Stable Sulfur Isotope Ratios Research Articles

Evaluating The Impact of Increased Heavy Oil Consumption on Urban Pollution Levels through Isotope (δ13C, δ34S, 14C) Composition

The impact of heavy fuel oil (HFO) on the chemical and isotopic composition of submicron particulate matter (PM1) was investigated. For this purpose, we conducted an analysis of water-soluble inorganic ions (WSIIs) and multiple isotopes (δ34S, δ13C, 14C) of PM1 and SO2 collected during two heating periods: before (2021–2022) and during the use of HFO (2022–2023) in Vilnius, Lithuania. The results showed that the combustion of HFO increased the concentrations of SO₂ (by 94%) and PM1-related sulfate (by 30%). It also altered the chemical composition of PM1, with sulfate becoming the predominant component (~40%) of WSIIs. The stable sulfur isotope ratios of SO2 (δ34SSO2) and sulfate (δ34SPM1) shifted significantly to more negative values (δ34SSO2 = 0.4‰, δ34SPM1 = −0.3‰) compared to the previous heating period. Anticorrelation between δ¹³C and δ³⁴S values indicated increased contributions of ¹³C-enriched fossil fuel sources (coal and HFO) in EC, although the share of fossil fuels in elemental carbon (EC) slightly decreased during the HFO period. The combustion of HFO affected the concentrations of PM1 chemical components and substantially impacted the isotopic composition and source contributions of sulfate and EC.

Oxygen and sulfur stable isotope ratios of Late Devonian vertebrates trace the relative salinity of their aquatic environments

Late Devonian aquatic environments hosted the fin-to-limb transition in vertebrates. Upper Devonian (ca. 365−360 Ma) strata in Pennsylvania, USA, preserve a diversity of fishes and tetrapods in coastal marine to fluvial depositional environments, making this region ideal for investigating the ecology and evolution of Late Devonian vertebrates. A key unresolved issue has been reconstructing the specific aquatic habitats that hosted various vertebrates during this period. Specifically, the salinity of environments spanning fresh to shallow marine water is difficult to discern from sedimentological and paleontological analyses alone. Here, we analyze rare earth elements and yttrium (REY) as well as stable oxygen and sulfur isotope compositions (δ18O, δ34S) in fossil vertebrate bioapatite from late Famennian (ca. 362−360 Ma) strata of the Catskill and Lock Haven formations in the Appalachian Basin, USA, to determine the relative salinity of their aquatic environments. These results confirm the ecological euryhalinity of several taxa (Bothriolepis sp., tristichopterids, and Holoptychius sp.). Our results are the first demonstrating that some early tetrapod species occupied unequivocally freshwater habitats by late Famennian time (ca. 362−360 Ma). Our study shows that integrating sedimentological and paleontological data with combined oxygen and sulfur isotope analysis allows precise tracing of the relative salinity of vertebrate habitats deep in the past.

Continuous-Flow Stable Sulfur Isotope Analysis of Organic and Inorganic Compounds by EA-MC-ICPMS.

Elemental analysis (EA) coupled to isotope ratio mass spectrometry (IRMS) is a well-established method to derive stable isotope ratios of sulfur (34S/32S). Conversion of sulfur to SO2 by EA and measurement of SO2 isotopologues by IRMS represents the simplest and most versatile method to accomplish isotope measurement of sulfur even in bulk samples. Yet, interferences by oxygen isotopes in SO2 often impair the precision and trueness of measured results. In the current study, we coupled EA to multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) to establish a method that avoids such interferences due to direct measurement of S+ ions. In addition, measurement of the 33S/32S isotope ratios is possible, thus representing the first bulk method that is suitable to study mass-independent isotope fractionation (MIF). Analytical precision (σ) of available Ag2S and BaSO4 reference materials (RMs) was, on average, 0.2 mUr for δ33S and δ34S, never exceeding 0.3 mUr within this study (1 mUr = 1‰ = 0.001). Measured δ34S values of reference materials agreed within ±0.2 mUr of officially reported values. Measurement of wood samples yielded good precision (0.2 mUr) for sulfur amounts as low as 3.5 μg, but precision deteriorated for samples at lower sulfur contents due to poor peak shape. Finally, we explored cross-calibration of organic liquids separated via gas chromatography (GC) against solid RMs combusted via EA that avoids challenging offline conversion of RMs. Results indicate good precision (≤0.08 mUr) and acceptable trueness (≤0.34 mUr) for determination of δ34S, demonstrating the future potential of such an approach.

