Stable Carbon Isotope Signatures Research Articles

Exploring marine zooplankton dynamics through carbon stable isotope signatures in a recently marine submarine volcano

Submarine emissions of gases from hydrothermal vents alter the surrounding chemical environment, influencing species responses to the resulting environmental gradients. The 2011 underwater eruption of the Tagoro volcano off the coast of El Hierro in the Atlantic Ocean changed the physical and chemical conditions, impacting the distribution of pelagic fauna. Post-eruptive stages from 2013 to 2018 revealed changes in both benthic and pelagic communities, with continuous eruptions further affecting local carbon cycle through shifts in nutrient concentrations and isotopic composition. The lowest δ13C values in zooplanktonic primary consumers were found in areas directly influenced by the Tagoro submarine volcano. Although the mixing model results show that phytoplankton is the primary carbon source for copepods, contributing an average of 28.3% of their carbon, magmatic CO2 and seawater dissolved inorganic carbon each account for approximately 17–18%. The isotopic signatures reveal a gradient of enrichment in copepods, reflecting the influence of inorganic nutrient and gas emissions from the volcano's centre to its periphery within the marine ecosystem. This data is useful for understanding the worldwide significance of environmental stressors such as volcanic eruptions on marine organisms.

Hydrocarbons, Hydrogen, and Organic Acids Generation by Ball Milling and Batch Incubation of Sedimentary Rocks

Pulverized rock samples are widely used in laboratory experiments, e.g., to assess microbial or abiotic processes in batch incubation tests. However, it is unclear if ball-milled samples accurately reflect in-situ conditions and if observed processes are affected by by-products artificially generated during the sample preparation procedure. As such, this study examined the effects of dry ball milling on the release of gases, which include C1-C4 hydrocarbons, carbon dioxide (CO2), hydrogen (H2), and low molecular weight organic acids (LMWOAs) from different sedimentary rocks. The experiments involved pulverization using a gas-tight zirconium oxide planetary ball mill followed by wet and dry batch incubation and thermal desorption up to 200 o C. During milling, all sedimentary rocks, except a low organic carbon sandstone sample, yielded methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H10), H2, CO2, and unsaturated hydrocarbons, e.g., ethene (C2H4). Sandstones only yielded H2, CH4, and CO2. Stable carbon isotope signatures of these products are similar to thermogenic gases. The gases were also detected in subsequent wet incubation experiments (after gases from milling had been removed). Additionally, formate, acetate, and citrate, were detected in all samples except for sandstone. Pyruvate, malate, and succinate were also detected in some samples. Thermal desorption products of powdered limestone, shale, and pyrite concretion samples included organic acids, such as acetate and formate, which were higher in milled samples than in crushed particles (∼1 mm). The original geological thermal maturity of the studied sedimentary rock samples was low (below “oil window”) and, thus, considerably below “gas window”, suggesting that most of the detected gases were generated during ball milling. H2 generated during ball milling may be derived from the reduction of water from fluid inclusion or phyllosilicates, involving the formation of reactive mineral surfaces or radicals. Notably, the concentrations of gaseous hydrocarbons derived from milling are relatively high and comparable to “wet” gases. At the same time, these data indicate that substantial amounts of gases and LWMOAs might be artificially generated during laboratory batch experiments with milled samples. Hence, ball milled rock samples must be used with caution if assessing (bio-)geochemical processes for natural environments.

Characterizing water solubility of fresh and aged secondary organic aerosol in PM2.5 with the stable carbon isotope technique

Abstract. The investigation of the water-soluble characteristics of secondary organic carbon (SOC) is essential for a more comprehensive understanding of its climate effects. However, due to the limitations of the existing source apportionment methods, the water solubility of different types of SOC remains uncertain. This study analyzed stable carbon isotope and mass spectral signatures of total carbon (TC) and water-soluble organic carbon (WSOC) in ambient PM2.5 samples for 1 year and established stable carbon isotope profiles of fresh and aged SOC. Furthermore, a Bayesian stable isotope mixing (BSIM) model was employed to reveal the water solubility characteristics of fresh and aged SOC in a coastal megacity of China. WSOC was dominated by secondary sources, with fresh and aged SOC contributing 28.1 % and 45.2 %, respectively. Water-insoluble organic carbon (WIOC) was dominated by primary sources, to which fresh and aged SOC contributed 23.2 % and 13.4 %. We also found that the aging degree of SOC has considerable impacts on its water solubility due to the much higher water-soluble fraction of aged SOC (76.5 %) compared to fresh SOC (54.2 %). Findings of this study may provide a new perspective for further investigation of the hygroscopicity effects of SOC with different aging degrees on light extinction and climate change.

