δ15N Signatures Research Articles

Estimating atmospheric nitrogen deposition within a large river basin using moss nitrogen and isotope signatures

Assessing flux and primary sources of the atmospheric nitrogen (N) deposition with high spatial resolution remained challenging. The epilithic moss is considered a suitable biological monitor to explore N deposition. Our study presented a detailed analysis of flux and major source contributions of ammonium (NH4+) and nitrate (NO3−) deposition using N and δ15N signatures of epilithic moss collected densely from the Yangtze River basin. The results showed a more negative δ15N and higher N concentration of the moss in cropland and urban area than in forest and grassland of the basin. A gradient of the estimated N deposition (9.6–34.0 kg ha−1 yr−1) occurred from the Tibetan Plateau to lower reaches, with amount of NH4+ was approximately three times higher than NO3− deposition. The contribution from volatilization to NH4+ deposition (33.28 ± 8.10%) was less than the contribution from combustion (66.72 ± 8.10%), inconsistent with the traditional findings that N fertilizer and livestock waste are the principal sources of NH3 emissions. Fossil fuel was the dominant sources of NO3− deposition, accounted for 70.22 ± 18.67%. From 2006 to 2019, the source contribution of N deposition in forest remained unchanged, while NH3 volatilization and fossil fuel emitted NOx in urban areas have increased. Our findings highlighted the importance of combustion sources to N deposition in the Yangtze River basin.

Subcretion of altered oceanic crust beneath the SW São Francisco Craton, Brazil – A stable isotope study on diamonds and their inclusions

The presence of diamonds of lherzolitic, eclogitic and websteritic paragenesis in proximal alluvial deposits on the southwestern edge of the São Francisco Craton documents the incorporation of subducted oceanic crust and associated metasomatism through slab dehydration fluids affecting the local SCLM. To better constrain the subduction-association of diamond substrates and metasomatic events, we conducted a combined study of the δ13C-δ15N-[N] characteristics of 81 diamonds and the δ18O values of four of their eclogitic garnet inclusions. Diamond carbon isotope compositions range from −25.5 to +0.5‰, with 13C-depleted diamonds (≤ −7‰) being exclusively of eclogitic/websteritic paragenesis while the 13C-enriched (≥ −2‰) tail of the distribution is related to diamonds with lherzolitic inclusions. Nitrogen isotope values range from −14.2 to +25.5‰, with about half of the values being positive. A general absence of coherent trends in δ13C-δ15N-[N] across growth zones implies that diamond formation did not occur under fluid-limited conditions. Instead, the observed heterogeneity in carbon and nitrogen isotope compositions reflects contributions of distinct source reservoirs hosted in both altered oceanic crust and Earth's mantle. Nitrogen contents peak around a δ15N value of −3.5‰, indicating that more N-rich fluids, presumably representing a primitive endmember composition, have a mantle-like δ15N signature. While positive and negative δ15N values occur equally near the δ13C mantle value (−5 ± 2‰), 13C-depleted diamonds have nitrogen isotope compositions skewed towards positive values.13C depletion and 15N enrichment is a signature of biogenic carbonates/organic matter and low-T clays in uppermost, basaltic sections of oceanic crust that experienced low-temperature seawater alteration prior to subduction. Correspondingly, the oxygen isotope compositions of eclogitic garnet inclusions fall in a restricted range between +5.5‰ to +7.0‰. For three of the four samples, the stable isotope signatures of inclusions and host diamonds display perfect agreement, with the intensity of seawater alteration signatures, in the form of garnet inclusion 18O enrichment and host diamond 13C depletion and 15N enrichment, increasing together. For the fourth sample, the δ18O signature of the garnet inclusion (+5.5‰) and δ13C-δ15N signatures of the diamond host (−25 and + 19‰, respectively) are decoupled. While the mantle-like δ18O signature indicates a diamond substrate derived from deeper levels in oceanic crust (e.g., deep sheeted dikes), the diamond-forming fluids must have originated from sources that originally resided near the sea water interface. A viable mode of mixing such disparate isotopic signatures is the interaction of diamond-forming fluids derived from shallow oceanic crust altered at low-temperatures with eclogitized substrates originally formed in deeper levels of oceanic crust. This process likely occurred during diamond formation in a tectonic subduction mélange, which juxtaposes deeper and shallower levels of oceanic crust. In the lithospheric mantle above the subcreted oceanic slab, the elevated carbon isotope and highly variable nitrogen isotope compositions of diamonds formed in lherzolitic substrates likely relate to devolatilization and/or melting of principally oceanic sediments containing marine carbonates and clays and subsequent mixing with mantle-derived volatile components. In combination, our diamond and inclusion stable isotope data provide insight into multiple processes that promote diamond formation both inside subducted slabs accreted to the São Francisco cratonic keel and in adjacent subcontinental lithospheric mantle.