Shrouded in history: Unveiling the ways of life of an early Muslim population in Santarém, Portugal (8th- 10th century AD).

In around 716 AD, the city of Santarém, Portugal, was conquered by the Berber and Arab armies that swept the Iberian Peninsula and went on to rule the region until the 12th century. Archaeological excavations in 2007/08 discovered an Islamic necropolis (Avenida 5 de Outubro #2-8) that appears to contain the remains of an early Muslim population in Santarém (8th- 10th century). In this study, skeletal material from 58 adult individuals was analysed for stable carbon (δ13Ccol; δ13Cap), nitrogen (δ15N) and sulphur (δ34S) isotope ratios in bones, and stable oxygen (δ18O), carbon (δ13Cen) and radiogenic strontium (87Sr/86Sr) isotopes in tooth enamel. The results of this study revealed a dietary pattern of predominantly C3-plant and domestic C3-fed herbivore consumption during adulthood (δ13Ccol and δ15N, respectively) but a higher proportion of C4-plant input during childhood (δ13Cen) for some individuals-interpreted as possible childhood consumption of millet porridge, a common practice in North Africa-in those with unorthodox burial types (Groups 1 and 2) that was not practiced in the individuals with canonical burials (Group 3). In this first mobility study of a medieval Muslim population in Portugal, δ18ODW values revealed greater heterogeneity in Groups 1 and 2, consistent with diverse origins, some in more humid regions than Santarém when compared to regional precipitation δ18O data, contrasting the more homogenous Group 3, consistent with the local precipitation δ18O range. Ancient DNA analysis conducted on three individuals revealed maternal (mtDNA) and paternal (Y-chromosome) lineages compatible with a North African origin for (at least) some of the individuals. Additionally, mobility of females in this population was higher than males, potentially resulting from a patrilocal social system, practiced in Berber and Arab communities. These results serve to offer a more detailed insight into the ancestry and cultural practices of early Muslim populations in Iberia.

Isotope ratios of total C, N, and S in particulate matter simultaneously calibrated by mixed USGS and IAEA reference materials

This study presents a method for calibrating the isotope ratios of the total carbon, nitrogen, and sulfur in particulate matter (PM) collected from the Seoul metro using an elemental analyzer-isotope ratio mass spectrometer (EA-IRMS). Mixtures of isotope reference materials (MRMs) from the U.S. Geological Survey (USGS) and International Atomic Energy Agency (IAEA) reference materials formed an input dataset for generalized least squares (GLS) regression to yield calibration lines. The analytical method proposed in this study enabled the measurement of stable isotope ratios of total carbon, nitrogen, and sulfur simultaneously. Results showed good linearity and repeatability for carbon and nitrogen isotopes, but poor results for sulfur isotopes due to peak broadening. Reference values with uncertainties for the isotope ratios of total carbon, nitrogen, and sulfur were determined for the collected PM, demonstrating twice as much uncertainty as that of the USGS and IAEA reference materials. Homogeneity was the biggest uncertainty source for the calibrated values.