Lipid biomarkers and stable isotopes uncover paleovegetation changes in extremely species-rich forest-steppe ecosystems, Central Europe

The historical development of the vegetation of semi-dry grasslands in Central Europe is not satisfactorily understood. Long-term continuity of open vegetation or, conversely, deep-past forest phases are considered possible sources of the current extreme species diversity of these ecosystems. We aimed to reveal the trajectory of paleovegetation development in these ecosystems through detailed analysis of terrestrial in-situ soil geoarchives. We measured the bulk soil carbon and nitrogen contents, lipid molecular distribution, and compound-specific stable carbon and hydrogen isotopic signatures of mid- and long-chain n-alkanes extracted from soil and modern plant material tissues (i.e., deciduous and Pinus leaves and grass/herbaceous species).The C23–C33 n-alkane homologues were identified in soils with different abundances. Normally, C27 and C29 n-alkanes were the most abundant homologues in tree-leaf samples, while grass-derived n-alkanes were mostly C31 and C33 homologues. Soils were largely dominated by C29 and C31 n-alkanes. Odd-numbered C27–C33 soil n-alkane δ13C values ranged from −36.2‰ to −23.2‰, whereas their δ2H values showed a wider range of variability that fluctuated from −224‰ to −172‰. Molecular distribution in combination with radiocarbon analysis of soil organic matter (SOM) and δ13C and δ2H values of n-alkanes revealed a large contribution of C3 trees (both deciduous and coniferous trees/pine trees) as the main source of n-alkanes between the late Pleistocene and early Holocene (ca 15,000–8200 calibrated year before present/cal year BP). A clear shift toward more grassy/herbaceous vegetation was observed from the early Holocene (ca 11,700–8200 cal year BP) onwards. Distribution patterns of lipids and soil geochemical parameters showed that plants are the main source of SOM and that biodegradation and kinetic isotope fractionation are not the main reasons for 13C enrichment in soil profiles. Past C3 vegetation shifts as well as paleoclimate changes (i.e., aridity) can have played a role in the observed 13C depth profiles.

Newly plant-derived carbon in the deeper vadose zone of a sandy agricultural soil does not stimulate denitrification

Analysis of stable carbon (C) isotopic signatures (δ13C) in various soil C pools provides useful information on soil C sources, transport, and availability. Understanding the extent of deeper soil (below 40 cm) sequestration and transport of plant derived C is of particular interest as this provides a source for microorganisms to drive biological denitrification (as indicated by denitrification enzyme activity, DEA) and hence mitigate the nitrate leaching to groundwater. Meanwhile, studies on deeper soil C sequestration are rare due to methodological constraints. This study was done in deeper vadose zone (0–160 cm) of a sandy agricultural soil in a humid and temperature zone after a C3-C4 vegetation change taking advantage of the marked isotopic differences between C3 and C4 plants. It took place in a site previously grown with C3 crops (beet, barley, grass), but where C4 crops (maize) were grown continuously for the last 20 years. The other site where C3 crops were continuously grown was used for comparison. Specifically, the δ13C signature in top and deeper soil layers was used to distinguish between old C3– and newly C4-plant derived C in four C pools, i.e., bulk soil C, hot- and cold-water extractable C, and respired CO2-C. The δ13C signature between C3 soils and C3-C4 shifted soils was similar for bulk soil C but significantly different for water extractable and respired C pools. Hence, we estimated that the contribution of newly derived C to bulk soil C was negligible, whereas the contributions to the other C pools amounted up to 28.4 % along the soil profile. This emphasizes the importance of simultaneously analysing δ13C signature in various soil C pools to accurately assess C vertical transport and distribution. The concentrations of cold-DOC and values of specific ultraviolet visible absorbance of the wavelengths 254 and 280 nm decreased from 50 to 130 cm soil depths, while they increased below these depths. However, this suggested rise in C chemical quality at the deepest soil depths did not cause an increase in soil respiration activity or DEA, which was attributed to the protective effects of iron and aluminium oxides on C decomposition. Upon the application of labile C and N substrates, the deepest soil layers displayed a significantly increased DEA, suggesting the presence of a relatively abundant population of active denitrifying organisms. Overall, this study documents the presence of plant-derived C in the deeper vadose zone. Meanwhile, this particular C pool might not be an important substrate to drive deep-soil denitrification due to constraints imposed by the protection by metal oxides.

