Enriched δ13C Research Articles

Dual‐isotope isoscapes for predicting the scale of fish movements in lowland rivers

AbstractAssessments of patterns of animal movements are important for understanding their spatial ecology. Geostatistical models of stable isotope (SI) landscapes (isoscapes) provide a complementary tool to telemetry for assessing and predicting animal movements, but are rarely applied to riverine species. Often single‐isotope gradients in freshwater environments are insufficiently variable to provide high isoscape resolution at relatively fine spatial scales. This is potentially overcome using dual‐isotope assignment procedures, and thus, the aim here was to apply single (δ13C) and dual (δ13C and δ15N) isoscapes to assigning riverine fish to origin and predicting their movements. Using the River Bure, England, as the study system, the foraging locations of a small‐bodied lowland river fish (roach Rutilus rutilus) of low vagility were predicted using their SI data and those of a common prey item (amphipods). These foraging locations were then compared to their capture locations, with the distance between these being their predicted displacement distance. The results indicated significant enrichment of δ13C and δ15N with distance downstream in roach fin tissue and amphipods; roach bivariate isotopic niches were spatially variable, with no niche overlap between upstream and downstream river reaches. Furthermore, the dual‐isoscape assignment procedure resulted in the lowest predicted displacement distances for roach, therefore enhancing model performance. The dual‐isoscape approach was then applied to determining the predicted displacement distance of individual common bream Abramis brama, a larger, more vagile species, with these data then compared against the subsequent spatial extent of their movements recorded by acoustic telemetry. When using a high probability density threshold for isotope assignment, the predicted displacement distance of common bream was a significant predictor of the spatial extent of their subsequent movements recorded by acoustic telemetry, although it was less able to predict the direction of displacement. This first probabilistic assignment to origin for riverine species using a dual‐isotope isoscape technique demonstrated that where the required spatial resolution of animal movements in freshwater is moderately broad (5–10 km), dual‐isotope isoscapes can provide a reliable alternative or complementary method to telemetry.

Geochemistry of clumped isotopologues of CH4 within fluid inclusions in Alpine tectonic quartz fissures

Petroleum-bearing fluid inclusions are small encapsulations of oil and gas that persist in the rock record long after their parent fluids have moved on. The chemical and isotopic compositions of inclusions offer a unique way to investigate hydrocarbon formation pathways in deep Earth environments and in ancient geological times. Here we use stable isotope compositions of methane, including clumped isotopologues 13CH3D and 12CH2D2, to evaluate the formation conditions of methane within fluid inclusions in Alpine tectonic quartz fissures. We observe that this CH4 is relatively 13C and 2H enriched (δ13C = −26 to −39‰; δ2H = −126 to −146‰), consistent with the formation by advanced catagenesis of organic matter, and has clumped isotope compositions indicating intramolecular isotopic equilibrium at catagenetic to low-grade (sub-greenschist) metamorphic temperatures (TΔ13CH3D: 120-300°C; TΔ12CH2D=2120-260°C). Our findings, combined with an analysis of the geographic distributions of inclusion-bearing fissures and fluid inclusion PVT behaviors, provide direct evidence of reservoirs of thermogenic methane trapped beneath the Alps during Mid-Miocene tectonic nappe emplacement (c.a. 25 to 15 Ma). The gas was sequestered in a concentrated form that likely favored the accumulation of up to 50,000-150,000 Megatons (Mt) of CH4 across the Helvetic domain in Switzerland. Following the subsequent tectonic uplift during the period 17 to 10 Ma, we suggest that the trapped methane-rich fluids migrated to shallower depths along faults, leading to the release of Alpine metamorphic methane into near-surface aquifers and the atmosphere at rates of 0.01 to 0.03 Mt⋅y−1.

Different climate sensitivity for radial growth, but uniform for tree-ring stable isotopes along an aridity gradient in Polylepis tarapacana, the world's highest elevation tree species.