Ammonium “nutrient capacitor” model for δ15N signatures associated with marine anoxic events

Abstract Geochemical records of ancient periods of warm climate can be useful to help understand the looming effects of modern anthropogenic warming, including changes to biogeochemical nutrient cycles. Stable nitrogen isotope compositions of marine sediments archive the balance of processes in the global nitrogen cycle. However, the unusual isotopic signals of Mesozoic oceanic anoxic events (OAEs) remain enigmatic, thus hindering our understanding of nitrogen cycle processes and dynamics under conditions of ocean deoxygenation. Here, we present an ammonium “nutrient capacitor” model of the water-column nitrogen cycle to explain the anomalously negative isotopic compositions seen in Mesozoic OAE sediments. Our model applies isotopic inferences derived from high-resolution records of Lake Kivu sediments to show how periodic chemocline overturning of redox-stratified water columns during Mesozoic OAEs may have delivered ammonium to the photic zone in excess of primary producer requirements. Smoothed, stochastic sampling of the changing fluxes within the nitrogen cycle across these events can simulate OAE nitrogen isotope records.

Speciation and repeated origins of hypertrophied lips in parallel adaptive radiations of cyprinid fish from East Africa.

The evolution of convergent phenotypes is one of the most interesting phenomena of repeated adaptive radiations. Here, we examined the repeated patterns of thick-lipped or "rubberlip" phenotype of cyprinid fish of the genus Labeobarbus discovered in riverine environments of the Ethiopian Highlands, East Africa. To test the adaptive value of thickened lips, identify the ecological niche of the thick-lipped ecomorphs, and test whether these ecomorphs are the products of adaptive divergence, we studied six sympatric pairs of ecomorphs with hypertrophied lips and the normal lip structure from different riverine basins. Trophic morphology, diet, stable isotope (δ15N and δ13C) signatures, as well as mtDNA markers and genome-wide SNP variation, were analyzed. Our results show that thick-lipped ecomorphs partition trophic resources with generalized ecomorphs in only one-half of the examined sympatric pairs despite the pronounced divergence in lip structure. In these thick-lipped ecomorphs that were trophically diverged, the data on their diet along with the elevated 15N values suggest an invertivorous specialization different from the basal omnivorous-detritivouros feeding mode of the generalized ecomorphs. Genetic data confirmed an independent and parallel origin of all six lipped ecomorphs. Yet, only one of those six thick-lipped ecomorphs had a notable genetic divergence with sympatric non-lipped ecomorphs based on nuclear SNPs data (F ST = 0.21). Sympatric pairs can be sorted by combinations of phenotypic, ecological, and genetic divergence from an ecologically non-functional mouth polymorphism via ecologically functional polymorphism to a matured speciation stage via divergent evolution.

Equilibrium partitioning and isotopic fractionation of nitrogen between biotite, plagioclase, and K-feldspar during magmatic differentiation