Trophic history of Hawaiian green turtles as revealed by stable isotope ratios (δ13C, δ15N and δ34S) in the bones of museum specimens

Abstract Understanding consumer trophic status and long‐term dietary changes can yield information about impacts of altered habitats on their ecology. In Hawai'i, coastal ecosystems have been significantly modified by the introduction of invasive seaweeds and mangroves, high nutrient load and overfishing, but so far, much is still to be understood about how these changes have affected the green turtle (Chelonia mydas). This study analyzed stable carbon, nitrogen, and sulfur isotope ratios in the bone tissue of modern and museum specimens of green turtles collected from 1901 to 2020 in Oahu and the North‐western Hawaiian Islands to understand how their isotopic niche has changed through time, a crucial step towards restoring the ecological role of a formerly decimated species. The standard ellipse size and the total area of the convex hull of the isotopic niche of green turtles in three periods (1901–1951, 1992–2008, and 2018–2020) were calculated. The stable isotope values of ancient green turtles (1901–1951) suggest that they relied heavily on macroalgae even before the introduction of exotic species and eutrophication promoted the development of algal pastures. However, a few ancient green turtles relied heavily on seagrasses, and others complemented their macroalgae‐based diets with significant amounts of animal matter. Such diet specialists were missing from the sample of current green sea turtles, suggesting that these foraging strategies are less common or perhaps even absent in the current population. The results suggest that green turtles have converged on the use of the most abundant resource, red macroalgae, likely because of the homogenization and simplification of coastal habitats and food webs due to anthropogenic influences. Restoring the population size of herbivorous fishes and a more diverse ecosystem structure may be necessary to recover the array of trophic strategies formerly present in the Hawaiian green turtle population.

Early Byzantine fish consumption and trade revealed by archaeoichthyology and isotopic analysis at Sagalassos, Turkey

We document the dietary and economic role of fish at Sagalassos, a town in ancient Pisidia (southwest Turkey) for the Early Byzantine period (c. 550 – 700 CE) through a detailed analysis of animal bones and stable isotopes. The role of fish in the diet is quantified, for the first time, based on large samples of sieved remains retrieved during the excavation of a number of spaces in an urban residence. The table and kitchen refuse from the mansion shows that fish was a regular part of the diet. However, past isotopic work focused on human individuals excavated in the city’s necropolises, slightly postdating the faunal remains examined, did not reflect this consumption of aquatic food. The studied assemblage comprises at least 12 different fish taxa, including five marine species, a Nilotic fish and six Anatolian freshwater species. Since the origin of the freshwater fishes could not be unambiguously determined by zoogeography alone, we analyzed carbon, nitrogen and sulphur stable isotope ratios in archaeological fish bones from Sagalassos as well as in bones of modern fish collected at different sites in Turkey. We show that most freshwater fish, i.e., all cyprinid species, came from Lake Eğirdir. No evidence was found for fish from the local Aksu River basin. The exact origin of pike, which account for 3% of all freshwater fish, could not be directly determined due to a shortage of modern comparative data. Using the data obtained on the provenance of the fish, the ancient trade routes possibly used in the Early Byzantine period are reconstructed using a combination of archaeological, numismatic and historical data on past commercial relations.

Using sulfur stable isotope ratios (δ34 S) for animal geolocation: Estimating the delay mechanisms between diet ingestion and isotope incorporation in tail hair.

Metabolism and diet quality play an important role in determining delay mechanisms between an animal ingesting an element and depositing the associated isotope signal in tissue. While many isotope mixing models assume instantaneous reflection of diet in an animal- tissue, this is rarely the case. Here we use data from wildebeest to measure the lag time between ingestion of 34 S and its detection in tail hair. We use time-lagged regression analysis of δ34 S data from GPS-collared blue wildebeest from the Serengeti ecosystem in combination with δ34 S isoscape data to estimate the lag time between an animal ingesting and depositing 34 S in tail hair. The best fitting regression model of δ34 S in tail hair and an individual- position on the δ34 S isoscape is generated assuming an average time delay of 78 days between ingestion and detection in tail hair. This suggests that sulfur may undergo multiple metabolic transitions before being deposited in tissue. Our findings help to unravel the underlying complexities associated with sulfur metabolism and are broadly consistent with results from other species. These findings will help to inform research aiming to apply the variation of δ34 S in inert biological material for geolocation or understanding dietary changes, especially for fast moving migratory ungulates such as wildebeest.