Tree growth is generally considered to be temperature limited at upper elevation treelines, yet climate factors controlling tree growth at semiarid treelines are poorly understood. We explored the influence of climate on stem growth and stable isotopes for Polylepis tarapacana Philipi, the world's highest elevation tree species, which is found only in the South American Altiplano. We developed tree-ring width index (RWI), oxygen (δ18O) and carbon (δ13C) chronologies for the last 60years at four P. tarapacana stands located above 4400 m in elevation, along a 500 km latitude aridity gradient. Total annual precipitation decreased from 300 to 200mm from the northern to the southern sites. We used RWI as a proxy of wood formation (carbon sink) and isotopic tree-ring signatures as proxies of leaf-level gas exchange processes (carbon source). We found distinct climatic conditions regulating carbon sink processes along the gradient. Current growing-season temperature regulated RWI at northern-wetter sites, while prior growing-season precipitation determined RWI at arid southern sites. This suggests that the relative importance of temperature to precipitation in regulating tree growth is driven by site water availability. By contrast, warm and dry growing seasons resulted in enriched tree-ring δ13C and δ18O at all study sites, suggesting that similar climate conditions control carbon-source processes along the gradient. Site-level δ13C and δ18O chronologies were significantly and positively related at all sites, with the strongest relationships among the southern drier stands. This indicates an overall regulation of intercellular carbon dioxide via stomatal conductance for the entire P. tarapacana network, with greater stomatal control when aridity increases. This manuscript also highlights a coupling (decoupling) between physiological processes at leaf level and wood formation as a function of similarities (differences) in their climatic sensitivity. This study contributes to a better understanding and prediction of the response of high-elevation Polylepis woodlands to rapid climate changes and projected drying in the Altiplano.

Isotopic variations of carbon and nitrogen and their implications on the conversion of Cerrado vegetation into pasture

Conversions of natural vegetation into pasture can, in a short time, change the carbon stock and the natural abundance of δ13C in the soil. The objective of this study was to evaluate changes in carbon (C) and nitrogen (N) stocks, as well as in the natural abundance of δ13C and δ15N of Argissolo Vermelho distrófico (Acrisol), in an area of natural vegetation and planted pasture in the Cerrado region of Aquidauana (MS), Brazil. In order to do this, an area of pasture (PA), cultivated for 25 years with Urochloa brizantha, and an area of natural vegetation (NV) were evaluated. Soil samples were collected at intervals of 0.05 m up to 0.60 m depth, and physical attributes, C and N stocks (CSt and NSt) and isotopic variations of δ13C and δ15N of soil were determined. In the 0–0.05 m layer, the highest C and N stocks occurred in NV, 21.99 and 1.9 Mg ha-1, respectively. In the conversion to PA, 14.62 Mg ha-1 of CSt and 1.36 Mg ha-1 of NSt were lost in the 0–0.05 m layer. The area with PA had greater isotopic enrichment of δ13C in the layers of 0–0.05 and 0.05–0.10 m, with values of -18.3 and -17.4‰, respectively, while in the other layers the isotopic values decreased with the mixture between C of C3 and C4 plants. NV showed enrichment in the isotopic signals, in the layers from 0.25–0.30 m up to 0.40–0.45 m, with values between -21.74 and -21.54‰, respectively, which is characteristic of mixed vegetation of C3 and C4 plants. The values of δ15 N showed isotopic enrichment as depth increased, indicating greater mineralization of soil organic matter in both areas. The conversion of Cerrado into pasture and its consequent fragmentation causes negative impacts on the C and N sequestration and storage capacity, both in pasture and in natural vegetation.

Carbon and oxygen stable isotopes of freshwater fish otoliths from the São Francisco River, northeastern Brazil.

Fish otoliths store geochemical and isotopic signatures that can be used as proxies for environmental conditions in ecological investigations. We investigated the δ13C and δ18O of otoliths of four freshwater fish species (Astronotus ocellatus, Serrasalmus brandtii, Plagioscion squamosissimus, and Cichla ocellaris) from the Moxotó Reservoir in the São Francisco River, Brazil. The enriched δ13C signatures that distinguish A. ocellatus from other species could be caused by dissolved inorganic carbon (δ13CDIC) in reservoir waters. Macrophytes growing along the reservoir margins would favor photosynthetic uptake of 12C, leading to enriched δ13CDIC incorporated into the otoliths of those fish. Otolith δ18O signatures appear to reflect water column preferences, in which species preferentially inhabiting surface waters (such as S. Brandtii) show more enriched values (due to high surface evaporation ratios), while bottom water species show depleted δ18O values. Our results represent the first investigation of the isotopic compositions of fish otoliths in freshwater environments in the São Francisco River, and shed light on the interpretation of isotopic information stored in otoliths and how they can be used to infer the ecological strategies of freshwater fish.