A significant portion of the continental crust is composed of plutonic igneous rocks. However, little is known about the geochemical behaviour of N between the different minerals during magmatic differentiation. To provide new constraints for the behaviour of N during crust formation, we have characterised the geochemistry of nitrogen (N) in the compositionally zoned calc-alkaline pluton at Loch Doon, SW Scotland. We present N concentration and N isotope values for whole-rock data alongside biotite, plagioclase and K-feldspar mineral separates and assess the degree to which these data preserve equilibrium partitioning during magmatic differentiation. We show that whole rock likely inherited its N contents and δ15N signatures from the initial source composition and that this signature is homogenous at a pluton scale. Whilst the whole-rock data are best explained as crust-derived N in the source, the degree of homogenisation across a pluton scale is inconsistent with empirical N diffusivities, ruling out syn-emplacement crustal assimilation as the source of N. Instead, our data suggest a crustal signature inherited from depth associated with the Iapetus subduction zone. At a mineral scale, we find that N preferentially partitions into the feldspars over mica in this system in the order K-feldspar > plagioclase ≈ biotite > quartz, with average mineral–mineral distribution coefficients of DN plagioclase-biotite = 1.3 ± 0.6 and DN Kspar-biotite = 2.8 ± 0.6. Partitioning is accompanied by a large and near constant equilibrium isotope fractionation factor between biotite and both feldspars (averages are Δ15NPlag-Biotite = +7.8 ± 1.2‰ and Δ15NKspar-Biotite = +7.9 ± 1.0‰). In contrast, Δ15NKspar-Plagioclase closely approximates 0‰, where both minerals show δ15N values overlapping with the bulk rock δ15N values. These results show that mica crystallisation generates a 15N-depleted reservoir within plutonic rocks. Moreover, our dataset suggests that feldspars might be a more significant host of N in the igneous portion of Earth’s continental and oceanic crust than previously thought.

Localising terrestrially derived pollution inputs to threatened near-shore coral reefs through stable isotope, water quality and oceanographic analysis

Near-shore coral reefs are at high-risk of exposure to pollution from terrestrial activities. Pollution impacts can vary with site-specific factors that span sources, rainfall and oceanographic characteristics. To effectively manage pollution, we need to understand how these factors interact. In this study, we detect terrestrially derived nutrient inputs on near-shore reefs at Norfolk Island, South Pacific by analysis of dissolved inorganic nitrogen (DIN) and stable isotopes. When compared to a reef site with predominantly oceanic inputs, we found that both the lagoon and a small reef adjacent to a catchment have signatures of human-derived DIN shown through depleted δ15N signatures in macroalgae. We find pollution exposure of reef sites is associated with known and unknown sources, rainfall and mixing of water with the open ocean. In characterising exposure of reef sites we highlight the role of site-specific context in influencing pollution exposure for benthic communities even in remote island systems.

Characterizing potential resource use of sargasso-dominant sea wrack by terrestrial invertebrate fauna during sargasso influxes in South Florida

Marine-derived macrophytes primarily compose beach-cast sea wrack that can be used by terrestrial invertebrate fauna in sandy beach system. Since 2011, the inundations of pelagic sargasso would accumulate and decompose at local, nearshore systems across the Tropical Atlantic. While ecological effects of pelagic sargasso influxes were considerably studied on tropical Atlantic nearshore coastal systems, not much has been known about their effects on the intertidal interface or terrestrial faunal communities. This study aims to investigate terrestrial invertebrate communities associated with landed sargasso and the sargasso's potential as habitat or food for these invertebrates. Surveys, sample collection of flora and fauna, and trials of a temperature experiment were conducted at Crandon Park and MJ State Park along Southeast Florida during the 2020 and 2021 sargasso seasons. Invertebrate communities were primarily composed of talitrid amphipods, coleopterans, and dipterans. The quantity of sargasso, dependent on year of sampling session, seemed to have a more discernible effect on invertebrate composition than location. HOBO logger microhabitat experiment trials showed treatments with sargasso-dominant wrack having lower temperatures than treatments with exposed or buried sand. Many invertebrate consumers showed δ13C and δ15N signatures closer to marine macrophytes than terrestrial plants. However, mixing models reveal amphipods and oligochaete worms having a trophic link with pelagic sargasso, while insect fauna had their resource use sourced from other marine macrophytes. However, any consumption of sargasso would likely be attributed to generalist resource use rather than a specific preference to sargasso. The potential uses of sargasso depend on the amount of biomass accumulated on the beach surface and the habitat requirements of specific invertebrate species.

Trophic ecology of Angolan cold-water coral reefs (SE Atlantic) based on stable isotope analyses