Multi-isotope analysis of bone collagen of Late Pleistocene ungulates reveals niche partitioning and behavioural plasticity of reindeer during MIS 3

Here we present stable carbon, nitrogen and sulfur isotope ratios of collagen extracted from Rangifer, Equus and Bison bone (n = 128) from different stratigraphic levels at the chronologically well-constrained Middle and Upper Palaeolithic site of Les Cottés, France. Samples were taken from five phases of site use (US08, US06, US04 [upper and lower], and US02; ~ 45.8–35.3 ka cal BP) to explore the dietary and spatial palaeoecology of these ungulate species during MIS 3, and the contemporary climate. Temporal trends in δ15N values of all species broadly align with other climatic indicators at the site and the lowest values in US04 correspond to the Heinrich 4 cooling event, reflecting changes in the composition of soil/plant nitrogen at this time. Rangifer collagen is 13C-enriched compared to the other species throughout, consistent with lichen consumption. However, this isotopic niche partitioning between Rangifer and Equus/Bison is most extensive during US04, indicating plasticity in reindeer feeding behaviour, and potentially overall increased lichen biomass during this cooler/more arid phase. Rangifer δ34S values are consistently lower than Equus and Bison, which could be indicative of their more extensive spatial ranges incorporating greater inland areas. Equus and Bison demonstrate a significant decrease in δ34S values through time, which may be linked to contemporary climatic decline.

Striped catfish (Pangasianodon hypophthalmus) exploit food sources across anaerobic decomposition- and primary photosynthetic production-based food chains

Dietary information from aquatic organisms is instrumental in predicting biological interactions and understanding ecosystem functionality. In freshwater habitats, generalist fish species can access a diverse array of food sources from multiple food chains. These may include primary photosynthetic production and detritus derived from both oxic and anoxic decomposition. However, the exploitation of anoxic decomposition products by fish remains insufficiently explored. This study examines feeding habits of striped catfish (Pangasianodon hypophthalmus) at both adult and juvenile stages within a tropical reservoir, using stable carbon, nitrogen, and sulfur isotope ratios (δ13C, δ15N, and δ34S, respectively) and fatty acid (FA) analyses. The adult catfish exhibited higher δ15N values compared to primary consumers that feed on primary photosynthetic producers, which suggests ingestion of food sources originating from primary photosynthetic production-based food chains. On the other hand, juvenile catfish demonstrated lower δ15N values than primary consumers, correlating with low δ34S value and large proportions of bacterial FA but contained small proportions of polyunsaturated FA. This implies that juveniles utilize food sources from both anoxic decomposition and primary photosynthetic production-based food chains. Our results indicate that food chains based on anoxic decomposition can indeed contribute to the dietary sources of tropical fish species.

Are Large Sulfur Isotope Variations Biosignatures in an Ancient, Impact-Induced Hydrothermal Mars Analog?

Discrepancies have emerged concerning the application of sulfur stable isotope ratios as a biosignature in impact crater paleolakes. The first in situ δ34S data from Mars at Gale crater display a ∼75‰ range that has been attributed to an abiotic mechanism. Yet biogeochemical studies of ancient environments on Earth generally interpret δ34S fractionations >21‰ as indicative of a biological origin, and studies of δ34S at analog impact crater lakes on Earth have followed the same approach. We performed analyses (including δ34S, total organic carbon wt%, and scanning electron microscope imaging) on multiple lithologies from the Nördlinger Ries impact crater, focusing on hydrothermally altered impact breccias and associated sedimentary lake-fill sequences to determine whether the δ34S properties define a biosignature. The differences in δ34S between the host lithologies may have resulted from thermochemical sulfate reduction, microbial sulfate reduction, hydrothermal equilibrium fractionation, or any combination thereof. Despite abundant samples and instrumental precision currently exclusive to Earth-bound analyses, assertions of biogenicity from δ34S variations >21‰ at the Miocene Ries impact crater are tenuous. This discourages the use of δ34S as a biosignature in similar environments without independent checks that include the full geologic, biogeochemical, and textural context, as well as a comprehensive acknowledgment of alternative hypotheses.