SOIL CHEMICAL CHANGES AND RESEMBLANCES IN A CHRONOSEQUENCE RAINFOREST-SUGARCANE-PASTURELAND IN THE ATLANTIC FOREST BIOME

This study evaluated soil chemical and isotopic changes in soils of a chronosequence rainforest-sugarcane-pasture in the Atlantic Forest biome, Brazil. Soil samples were collected (0-20 cm) in areas of native Brazilian Atlantic rainforest, sugarcane plantation and pastures of Brachiaria decumbens. The soil analyses performed were: pH (water 1:2.5), P (Mehlich-I), (Al+3, H+Al, K+, Ca+2, Mg+2 and Na+), soil organic matter (SOM), N, organic carbon and δ13C and δ15N stable isotopes. The conversion of rainforest to sugarcane and pastures resulted in a reduction of the soil natural acidity. Forest areas had greater Al+3 and H+Al concentrations than cultivated areas. The conversion from forest to agricultural soil reduced Al+3 (44%) and H+Al (11%), approximately. Soils from pasture had a greater percentage of base saturation (37.3%) than forest soils (25.4%). Cation exchange capacity was strongly influenced by concentrations of K+, Ca+2 and Mg+2, but not by Na+. Carbon stable isotope (δ13C) was more depleted in forest areas (-28.14‰), followed by sugarcane (-21.33‰), and pastures (-19.54‰). The greatest δ15N values were found in sugarcane areas. The short chronosequence studied, had a strong influence of the conversion of the forest on the decrease of the natural acidity and modifications of the isotopic profile. The enrichment of soil δ13C was attributed to the changes from predominant C3 vegetation to C4 grasses.

Onset of the Paleoanthropocene in the Lower Great Lakes Region of North America: An Archaeological and Paleoecological Synthesis

Beyond its centrality to debates on the definition of a global chronostratigraphic geologic unit, the Anthropocene concept has served as a useful theoretical construct with which to assess regional-scale anthropogenic impacts on prehistoric ecological systems through the recognition of earlier “Paleoanthropocene” events predating the onset of modern, industrial, global-scale effects. To this end, we present data derived from the archaeological and paleoecological records of the lower Great Lakes region of northeastern North America to evaluate the nature, magnitude, and timing of Native American land use impacts over the course of the Holocene. We identified three phases of emerging and progressively intensifying anthropogenic influence coinciding with initial human paleopopulation increase (5400–2500 BP), regional introduction of maize (Zea mays; 2500–1100 BP), and the regional adoption of maize-based agriculture (1100–300 BP). Each phase was accompanied by notable shifts in one or more proxy indicators of amplified fire regimes (increased soil charcoal deposition, higher lake sediment charcoal influx, greater percentages of fire-tolerant pollen taxa), decreased forest canopy density (increased herbaceous pollen taxa, enriched speleothem δ13C values), paleopopulation growth (increased archaeological 14C date frequencies), and dietary innovations (increased cultigen 14C date frequencies, enriched pottery residue δ13C values). Although prominent climate excursions also greatly influenced forest species composition, forest structure, and disturbance regimes, demographic and cultural factors impinging on Native American subsistence regimes and settlement patterns became increasingly important modulators of ecological processes over the course of the Holocene.

No evidence for carryover effect in tree rings based on a pulse-labelling experiment on Juniperus communis in South Germany

A clear carryover effect of tree-ring formation was not detected based on a pulse-labelling experiment conducted on Juniperus communis in South Germany. The inherent linkage between photosynthesis and the formation of wood is important for the understanding of relationships between tree-ring series and climate/environmental data in dendroclimatology studies. However, it is impossible to reach a mechanistic procedure of tree stem radial growth depending on its carbon balance from a traditional statistical point of view alone. Pulse labelling experiment with stable carbon isotope (13CO2) has provided innovative insights into the fate of recently assimilated carbon in organs and carbon-containing compounds. In this study, we conducted an in situ pulse labelling experiment on 27 July 2016 to examine the response of tree ring and different-aged needles to short-term elevated 13CO2 of a juniper shrub growing on a heathland in South Germany. New and old needles from four expositions were sampled before and after the experiment. A wood segment was taken from the main branch and stable carbon isotope composition (δ13C) was analysed at an intra-annual time scale. Before the experiment, the mean δ13C was − 26.8 ± 0.4‰ (mean ± standard deviation) for both needle ages, while woody tissue showed about 3‰ higher δ13C compared to needles. Substantial enriched 13C was detected in the needles after the experiment. New needles showed significant higher δ13C than the old ones 1–7 days after the experiment. Significant enriched δ13C was detected in the wood from 35 to 61% of the annual tree ring in 2016, indicating that the short-term enrichment of 13C can affect wood formation for a large section. No enhancement in 13C signal appeared in the tree ring of the subsequent year 2017, suggesting the absence of a carryover effect. Wood formation did not reply on the carbohydrates stored even 1 year before and thus tree-ring ecophysiological modelling as well as dendrochronological studies should therefore benefit from such result.