Cold-water coral (CWC) reefs of the Angolan margin (SE Atlantic) are dominated by Desmophyllum pertusum and support a diverse community of associated fauna, despite hypoxic conditions. In this study, we use carbon and nitrogen stable isotope analyses (δ13C and δ15N) to decipher the trophic network of this relatively unknown CWC province. Although fresh phytodetritus is available to the reef, δ15N signatures indicate that CWCs (12.90 ± 1.00 ‰) sit two trophic levels above Suspended Particulate Organic Matter (SPOM) (4.23 ± 1.64 ‰) suggesting that CWCs are highly reliant on an intermediate food source, which may be zooplankton. Echinoderms and the polychaete Eunice norvegica occupy the same trophic guild, with high δ13C signatures (-14.00 ± 1.08 ‰) pointing to a predatory feeding behavior on CWCs and sponges, although detrital feeding on 13C enriched particles might also be important for this group. Sponges presented the highest δ15N values (20.20 ± 1.87 ‰), which could be due to the role of the sponge holobiont and bacterial food in driving intense nitrogen cycling processes in sponges’ tissue, helping to cope with the hypoxic conditions of the reef. Our study provides first insights to understand trophic interactions of CWC reefs under low-oxygen conditions.

Trophic Positions of Polyp and Medusa Stages of the Freshwater Jellyfish Craspedacusta sowerbii Based on Stable Isotope Analysis.

When species spread into new regions, competition with native species and predatory-prey relationships play a major role in whether the new species can successfully establish itself in the recipient food web and become invasive. In aquatic habitats, species with a metagenetic life cycle, such as the freshwater jellyfish Craspedacusta with benthic polyps and planktonic medusae, have to meet the requirements of two distinct life stages occurring in two habitats with different food webs. Here, we examined the trophic position of both life stages, known to be predatory, and compared their niches with those of putative native competitors using stable isotope analysis. We found that δ13C and δ15N signatures of medusae overlapped with those of co-occurring Chaoborus larvae and juvenile fish (Rutilus rutilus) in a well-studied lake, implying high competition with these native predators. The comparison of δ15N signatures of Hydra and Craspedacusta polyps in four additional lakes revealed their similar trophic position, matching their predatory lifestyle. However, their δ13C signatures differed not only across all four of the lakes studied but also within one lake over time, suggesting a preference for pelagic or benthic food sources. We conclude that invasive and native polyps differ in their niches due to different food spectra, which favors the invasion success of Craspedacusta.

Changes to the trophic structure of a desert fish community following river regulation and species turnover: Implications for an endangered top predator

AbstractA poor understanding of factors leading to species decline can result in inefficient or ineffective species restoration. Endangered Colorado pikeminnow (Ptychocheilus lucius) was nearly extirpated from the San Juan River, NM, USA and recent efforts to reestablish the species via hatchery augmentation of juveniles has yet to reach the target number of adults in the system. To assess how changes to the river's food web could be limiting reestablishment of this top predator, we used stable isotope (δ13C and δ15N) signatures of the fish community pre‐ (museum specimens) and post river regulation with coincident extirpations and invasions. Following river regulation, four of five community‐wide trophic structure metrics that quantify overall resource use were reduced and species turnover likely had little effect per se. For species sampled in both time periods, shared trophic resources generally increased (mean niche overlap = +35.7%). Additionally, Colorado pikeminnow experienced the largest decrease in niche breadth (−72%) and diet mixing models suggested a shift from piscivory towards insectivory in contemporary collections. Our results suggest an overall reduction in basal resource availability after river regulation. We propose increased reliance on similar resources may be limiting fish prey for Colorado pikeminnow, ultimately contributing to the slow and limited reestablishment in the San Juan River. This study adds to the growing body of knowledge provided by museum specimens and stable isotope analyses to identify food‐web dynamics that are a departure from historical conditions, which can provide novel information critical to imperiled species management in modified systems.

High spatial resolution assessment of air quality in urban centres using lichen carbon, nitrogen and sulfur contents and stable-isotope-ratio signatures

