH3 to regional atmospheric bulk ammonium deposition during July-October, further demonstrating that it is essential to distinguish seasonal δ15N profile of agricultural volatile NH3 in regional source apportionment.

Degradation of peat-forming plants at the first stages of decomposition in natural and post-pyrogenic peatlands of West Siberia

The aim of the study. Assessment of the phytomass stocks and decomposition rate of peat-forming plants’ residues in peat deposits of natural and post-pyrogenic peatlands at the initial stages of decomposition. Location and time of the study. The study was carried out in 2022 (May-September) at two oligotrophic bog sites: “Bakcharskoye” (field station “Vasyuganye”, IMCES SB RAS) and “Iksinskoye”, which are located in the north eastern spurs of the Great Vasyugan mire in the Bakcharsky and Shegarsky districts of the Tomsk region, Russia. Methods. The phytomass stocks were determined by the cutting method. The following fractions were separated: living phytomass (annual and perennial photosynthetic phytomass, i.e. green parts of grasses, shrubs leaves, mosses); perennial non-photosynthetic phytomass, i.e. shrubs stems, roots of grasses and shrubs; and dead phytomass (mortmass), i.e. litter, moss litter, standing dead phytomass. The decomposition rate of plant residues was determined by the method of litter bags placement in peat (Chamaedaphne calyculata, Sphagnum fuscum, Mixed sample consisting of 60% S. fuscum and 40% Ch. calyculata). In the initial and decomposed samples, the ash content was determined by the dry combustion method. The total carbon and nitrogen content, as well as the carbon and nitrogen isotopic composition, were determined using a DELTA V Advantage isotope ratio mass spectrometer. Results. This short-term study conducted during the growing season in conditions of undisturbed (Natural Ryam) and post-pyrogenic (Gar) phytocenoses showed that due to a significant amount of mortmass (2402 g/m2) Natural Ryam had organic matter stock exceeding that in the Gar by 1.7 times. On average, 59% of organic matter loss from the total losses during the growing season occurred in the first month. In both Gar and Natural Ryam conditions, minimal losses of organic matter were characteristic for Sphagnum fuscum (3.1 and 3.5% respectively). For the remaining samples the Gar conditions were more favorable for the degradation at the initial stages of decomposition. The Mixed sample occupied an intermediate position between its individual components in terms of mass losses. Carbon losses correlated well with mass losses both over 1 month of degradation (r=0.87) and over 4 months (r=0.96). In contrast to carbon, nitrogen accumulated in the Mixed sample at the initial stages of degradation, both after 1 month and 4 months. Conclusions. With smaller phytomass stocks in areas of post-pyrogenic succession, more active decay at the initial stages of organic matter decomposition occurs exactly under these conditions. The impact of post-pyrogenic succession on the rate of organic matter decomposition of Chamaedaphne calyculata plant residues and the Mixed sample was demonstrated. The most intensive decomposition of litter occured during the first month of degradation. Additionally, in the conditions of a burnt bog, a more intense release of nitrogen from all plant residues and accumulation of ash elements in Sphagnum fuscum samples were observed. The mixing of litter components influenced both the rate and dynamics of decomposition. The carbon and nitrogen isotopic composition began to change during the initial stages of decomposition, leading to enrichment with heavier isotopes 15N and 13C. This research emphasizes the importance of studying the processes of plant litter decomposition at the initial stages and considering the plant residue composition when studying the processes of organic matter transformation.