Stable Isotopes and Parasites Indicate Feeding Ecology in Florida, USA, Wading Birds

We assessed δ13C and δ15N profiles and endoparasite community composition in Great Egrets (Ardea alba), Great Blue Herons (A. herodias), and White Ibis (Eudocimus albus) from four wildlife rescue centers (two mainland, two on islands in the Florida Keys) in south Florida, USA to elucidate feeding ecology. We detected among-species differences for δ15N but not δ13C and noted decreased δ13C enrichment in Great Egrets and Great Blue Herons (but not White Ibis) from these centers. Parasite component community and infracommunity species richness were higher in Great Egrets and Great Blue Herons relative to White Ibis, and higher in birds of the same species from mainland centers. Multivariate analysis of parasite infracommunity structure detected co-occurring clusters of parasite taxa characteristic of Great Egrets and Great Blue Herons on the one part, and of White Ibis on the other; mainland Great Egrets and Great Blue Herons had similar parasite communities and clustered separately from conspecifics from the islands. We detected a significant (negative) correlation of infracommunity species richness with δ13C but not δ15N. Lastly, parasite infracommunity Bray-Curtis similarity correlated significantly with stable isotope Euclidean distances. We conclude that the two approaches converge towards similar outcomes, providing complementary and consilient information on host feeding ecology.

Rhizosphere effects promote soil aggregate stability and associated organic carbon sequestration in rocky areas of desertification

Soil aggregate stability is an important index for predicting soil water loss and soil erosion resistance. Plant roots effectively control soil erosion and stabilize soil structure, which has a crucial influence on the formation of aggregates and soil organic carbon (SOC) sequestration. We examined how rhizosphere effects influence soil aggregate stability and its associated SOC contents and δ13C values, following a proposed extended model of carbon (C) flows between the aggregate size classes in the root systems based on 13C fractionation in each step of SOC formation. The results show that the rhizosphere effects significantly improved the stability of aggregates. The mean weight diameter (MWD) and geometric mean diameter (GMD) of rhizosphere soil aggregates were significantly higher than those of non-rhizosphere soil aggregates associated with plants with fibrous roots. SOC levels of all size aggregates in the rhizosphere soil of both fibrous and tap root plants were higher than those of non-rhizosphere soil. Moreover, SOC contents increased in the order of silt-clay particles (SCP, <0.05 mm), microaggregates (MIA, 0.05-0.25 mm) and small macroaggregates (SMA, 0.25-1 mm), and then decreased from SMA to large macroaggregates (LMA,> 1 mm). The δ13C values in non-rhizosphere soil were generally higher than those in rhizosphere soil in aggregates of the same size class, especially in the tap root plants. Except for the rhizosphere soil of fibrous root plants, the other three soil types (rhizosphere and non-rhizosphere soil of tap root plants, and non-rhizosphere soil of fibrous root plants) were shown to have aggregate δ13C values that decreased with increasing soil aggregate size. Δ13C enrichment of the SOC fractions showed that the general flow direction of SOC was from rhizosphere to non-rhizosphere, and from large aggregates to small aggregates. The C flow in the aggregates of rhizosphere soil was clearly greater than that in the non-rhizosphere soil, especially with the fibrous root plants. These findings suggest that plant roots have the potential to regulate soil structural stability, and enhance soil erosion resistance and SOC sequestration.