Air pollution and poor air quality is impacting human health globally and is a major cause of respiratory and cardiovascular disease and damage to human organ systems. Automated air quality monitoring stations continuously record airborne pollutant concentrations, but are restricted in number, costly to maintain and cannot document all spatial variability of airborne pollutants. Biomonitors, such as lichens, are commonly used as an inexpensive alternative to assess the degree of pollution and monitor air quality. However, only a few studies combined lichen carbon, nitrogen and sulfur contents, with their stable-isotope-ratio signatures (δ13C, δ15N and δ34S values) to assess spatial variability of air quality and to ‘fingerprint’ potential pollution sources. In this study, a high-spatial resolution lichen biomonitoring approach (using Xanthoria parietina and Physcia spp.) was applied to the City of Manchester (UK), the centre of the urban conurbation Greater Manchester, including considerations of its urban characteristics (e.g., building heights and traffic statistics), to investigate finer spatial detail urban air quality. Lichen wt% N and δ15N signatures, combined with lichen nitrate (NO3−) and ammonium (NH4+) concentrations, suggest a complex mixture of airborne NOx and NHx compounds across Manchester. In contrast, lichen S wt%, combined with δ34S strongly suggest anthropogenic sulfur sources, whereas C wt% and δ13C signatures were not considered reliable indicators of atmospheric carbon emissions. Manchester’s urban attributes were found to influence lichen pollutant loadings, suggesting deteriorated air quality in proximity to highly trafficked roads and densely built-up areas. Lichen elemental contents and stable-isotope-ratio signatures can be used to identify areas of poor air quality, particularly at locations not covered by automated air quality measurement stations. Therefore, lichen biomonitoring approaches provide a beneficial method to supplement automated monitoring stations and also to assess finer spatial variability of urban air quality.Graphical abstract

Nitrogen isotopes suggest agricultural and non-agricultural sources contribute equally to NH3 and NH4+ in urban Beijing during December 2018

Agricultural and non-agricultural sources emission contribute to atmospheric ammonia (NH3) and particulate ammonium (NH4+). However, our understanding on the sources of NH3 and NH4+ in PM2.5 (particles smaller than 2.5 μm) during the winter period in the urban atmosphere is limited. Here, we measured the concentrations and stable nitrogen isotopic composition (δ15N) of NH3 and NH4+ in parallel during December 2018 in urban Beijing to assess the non-agricultural and agricultural sources contributions to NH3 and NH4+ in ambient air based on the Chemical Transport Model (CTM), a Bayesian isotope mixing model (SIMMR), and the δ15N signatures that we developed. Our study found weekly NH4+ and NH3 concentrations were on average 2.5 ± 1.4 μg m−3 and 3.8 ± 1.7 μg m−3, respectively during December 2018. Weekly concentration weighted δ15N(NH4+) values ranged from 4.5‰ to 13.7‰ with an average value of 8.2 ± 3.9‰ during December 2018. After accounting for nitrogen isotopic fractionation from NH3 gas to NH4+ conversion, initial δ15N(NH3) values ranged from −22.5‰ to −12.8‰ with an average value of −17.4 ± 3.5‰. Further, weekly measured δ15N(NH3) values ranged from −22.2‰ to −10.2‰ (after correction) with an average value of −15.6 ± 5.3‰ during December 2018. Results from two different isotope-based method showed non-agricultural sources contributed 31.2%–63.1%, with an average value of 47.5 ± 14.6%, to NH4+ and 32.3%–71.2%, with an average of 53.4 ± 16.1%, to ambient NH3 during December 2018 in Beijing. Results from CMAQ-ISAM suggest non-agricultural sources contributed on average 66.2 ± 1.9% to ambient NH4+ and 66.4 ± 1.9% to ambient NH3 during December 2018. Results from this study suggest that agricultural and non-agricultural sources nearly equally contributed to NH3 and NH4+ in urban Beijing during December 2018 with an uncertainty range of 13%–19% between isotope-based methods and CTM method.

Eutrophication history and organic carbon burial rate recorded in sediment cores from the Mar Piccolo of Taranto (Italy)

During the second half of the twentieth century, coastal lagoons in densely populated regions experienced eutrophication due to excessive nutrient inputs. Detrimental effects, including hypoxia/anoxia and harmful algae blooms, have occurred in many Mediterranean lagoons, but their trophic evolution is poorly documented. The lack of adequate monitoring data can partly be offset by examining sedimentary records. In the Mar Piccolo, a lagoon comprising two basins near Taranto (Italy), eutrophication has followed population growth and pollution resulting from naval activities and massive industrialisation. Based on 210Pb-dated sediment cores, continuous in situ density profiles obtained with computed tomography, organic carbon (OC) and total nitrogen (TN) content and OC and TN isotopic signatures, this paper reconstructs the history of eutrophication, discusses the sources of organic matter and provides an estimate of the OC burial rate before and during the eutrophic period. OC burial increased in the period 1928–1935 and peaked in the decade 1960–1970. OC and TN content were still high in the surface sediments collected in 2013, despite partial diversion of sewage outfalls in the period 2000–2005. The divergent δ13C and δ15N signatures of the two basins during the eutrophic period suggest they were affected by different nutrient sources. The OC burial rate during the eutrophic phase (≈ 46 g m−2 y−1) was close to the world median value for lagoon sediments, and was about twice the burial rate recorded in the preceding oligotrophic phase.