Trait based niche differentiation in tetrakas (Bernieridae) endemic to Madagascar: A multi-isotope approach

Introduction Tropical rainforest species interact with each other and their environment over a wide range of spatiotemporal scales. However, our understanding of resource partitioning and the mechanisms of avian species coexistence is largely restricted to subjective visual observations or acoustic monitoring. Therefore, the relative magnitudes of interspecific and intraspecific differences in resource use have remained difficult to quantify, particularly regarding different diets and habitat use. The eastern rainforest belt of Madagascar is inhabited by several species of insectivorous tetrakas belonging to an endemic bird family of Madagascar (Bernieridae). These species occupy similar habitats in the forest understory and are morphologically similar but because of likely differences (e.g., in foraging behaviors) we expect their foraging niches to be segregated allowing coexistence. Methods We examined the niche differentiation of four of these species: the Grey-crowned Tetraka ( Xanthomixis cinereiceps ), Long-billed Tetraka ( Bernieria madagascariensis ), Spectacled Tetraka ( Xanthomixis zosterops ), and White-throated Oxylabes ( Oxylabes madagascariensis ) in the Maromizaha rainforest in eastern Madagascar combining morphometry with stable carbon, nitrogen, and sulfur isotope ratios (δ 13 C, δ 15 N, and δ 34 S) from feathers. Results We show considerable variation in isotopic niche positions, niche breadth and interspecific niche overlap. In two species, the Long-billed Tetraka and Spectacled Tetraka, we found an indication of sex-specific niche space, with males exhibiting a larger isotopic niche-area relative to females. Morphological traits of five species (including the Wedge-tailed Tetraka, Hartertula flavoviridis ) coupled with stable isotope data provided explanations of patterns of niche overlap and isotopic position. Discussion The observed isotopic niche differences may be explained by differences in resource acquisition strategies that might be associated with specific morphological traits and spatial distribution. This may play an important role in niche differentiation among coexisting and phylogenetically closely related species.

Tracing carbon flow and trophic structure of a coastal Arctic marine food web using highly branched isoprenoids and carbon, nitrogen and sulfur stable isotopes

Climate-driven alterations of the marine environment are most rapid in Arctic and subarctic regions, including Hudson Bay in northern Canada, where declining sea ice, warming surface waters and ocean acidification are occurring at alarming rates. These changes are altering primary production patterns that will ultimately cascade up through the food web. Here, we investigated (i) the vertical trophic structure of the Southampton Island marine ecosystem in northern Hudson Bay, (ii) the contribution of benthic and pelagic-derived prey to the higher trophic level species, and (iii) the relative contribution of ice algae and phytoplankton derived carbon in sustaining this ecosystem. For this purpose, we measured bulk stable carbon, nitrogen and sulfur isotope ratios as well as highly branched isoprenoids in samples belonging to 149 taxa, including invertebrates, fishes, seabirds and marine mammals. We found that the benthic invertebrates occupied 4 trophic levels and that the overall trophic system went up to an average trophic position of 4.8. The average δ34S signature of pelagic organisms indicated that they exploit both benthic and pelagic food sources, suggesting there are many interconnections between these compartments in this coastal area. The relatively high sympagic carbon dependence of Arctic marine mammals (53.3 ± 22.2 %) through their consumption of benthic invertebrate prey, confirms the important role of the benthic subweb for sustaining higher trophic level consumers in the coastal pelagic environment. Therefore, a potential decrease in the productivity of ice algae could lead to a profound alteration of the benthic food web and a cascading effect on this Arctic ecosystem.