Organic matter stabilization in aggregates and density fractions in paddy soil depending on long-term fertilization: Tracing of pathways by 13C natural abundance

Previous studies on upland soils showed that 13C natural abundance can successfully reveal C stabilization pathways between aggregates and soil organic matter (SOM) density fractions. The direction of C stabilization in paddies can, however, deviate from that in upland soils owing to i) periodic drying–rewetting cycles, with oxygen pulses under oxic conditions, and thus, shifts in microbial processing of organic residues, and ii) intensive organic and mineral fertilization. To trace C stabilization in paddies, soil was sampled from a long-term field experiment under an unfertilized Control and NPK, NPK + straw, and NPK + manure fertilizer regimes. Soil was analyzed for total C, microbial biomass (MB), and dissolved organic C, and separated into three classes based on aggregate size (>250 μm, 53–250 μm, and <53 μm) followed by density fractionation of each class to obtain free and occluded light fractions as well as dense and mineral heavy fractions. Pathways of C were determined based on C content and δ13C in all pools. The highest increase in total C (69%) was in NPK + manure, whereas the MBC increased with fertilization by at least 29% compared with the Control. All fertilizers increased macro-aggregation by at least 111% compared with the Control. The highest C content in the aggregates was in the mineral fractions of macroaggregates. Fertilization decreased the δ13C of total SOM compared with the Control, indicating suppressed decomposition of organic compounds. Aggregate size classes showed a typical δ13C enrichment trend from macro-to microaggregates, reflecting similarities between paddy and upland soils. A detailed scheme of C flows within aggregates and SOM fractions based on the δ13C natural abundance revealed the following general sequence: mineral → dense → free light → occluded light fractions. This trend, which is partly opposite to that observed in upland soils, reflects the anoxic and variable redox conditions of paddies. This facilitates the predominant stabilization of recent C input in the mineral fraction with Fe oxides due to Fe2+/Fe3+ dynamics, whereas light fractions are processed by microorganisms mainly in periods without overflooding. The C pathways in the two heavy fractions were separate from those in the two light fractions, which also indicates differences in the C stabilization processes between paddy and upland soils. Thus, the present study provides further detailed insights into the C stabilizing mechanisms in paddy soils which depend on management.

Natural geochemical markers reveal environmental history and population connectivity of common cuttlefish in the Atlantic Ocean and Mediterranean Sea

Natural markers (δ13C and δ18O stable isotopes) in the cuttlebones of the European common cuttlefish (Sepia officinalis) were determined for individuals collected across a substantial portion of their range in the Northeast Atlantic Ocean (NEAO) and Mediterranean Sea. Cuttlebone δ13C and δ18O were quantified for core and edge material to characterize geochemical signatures associated with early (juvenile) and recent (sub-adult/adult) life-history periods, respectively. Regional shifts in cuttlebone δ13C and δ18O values were detected across the 12 sites investigated. Individuals collected from sites in the NEAO displayed more enriched δ13C and δ18O values relative to sites in the Mediterranean Sea, with the latter also showing salient differences in both markers among western, central and eastern collection areas. Classification success based on cuttlebone δ13C and δ18O values to four geographical regions (NEAO, western, central and eastern Mediterranean Sea) was relatively high, suggesting that environmental conditions in each region were distinct and produced area-specific geochemical signatures on the cuttlebones of S. officinalis. A modified δ13C and δ18O baseline was developed from sites proximal to the Strait of Gibraltar in both the NEAO and Mediterranean Sea to assess potential mixing through this corridor. Nearly, all (95%) of δ13C and δ18O signatures of S. officinalis collected in the area of the NEAO closest to the Strait of Gibraltar (Gulf of Cadiz) matched the signatures of specimens collected in the western Mediterranean, signifying potential movement and mixing of individuals through this passageway. This study extends the current application of these geochemical markers for assessing the natal origin and population connectivity of this species and potentially other taxa that inhabit this geographical area.

Soil organic matter as affected by the conversion of natural tropical rainforest to monoculture rubber plantations under acric ferralsols

Land-use change (LUC) in the tropics, such as the exponential rate of conversion of natural habitats into intense monocultures focusing on cash-crop cultivation, is a major causal factor of global environmental change. To understand the effects of LUC on soil organic matter (SOM) stability and the dynamics of C and N within SOM fractions, we measured the C and N content and δ13C and δ15N in fractions of different aggregate- and density-size of acric ferralsols in tropical rainforests and rubber plantations. The proportion of macroaggregates, heavy and light fractions significantly decreased after LUC. The results showed that, in general, conversion of tropical rainforest to rubber plantation significantly decreased the C and N content in bulk soil and the aggregate- and density-size to 20 cm soil depth. The decrease in C and N content in bulk soil was mainly driven by decreasing C and N associated with macroaggregates and light fractions, which accounted for > 50%. We found significant correlations among mean weight diameter, aggregate-, and density-size fractions C, N, and C/N ratios. The conversion of tropical rainforest to rubber plantation significantly enriched soil δ13C while depleting δ15N. Enrichment of δ13C in rubber plantations could be explained by the mixing of old and fresh C. We conclude that, C and N dynamics within SOM fractions were greatly affected by LUC and the δ13C and δ15N signature confirms the changes in SOM stability after forest conversion. We suggest that planting intercrops within rubber monocultures may improve SOM accumulation, soil aggregation, and C and N sequestration.