High Hg biomagnification in North Atlantic coast ecosystems and limits to the use of δ15N to estimate trophic magnification factors

Mercury contamination is a global environmental problem. This pollutant is highly toxic and persistent which makes it extremely susceptible to biomagnify, i.e. increase its concentrations as it moves up the food chain, reaching levels that threaten wildlife and, ultimately, ecosystems’ function and structure. Mercury monitoring is thus crucial to determine its potential to damage the environment. In this study, we assessed the temporal trends of the concentrations of Hg in two coastal animal species closely connected by a predator-prey interaction, and evaluated its potential transfer between trophic levels using the δ15N signatures of the two species. For this, we performed a multi-year survey of the concentrations of total Hg and the values of δ15N in the mussel Mytilus galloprovincialis (prey) and the dogwhelk Nucella lapillus (predator) sampled along ∼1500 km of the North Atlantic coast of Spain over a 30-year period (five surveys between 1990 and 2021). Concentrations of Hg decreased significantly between the first and the last survey in the two species studied. Except for the 1990 survey, the concentrations of Hg in mussels were amongst the lowest registered in the literature for the North East Atlantic Ocean (NEAO) and the Mediterranean Sea (MS) between 1985 and 2020. Nonetheless, we detected Hg biomagnification in almost all surveys. Worryingly, trophic magnification factors obtained here for total Hg were high and comparable to the found in the literature for methylmercury, the most toxic and readily biomagnified form of this element. The δ15N values were useful to detect Hg biomagnification under normal circumstances. However, we found that nitrogen pollution of coastal waters differentially affected the δ15N signatures of mussels and dogwhelks limiting the use of this parameter for this purpose. We conclude that Hg biomagnification could constitute an important environmental hazard even when found at very low concentrations in the lower trophic levels. Also, we warn that use of δ15N in biomagnification studies when there is some underlying nitrogen pollution problem might lead to misleading conclusions.

Permafrost degradation and nitrogen cycling in Arctic rivers: insights from stable nitrogen isotope studies

Abstract. Across the Arctic, vast areas of permafrost are being degraded by climate change, which has the potential to release substantial quantities of nutrients, including nitrogen into large Arctic rivers. These rivers heavily influence the biogeochemistry of the Arctic Ocean, so it is important to understand the potential changes to rivers from permafrost degradation. This study utilized dissolved nitrogen species (nitrate and dissolved organic nitrogen (DON)) along with nitrogen isotope values (δ15N-NO3- and δ15N-DON) of samples collected from permafrost sites in the Kolyma River and the six largest Arctic rivers. Large inputs of DON and nitrate with a unique isotopically heavy δ15N signature were documented in the Kolyma, suggesting the occurrence of denitrification and highly invigorated nitrogen cycling in the Yedoma permafrost thaw zones along the Kolyma. We show evidence for permafrost-derived DON being recycled to nitrate as it passes through the river, transferring the high 15N signature to nitrate. However, the potential to observe these thaw signals at the mouths of rivers depends on the spatial scale of thaw sites, permafrost degradation, and recycling mechanisms. In contrast with the Kolyma, with near 100 % continuous permafrost extent, the Ob River, draining large areas of discontinuous and sporadic permafrost, shows large seasonal changes in both nitrate and DON isotopic signatures. During winter months, water percolating through peat soils records isotopically heavy denitrification signals in contrast with the lighter summer values when surface flow dominates. This early year denitrification signal was present to a degree in the Kolyma, but the ability to relate seasonal nitrogen signals across Arctic Rivers to permafrost degradation could not be shown with this study. Other large rivers in the Arctic show different seasonal nitrogen trends. Based on nitrogen isotope values, the vast majority of nitrogen fluxes in the Arctic rivers is from fresh DON sourced from surface runoff through organic-rich topsoil and not from permafrost degradation. However, with future permafrost thaw, other Arctic rivers may begin to show nitrogen trends similar to the Ob. Our study demonstrates that nitrogen inputs from permafrost thaw can be identified through nitrogen isotopes, but only on small spatial scales. Overall, nitrogen isotopes show potential for revealing integrated catchment wide nitrogen cycling processes.