Trophic Position of Wintering Common Loons (Gavia immer ) in Barataria Bay, Louisiana Following the Deepwater Horizon Oil Spill

Common Loons (Gavia immer) wintering in watercourses of Barataria Bay, in coastal Louisiana were sampled in 2011–2014 following the Deepwater Horizon oil spill of 2010. Blood samples were analyzed for stable isotope ratios of carbon, nitrogen and sulfur as proxies for habitat use and diet in order to expand our understanding of the trophic position of wintering loons. The δ 13C and δ 34S values indicated that these Common Loons feed in coastal estuarine habitats. Trophic position was estimated indirectly by comparing loon stable isotope ratios with those of Brown Pelicans (Pelecanus occidentalis), a known piscivore, sampled concurrently in 2014. The isotopic signatures of the two species were not significantly different; this is consistent with the hypothesis that both species foraged primarily in coastal estuarine habitats and mainly as piscivores. No significant differences were found between subadult and adult Common Loons with respect to isotopic signatures, suggesting similar habitat usage and diet. Adults weighed more and were in better body condition than subadults. Stable isotope composition and body condition were not significantly related. Using a parallel data set of polycyclic aromatic hydrocarbons (PAH, an indicator or oil contamination) in the blood of the same loons, there was no significant relationship between PAH contamination and stable isotopic composition. Therefore, PAH-contamination could not be linked to a distinctive foraging habitat or diet.

Using Stable Sulfur Isotope to Trace Sulfur Oxidation Pathways during the Winter of 2017-2019 in Tianjin, North China.

After the implementation of the Coal Replacing Project (CRP) in the northern parts of China in 2017, its effect on PM2.5 composition is still unclear. In the study, water-soluble ionic components (WSICs) and stable sulfur isotope ratios (δ34S) of SO42− in PM2.5 collected during the domestic heating period before and after the implementation of CRP in Tianjin were analyzed. Results showed that the average concentrations of both PM2.5 and WSICs have dropped dramatically after the CRP, especially for the SO42− (by approximately 57–60%). After the CRP, the range of δ34Ssulfate was significantly narrowed to 4.1–7.5‰ in January 2018 and 1.4–6.1‰ in January 2019, which suggested that the sulfur source was becoming simple. It was interesting that the δ34Ssulfate value in the pollution period before the CRP was higher than that in the clean period, whereas it showed the opposite tendency after the CRP, which implied that the contribution of sea salt was high during the pollution period before the CRP. The MIXSIAR model calculated that the contributions of the transition-metal ion (TMI) oxidation and NO2 oxidation pathways in the three sampling stages were higher than those of the OH radical oxidation and H2O2/O3 oxidation pathways, indicating that the formation pathway of sulfate was mainly dominated by heterogeneous oxidation. Before the CRP, the NO2 oxidation pathway was the dominant sulfate oxidation pathway during a haze episode, and the TMI oxidation pathway dominated the formation of sulfates after the CRP.

What is the menu today in a subantarctic kelp food web from the Kerguelen Islands? Phytodetritus, phytoplankton and phytobenthos; not living kelp