Distribution, sources and burial flux of sedimentary organic matter in the East China Sea

Distribution of total organic carbon (TOC), total nitrogen (TN), stable isotope ratio of organic carbon and nitrogen (δ13C and δ15N) in 31 surface sediments were examined to quantitatively discriminate the source and burial of sedimentary organic matter (SOM) in the East China Sea (ECS). Results show that high content of TOC and TN occurred in the southern inner shelf and the northeast area due to the transport of organic matter (OM) from the Changjiang (Yangtze) River southwards by the Zhejiang Fujian Coastal Current (ZFCC) and the delivery from the old Huanghe (Yellow) River estuary by the Subei Coastal Current (SbCC), respectively. The significant relationship of TOC to clay provided evidence that the fine-grained sediment was the primary carrier for SOM from the inner shelf to open sea. The TN varied proportionally to the TOC with the neglected intercept, suggesting that most of nitrogen measured was related to the SOM and the influence of the sorption of inorganic nitrogen was insignificant. The seaward enrichment of δ13C and seaward depletion of C/N and δ15N illustrated the decrease of terrestrial OM (TOM) and the increase of marine OM (MOM). The close of average C/N ratio to the Redfield ratio indicated the minor role of terrestrial plant debris in the SOM. Distribution of bulk OM properties was ascribed to the terrestrial and marine input by the shelf circulation and phytoplankton with the contributions of 76.1% MOM and 23.9% TOM to SOM, respectively. The burial flux of OC ranged within 0.34-7.56 mg/(cm2·a) (averaged 2.80 mg/(cm2·a)) and enriched along the shore and in the fine-grained area, manifesting the significant input of the land-based sources and the effect of shelf mud depositional process on the fate of SOM. The sharp seaward decrease of burial fluxes of terrestrial and marine OC gave evidences that the majority of organic carbon were settled in the inner shelf with the small fraction of them further transported eastwards.

Resolving sea ice dynamics in the north-western Ross Sea during the last 2.6 ka: From seasonal to millennial timescales

Time-series analyses of satellite images reveal that sea ice extent in the Ross Sea has experienced significant changes over the last 40 years, likely triggered by large-scale atmospheric anomalies. However, resolving how sea ice in the Ross Sea has changed over longer timeframes has until now remained more elusive. Here we used a laminated sediment piston core (14.6 m) collected from the Edisto inlet (Western Ross Sea) to reconstruct fast ice dynamics over the last 2.6 ka. Our goal was to first understand the climate expression of selected well-defined sediment laminae and then use these characteristics for reconstructing past sea ice behaviour across the whole sedimentary sequence. We used the recently established sea ice diatom biomarker proxy IPSO25 in combination with diatom census counts and bulk analyses. Analyses performed on a suite of discrete laminae revealed statistically significant differences between dark and light laminae reflecting different depositional conditions. Based on their respective biogeochemical fingerprints, we infer that dark laminae accumulated during sea ice thaws in early summer. Under these conditions, laminae contain relatively high concentrations of IPSO25 and display an enriched δ13C composition for the bulk organic matter (OM). While diatom assemblages in dark laminae are relatively homogenous, as the thaw continues later in the summer, Corethron pennatum becomes the dominant diatom species, resulting in the formation of light laminae characterized by low IPSO25 concentrations. Since C. pennatum can migrate vertically through the water column to uptake nutrients and avoid competition in oligotrophic waters, its high concentration likely reflects stratified and ice-free surface waters typical of late summer.Down-core trends show that the correlation between sediment brightness and geochemical fingerprint (i.e., IPSO25 and δ13C) holds throughout the record. Based on the knowledge gained at lamina level, our down-core high-resolution reconstruction shows that the summer fast ice coverage changed dramatically during the late Holocene. Specifically, we conclude that the Edisto inlet experienced regular early summer opening between 2.6 ka, and ca. 0.7 ka, after which, coastal fast ice persisted during summer months and ice-free conditions became less frequent. Comparison with previous regional ice core data suggests that the sudden cooling recorded over the Victoria Land Coast region since 0.7 ka might potentially explain our observation of persistent summer fast ice in the Western Ross Sea. Our study has shown that multi-proxy data derived from laminated sediments can provide hitherto unknown detail regarding past summer sea ice dynamics in coastal Antarctic regions.