Nitrogen isotope signatures of oxidized nitrogen species from biomass burning

Because nitrogen isotopes (δ15N) of emitted nitric oxide (e-NO) from combustion-related sources (mainly fossil fuels and biomasses) remain unknown, the δ15N values of emitted N oxides (e-NOx, the sum of emitted N dioxide (e-NO2) and e-NO) have long been employed in the isotopic tracing of nitrate (NO3−) in the atmosphere, causing substantial uncertainties in the isotope differentiation of source contributions. Here we measured concentrations and δ15N values of e-NOx and NO3− from the burning of four biomass materials (corn, wheat, poplar, and pine) in northern China, based on which we calculated concentrations and δ15N values of the corresponding e-NO, e-NO2, initially produced NO (i-NO) and NO2 (i-NO2) before emissions and oxidizations. We found that 58 ± 12% of i-NO emitted as e-NO and 42 ± 10% was oxidized to i-NO2, 77 ± 7% of i-NO2 emitted as e-NO2 and 23 ± 3% was oxidized to NO3−, and the mean δ15Ne-NO (−10.2 ± 6.0‰) was distinctly lower than the δ15Ne-NOx (−2.3 ± 3.9‰) and δ15Ne-NO2 (11.8 ± 3.6‰). Based on the δ15Ni–NO (−0.2 ± 3.2‰) and δ15Ni–NO2 (13.5 ± 3.8‰), we obtained the theoretical N isotope fractionations for the transformations from i-NO to i-NO2 (23.8 ± 14.3‰) and from i-NO2 to NO3− (8.0 ± 11.3‰) during biomass burning. These results filled the long-standing knowledge gap of species-specific δ15N signatures of NOx produced by biomass burning, expanded the understanding of N isotope fractionations of N oxidization under burning processes, and provided critical parameters for isotope source apportionment of NOx and NO3− in the atmosphere.

Inferring the ecological quality status based on living benthic foraminiferal indices in transitional areas of the Guanabara bay (SE Brazil)

Using benthic foraminifera, we evaluate the ecological quality status (EcoQS) of transitional waters of the Guanabara Bay (SE Brazil) by applying the diversity-based index exp (H′bc) and the sensitivity-based Foram-AMBI for the first time in South America. The Guanabara Bay was selected for this study as it is one of the largest transitional ecosystems in the State of Rio de Janeiro and has been severely impacted by anthropogenic activities. Concentrations of potentially toxic elements (PTEs) were assessed by sequential chemical extraction in three phases (i.e., dissolved in water, adsorbed on organic matter, and Mn oxy-hydroxides). Total organic carbon, total nitrogen, and stable isotope (δ13C and δ15N) signatures of organic matter were analyzed to trace environmental stress. The Ammonia/Elphidium ratio suggests hypoxic conditions at most of the sampled sites. Principal component analysis identifies the first component as environmental stress underlying organic matter and PTE enrichment (in all three phases), which is positively related to Foram-AMBI and negatively to exp (H′bc). The exp (H′bc) and Foram-AMBI indices reveal that stations near the Governador Island and Niterói margin have the worst EcoQS, showing medium to extreme pollution. Additionally, Foram-AMBI and exp (H′bc) provide a congruent EcoQS classification for ∼64% of the sites. Although these results are promising, they suggest that a significant effort should be made to obtain better knowledge of foraminiferal ecological requirements to employ benthic foraminifera as a biomonitoring and management method.

Tidal Flushing Rather Than Non-Point Source Nitrogen Pollution Drives Nutrient Dynamics in A Putatively Eutrophic Estuary.