Kelp forests dominated by Macrocystis pyrifera are widely distributed in coastal waters from boreal, temperate and subantarctic regions. This widespread distribution may result in regional differences in food web structure and functioning. In temperate northern regions, where most studies on kelp forest benthic food webs have been conducted, kelp grazing is a well-documented phenomenon and can lead to the overgrazing of M. pyrifera by sea urchins when their predators (e.g., sea otters) are absent. In contrast, little is known about their counterparts in subantarctic areas. The present study aimed to reconstruct the benthic food web of a kelp forest dominated by M. pyrifera in a subantarctic environment using stable isotope analysis. Stable carbon (δ13C), nitrogen (δ15N) and sulfur (δ34S) isotope ratios were measured from food sources (macrophytobenthos, suspended particulate organic matter SPOM, and sediment) and consumers (sponges, bivalves, gastropods, sedentary and mobile polychaetes, arthropods and echinoderms) which were sampled in a kelp forest of the Kerguelen archipelago. Mixing models highlighted two interconnected trophic pathways which were either supported by SPOM and resuspended macrophytobenthos detritus (bentho-pelagic), or by live micro/macrophytobenthos (phytobenthos-based). No major prey were highlighted for several consumers, indicating the existence of potential supplementary trophic pathways. No consumer relying primarily on living M. pyrifera was highlighted by the mixing models. The investigated kelp forest is hence a complex ecosystem supporting multiple trophic pathways, and direct consumption of M. pyrifera is limited. Nonetheless, M. pyrifera and other macrophytobenthos species may constitute a pool of detritus supporting several trophic pathways.

Stable sulphur isotope (δ 34S) ratios in bird feathers from India indicate strong segregation between the Himalaya and Gangetic plain, and the rest of India

ABSTRACT Although stable hydrogen (δ 2H) and carbon (δ 13C) isotopic compositions of bird feathers have been increasingly used to understand the migration of birds through assignment of individuals to established isoscapes, far less is known about the structure of feather isoscapes based on stable sulphur isotope (δ 34S) assays. While δ 2H isoscapes have been used to investigate the migratory origins of the Globe Skimmer (Pantala flavescens) dragonfly in India, no isotope studies have been applied to avian migration patterns in that region. Here, based on museum collections, we report the feather δ 34S values of 13 avian species that included marine birds with expected 34S enriched feathers, resident birds throughout India and a single migratory species, Bar-headed Goose (Anser indicus). Feathers from the marine birds were the most enriched (20.6 ± 1.2 ‰, n = 10; range = 4.4 ‰) in 34S but terrestrial resident species also showed unexpectedly high δ 34S values (11.7 ± 4.8 ‰, n = 74; range = 19.9 ‰) throughout most of India but the Himalayan region and Gangetic plain typically showed δ 34S values less than 6.4 ‰. Our results show the utility of feather δ 34S studies to decipher avian and other animal migration between these two regions.

Sand supplementation favors tropical seagrass Thalassia hemprichii in eutrophic bay: implications for seagrass restoration and management

BackgroundSediment is crucial for the unique marine angiosperm seagrass growth and successful restoration. Sediment modification induced by eutrophication also exacerbates seagrass decline and reduces plantation and transplantation survival rates. However, we lack information regarding the influence of sediment on seagrass photosynthesis and the metabolics, especially regarding the key secondary metabolic flavone. Meanwhile, sulfation of flavonoids in seagrass may mitigate sulfide intrusion, but limited evidence is available.ResultsWe cultured the seagrass Thalassia hemprichii under controlled laboratory conditions in three sediment types by combining different ratios of in-situ eutrophic sediment and coarse beach sand. We examined the effects of beach sand mixed with natural eutrophic sediments on seagrass using photobiology, metabolomics and isotope labelling approaches. Seagrasses grown in eutrophic sediments mixed with beach sand exhibited significantly higher photosynthetic activity, with a larger relative maximum electron transport rate and minimum saturating irradiance. Simultaneously, considerably greater belowground amino acid and flavonoid concentrations were observed to counteract anoxic stress in eutrophic sediments without mixed beach sand. This led to more positive belowground stable sulfur isotope ratios in eutrophic sediments with a lower Eh.ConclusionsThese results indicated that coarse beach sand indirectly enhanced photosynthesis in T. hemprichii by reducing sulfide intrusion with lower amino acid and flavonoid concentrations. This could explain why T. hemprichii often grows better on coarse sand substrates. Therefore, it is imperative to consider adding beach sand to sediments to improve the environmental conditions for seagrass and restore seagrass in eutrophic ecosystems.