Growth, health and biochemical composition of the sea cucumber Cucumaria frondosa after multi-year holding in effluent waters of land-based salmon culture

Methods have been proposed to mitigate the environmental footprint of aquaculture, including co-culture of species occupying different trophic levels. In this study, sea cucumbers Cucumaria frondosa, either from production tanks fed with effluent water from land-based salmon culture over 4 yr or collected from the field, were compared using stable isotope, lipid and fatty acid (FA) signatures as indicators of waste assimilation, health and biochemical composition. Enrichment of δ13C in muscle bands and intestine and of δ15N in muscle bands, gonad and intestine was detected in captive individuals relative to wild individuals, suggesting the uptake and assimilation of waste from salmon culture. The higher levels of FA biomarkers typical of salmon feed (18:1ω9, 18:2ω6 and 20:1ω9) and lower ω3/ω6 ratio in the captive sea cucumbers were also in line with assimilation of the waste. However, male and female sea cucumbers from the co-culture became smaller with time, their organ indices were lower than those of wild individuals (e.g. poorly developed gonad), and their biochemical composition differed: triacylglycerol content was greater in wild individuals and phospholipid content was greater in captive individuals. Also, FA profiles of all tissues differed between the 2 groups, whereas total lipid in muscle bands and gonad remained similar. Overall, results support that co-culture with suspension-feeding sea cucumbers may help mitigate the salmon industry footprint. In turn, the biochemical composition of the sea cucumbers changed, and their reduced size and body indices suggest that this food source does not provide suitable nutrients to sustain growth and reproduction.

Seasonal changes of sources and volatility of carbonaceous aerosol at urban, coastal and forest sites in Eastern Europe (Lithuania)

We measured stable carbon isotope ratios of total carbon (TC) and organic carbon (OC) in fine carbonaceous aerosol fraction sampled in August and September 2013 at urban, coastal and forest sites in Lithuania. δ13C values of TC for all three sites over the whole measurement period varied from −29.3 to −26.6‰, which is in the range of particles emitted by fossil fuel combustion in Eastern Europe. The isotopic composition at the forest and coastal site showed a similar variation during two contrasting pollution periods. δ13C values in the clean period were more variable, whereas the polluted period was characterized by a gradual enrichment in δ13C compared to the clean period. In the polluted period air masses originated from southern, southeastern or southwestern direction, indicating long-range transport of pollutants from Eastern Europe and Southern Europe to Lithuania. Oxidative processing during long-range transport or the different source signatures (e.g., enriched 13C signature of gasoline used in Western Europe vs. Eastern Europe) could cause the less negative δ13COC values during the polluted episode. δ13C for OC desorbed from the filter samples was separately measured during three different temperature steps (200 °C, 350 °C and 650 °C). OC desorbed at 200 °C had the most depleted 13C signature of around −29‰ at all three sites.A comparison with previously published data measured during the winter at the same sites showed that both TC and OC had less negative δ13C values in winter than in summer, which can be explained by the contribution of biomass/coal burning sources in winter. At the urban site δ13C of OC did not change much with increasing desorption temperature in winter, which is typical for primary sources, but in the summer δ13C of OC was depleted for lower desorption temperatures, possibly due to the influence of SOA formation. A higher fraction of more refractory OC in summer compared to winter-time suggests active photochemical processing of the primary organic aerosol as an important process at all three sites.

Formula omitted]C signatures of organic aerosols: Measurement method evaluation and application in a source study