The effects of nonpoint source nutrients on estuaries can be difficult to pinpoint, with researchers often using indicator species, monitoring, and models to detect influence and change. Here, we made stable isotope measurements of nitrogen and carbon in sediment, water column particulates, primary producers, and consumers at 35 stations in the reportedly eutrophic Barnegat Bay (New Jersey) to assess N sources and processing pathways. Combined with water quality and hydrological data, our C and N isoscapes revealed four distinct geographic zones with diverging isotopic baselines, indicating variable nutrient sources and processing pathways. Overall, the carbon stable isotopes δ13C) reflected the terrestrial-marine gradient with the most depleted values in the urban and poorly flushed north of the estuary to the most enriched values in the salt marsh-dominated south. In contrast, the nitrogen stable isotope values δ15N) were most enriched near the oceanic inlets and were consistent with offshore δ15N values in particulate organic matter. Several biogeochemical processes likely alter δ15N, but the relatively lower δ15N values associated with the most urbanized area indicate that anthropogenic runoff is not a dominant N source to this area. Our findings stand in contrast to previous studies of similar estuaries, as δ15N signatures of biota in this system are inversely correlated to population density and nutrient concentrations. Further, our analyses of archival plant (Spartina sp., Phragmites australis) and shell (Geukensia demissa, Ilyanassa obsoleta) samples collected between 1880 and 2020 indicated that δ15N values have decreased over time, particularly in the consumers. Overall, we find that water quality issues appear to be most acute in the poorly flushed parts of Barnegat Bay and emphasize the important role that oceanic exchange plays in water quality and associated estuarine food webs in the lagoon.

Metal bioaccumulation and transfer in benthic species based on isotopic signatures of individual amino acids in South China Sea cold seep environments

Cold seeps are deep-sea ‘oases’ with dense and dominant coexisting populations of large mussels and tubeworms under extreme environments. Under such natural source of high metal concentrations, the present study investigated the metal bioaccumulation and transfer with trophic positions in six benthic species by the isotopic δ15N and δ13C signatures in the active Haima cold seep, South China Sea. Comparing the isotopic signatures of bulk-tissue and amino acids by compound-specific isotopic analysis (CSIA-AA), we found that the bulk trophic (TPB) values in the benthos except mussels were significantly higher than those of CSIA-based TPGlu-Phe values. The estimated CSIA-based TPGlu-Phe values showed a relatively compressed food chain with much changeable and unique amino acid isotopic heterogeneity, followed slim tubeworms (1.20)<mussels (1.38)<clams (1.52)<brittle stars (1.82)<giant tubeworms (2.16)<shrimps (2.31). All species accumulated relatively high concentrations of Fe, Zn, Cu, and Cr, especially for Zn in clams. Pearson correlation analysis showed that most metals had no significant relationship between their bioaccumulation and trophic positions, whereas Hg showed a significantly positive bioaccumulation through trophic transfer in such a compressed food chain. Water exposure was a major metal source rather than bacterial assimilation for most metals in the cold seep higher consumers. Hyperaccumulation of specific metals in some tissues of different benthos indicated different metal overflows in the Haima cold seep (As and Ni for tubeworms, Zn and Cd for clam gills, Ag and Cu for mussel gills). This study demonstrated high metal adaptations in different species and stable isotopic characteristics of amino acid metabolism in a natural high metal source of an active deep-sea cold seep, which is important for deep-sea development and environmental protection.

Dual isotopes of nitrate reveal varying flow paths to stormwater retention basins

Nitrate (NO3–) isotope ratios have been used to track sources of urban runoff, but their use as a tracer of flow paths has not been explored in detail. Urban flow paths are complex, and there is a gap in understanding how spatial and temporal variability impacts runoff chemistry. NO3– in urban systems can originate from atmospheric deposition, leaching from organic material, leaking from sewers, and fertilizer. Sources can be distinguished by their δ15N and δ18O signatures. We collected time series samples of stormwater runoff entering two stormwater retention basins, one large (0.32 km2 catchment) and one small (0.016 km2 catchment) in suburban Philadelphia. We used a Bayesian mixing model to determine that NO3– sources in the stormwater basin inlets were a mix of soil nitrogen (N) and atmospheric deposition across six storm events. Activation of impervious surfaces which collect atmospheric nitrogen was observed at the beginning of storm events and the portion of atmospheric versus soil N sources varied throughout the storms. However, storms with the same characteristics did not lead to the same isotopic patterns. Further evidence of the importance of flow paths was the contrast between the large and small basin. The large basin had more NO3– source variability between samples (ranging 6 % to 58 % atmospheric NO3–) compared to the small basin (16 % to 43 %). Thus, the NO3– isotopes suggest more distinct flow paths in the basin with the large catchment and more mixing of flow across land uses in the small basin’s catchment. Quantifying flow path variability from storm to storm and between different catchments can improve design and placement of urban stormwater control measures.