Ancient and recycled sulfur sampled by the Iceland mantle plume

Stable sulfur isotope ratios of mid-ocean ridge and ocean island basalts (MORBs and OIBs) preserve unique information about early Earth processes and the long-term volatile cycles between Earth's mantle and the surface. Icelandic basalts present ideal material to examine the oldest known terrestrial mantle reservoir, accessed through a deep-rooted mantle plume, but their multiple sulfur isotope systematics have not been explored previously. Here, we present new sulfur concentration (30–1570 ppm) and isotope data (δ34S = −2.5 to +3.8‰ and Δ33S = −0.045 to +0.016‰; vs. Canyon Diablo Troilite) from a sample suite (n = 62) focused on subglacially erupted basaltic glasses obtained from Iceland's neovolcanic zones. Using these data along with trace element systematics to account for the effects of magmatic processes (degassing and immiscible sulfide melt formation) on δ34S, we show that primitive (MgO > 6 wt.%), least degassed glasses accurately record the δ34S signatures of their mantle sources. Compared to the depleted MORB source mantle (DMM; δ34S = −1.3±0.3‰), the Iceland mantle is shown to have a greater range of δ34S values between −2.5 and −0.1%. Similarly, Icelandic basalts are characterized by more variable and negatively shifted Δ33S values (−0.035 to +0.013‰) relative to DMM (0.004±006‰). Negative δ34S-Δ33S signatures are most prominent in basalts from the Snæfellsnes Volcanic Zone and the Kverkfjöll volcanic system, which also have the lowest, most MORB-like 3He/4He (8–9 R/RA, where RA is the 3He/4He of air) and the highest Ba/La (up to 12) in Iceland. We propose that subduction fluid-enriched, mantle wedge type material, possibly present in the North Atlantic upper mantle, constitutes a low-δ34S-Δ33S component in the Icelandic mantle. This suggests that volatile heterogeneity in Iceland, and potentially at other OIBs, may originate not only from diverse plume-associated mantle components, but also from a heterogeneous ambient upper mantle. By contrast, a set of samples with high 3He/4He (up to 25.9 R/RA) and negative μ182W anomalies define an ancient lower mantle reservoir with a near-chondritic Δ33S and δ34S signature of ∼0‰. The difference between DMM and the high high-3He/4He mantle may reflect separate conditions during core-mantle differentiation, or a previously unidentified flux of sulfur from the core to the high-3He/4He reservoir.

Dining in Tuva: Social correlates of diet and mobility in Southern Siberia during the 2nd–4th centuriesCE

ObjectivesContemporary archeological theory emphasizes the economic and social complexity of Eurasian steppe populations. As a result, old notions of “nomadic” cultures as homogenously mobile and economically simple are now displaced by more nuanced interpretations. Large part of the literature on diet and mobility among Eurasian pastoralists is focused on the Bronze and Iron Ages. The underrepresentation of more recent contexts hampers a full discussion of possible chronological trajectories. In this study we explore diet and mobility at Tunnug1 (Republic of Tuva, 2nd–4th century CE), and test their correlation with social differentiation.Materials and MethodsWe compare demographic patterns (by age‐at‐death and sex) of carbon, nitrogen, and sulfur stable isotope ratios (δ13C, δ15N, and δ34S) among 65 humans and 12 animals from Tunnug1 using nonparametric tests and Bayesian modeling. We then compare isotopic data with data on perimortal skeletal lesions of anthropic origin and funerary variables.ResultsOur analyses show that: (1) diet at Tunnug1 was largely based on C4 plants (likely millet) and animal proteins; (2) few individuals were nonlocals, although their geographic origin remains unclarified; (3) no differences in diet separates individuals based on sex and funerary treatment. In contrast, individuals with perimortal lesions show carbon and nitrogen stable isotope ratios consistent with a diet incorporating a lower consumption of millet and animal proteins.DiscussionOur results confirm the previously described socioeconomic variability of steppe populations, providing at the same time new data about the economic importance of millet in Southern Siberia during the early centuries CE.