Analysis of the stable carbon isotope 13C in organic carbon (OC) can give insight into sources and atmospheric processing of carbonaceous aerosols, provided the 13C source signatures are known. However, only few data on 13C signatures of OC emitted by common sources of carbonaceous aerosol are available in Europe. We present and evaluate an improved version of a measurement method to obtain δ13C signatures on organic aerosols desorbed from filter samples at three different desorption temperatures (200 °C, 350 °C and 650 °C) and apply it in a source study.With our calibration approach, the reproducibility of a L-Valine reference material desorbed at a single temperature step of 650 °C shows a standard deviation of 0.19‰ over a period of more than one year. The average δ13C value for this reference material over 248 measurements is −24.10‰, which shows only a slight bias to the nominal value of −24.03‰. Repeated analysis of ambient filter samples desorbed at three temperature steps show typical standard deviations of about 0.3‰ for all temperature steps (200 °C, 350 °C and 650 °C). Isotopic fractionation due to partial thermal desorption during the individual temperature steps was tested on single compound reference materials. It showed significant isotopic fractionation only at temperature steps, in which a very minor fraction of the compound was desorbed. Possible isotope effects caused by charring of organic material were investigated and found to be not significant.The thermal desorption method was applied to various source filter samples from the region of Naples, Italy. We analyzed two different biomass burning sources, exhaust from a city bus and traffic emissions collected in a tunnel and compared these to ambient filter samples from the same region. δ13C signatures of the total OC show values in a narrow range of about −28‰ to −26‰ for all sources, which does not allow a source apportionment only based on 13C. Nevertheless, the results add information to a source inventory of δ13C, where information of 13C in organic aerosol from specific emission sources are rare. City bus emissions show little variation of δ13C over the temperature steps, whereas biomass burning aerosol is enriched in 13C for OC desorbed at 650 °C. For PM10 samples in the urban tunnel an enrichment in δ13C at the 650 °C temperature steps was observed, which is likely caused by the contribution of carbonate carbon to the carbonaceous material desorbed at this temperature step.

A comparison of hydro-geochemistry and stable isotope composition of travertine-depositing springs, Garab in NE Iran and Pamukkale in SW Turkey

In this study, the hydro-geochemistry and stable isotope compositions (δ18O, δ2H, and δ13C) of travertine-depositing springs were investigated in two regions of Garab and Pamukkale, located in NE-Iran and SW-Turkey, respectively. The physical, chemical and isotopic dataset of water and travertine samples were obtained in situ measurements, laboratory analysis and from the literature. According to the high EC values (~ 2400 and ~ 10,500 μS/cm), the average δ13C-DIC values of water samples (10.4 and 7.2‰ VPDB), and its δ13C–CO2 values (1.5 and − 1.8‰ VPDB), it seems that the Garab and Pamukkale spring water were supplying from deep thermal groundwater with thermogenic origins and with contribution of carbonate dissolution through the rock-water interactions process. The more concentrations of Na+, K+, and Cl− in Garab water are related to subsequent admixture processes, which is originated from dissolving overloaded impure dissolve materials during upwelling water toward the ground level. The more enriched δ13C and δ18O values of Garab travertine samples (10.4 and − 7.1‰ VPDB, respectively) than that of Pamukkale travertine (7.2 and − 10.4‰ VPDB, respectively) is due to more CO2 degassing. The isotopic compositions of precipitation in both Garab (δ2H = 7.2∗δ18O + 11.2‰) and Pamukkale (δ2H = 8∗δ18O + 16‰) areas are characterized by greater d-excess compared to GMWL but smaller than of Mediterranean area. Although the isotopic compositions of both Garab and Pamukkale springs show the meteoric origin; however, the deviation from meteoric water lines is probably evident to oxygen isotope exchange with the deep host bedrock.

Isotope analysis method for the herbicide bromoxynil and its application to study photo-degradation processes

Bromoxynil is an increasingly applied nitrile herbicide used for post-emergent control of annual broadleaved weeds. Compound-specific isotope analysis (CSIA) of the compound is of interest for studying its environmental fate, yet is challenging following its polar nature. We present a CSIA method for bromoxynil that includes offline thin-layer chromatography purification followed by an elemental analyzer isotope ratio mass spectrometer (EA-IRMS). This method was shown to be accurate and precise for δ13C and δ15N analysis of the compound (standard deviation of replicate standards <0.5‰). The method was applied to photodegraded samples, either radiated under laboratory condition with a UV lamp, or exposed to sunlight under environmental conditions. Dominating degradation products were similar in both cases. Nevertheless, isotope effects differed, presenting a strong inverse carbon isotope effect (εC = 4.74 ± 0.82‰) and a weak inverse nitrogen isotope effect (εN = 0.76 ± 0.12‰) for the laboratory experiment, and an insignificant carbon isotope effect (εC = 0.34 ± 0.44‰) and a normal nitrogen isotope effect (εN = −3.70 ± 0.30‰) for the natural conditions experiment. The differences in δ13C vs. δ15N enrichment trends suggest different mechanism for the two processes. Finally, the obtained dual isotope trend for natural conditions provide the basis for studying the dominance of photodegradation as a degradation route in the environment.