Diet choices determine mercury exposure risks for people living in gold mining regions of Peru

Artisanal and small-scale gold mining (ASGM) is the largest global anthropogenic mercury (Hg) source and is widespread in the Peruvian Amazon. Consuming Hg-laden foods exposes people to this potent neurotoxin. While numerous studies have examined fish Hg content near ASGM, Hg accumulation in other commonly consumed animal-and plant-based foods from terrestrial environments is often overlooked. In this study, we aim to address understudied dietary Hg exposures.To understand Hg exposure from food staples in the Peruvian Amazon, we measured total and methyl Hg in local crops, fish, chicken meat, chicken feathers, and eggs from ASGM-impacted and upstream (reference) communities. Diet surveys were used to estimate probable weekly Hg intake from each food. Fish and chicken stable carbon and nitrogen isotope signatures were analyzed to evaluate trophic magnification.Though few crops exceeded food safety recommendations, rice methyl Hg proportions were high (84%). Trophic level was an expected key predictor of fish Hg content. 81% (17 of 21) of local carnivorous fish exceeded WHO and EPA recommendations. Compared to upstream communities, mining-impacted communities demonstrated elevated total Hg in crops (1.55 (interquartile ranges (IQR): 0.60–3.03) μg kg−1 upstream versus 3.38 (IQR: 1.62–11.58) in mining areas), chicken meats (2.69 (IQR: BDL–9.96) μg kg−1 versus 19.68 (IQR: 6.33–48.1)), and feathers (91.20 (IQR: 39.19–216.13) μg kg−1 versus 329.99 (IQR: 173.22–464.99)). Chicken meats from mining areas exhibited over double the methyl Hg concentrations of those upstream. Methyl Hg fractions in chicken muscle tissue averaged 93%. Egg whites and livers exceeded Hg recommendations most frequently. Proximity to mining, but not trophic position, was a predictor of chicken Hg content.Our results demonstrate that terrestrial and aquatic foods can accumulate Hg from mining activity, introducing additional human Hg exposure routes. However, locally sourced carnivorous fish was the largest contributor to an estimated three-fold exceedance of the provisional tolerable weekly Hg intake.

Methane pumping by rapidly refreezing lead ice in the ice-covered Arctic Ocean

If and how the sea ice cycle drives the methane cycle in the high Arctic is an open question and crucial to improving source/sink balances. This study presents new insights into the effects of strong and fast freezing on the physical–chemical properties of ice and offers implications for methane fluxes into and out of newly formed lead ice. During the 2019–2020 transpolar drift of the Multidisciplinary Drifting Observatory for the Study of Arctic Climate (MOSAiC), we took weekly samples of growing lead ice and underlying seawater at the same site between January and March 2020. We analyzed concentrations and stable carbon isotopic signatures (δ13C–CH4) of methane and calculated methane solubility capacities (MSC) and saturation levels in both environments. During the first month, intense cooling resulted in the growth of two-thirds of the final ice thickness. In the second month, ice growth speed decreased by 50%. Both growth phases, disentangled, exposed different freeze impacts on methane pathways. The fast freeze caused strong brine entrapment, keeping the newly formed lead ice permeable for 2 weeks. These physical conditions activated a methane pump. An increased MSC induced methane uptake at the air–ice interface, and the still-open brine channels provided top-down transport to the ocean interface with brine drainage. When the subsurface layer became impermeable, the top-down pumping stopped, but the ongoing uptake induced a methane excess on top. During the second growth phase, methane exchange exclusively continued at the ice–ocean interface. The shift in the relative abundance of the 12C and 13C isotopes between lead ice and seawater toward a 13C-enrichment in seawater reveals brine drainage as the main pathway releasing methane from aging lead ice. We conclude that in winter, refrozen leads temporarily function as active sinks for atmospheric methane and postulate that the relevance of this process may even increase when the Arctic fully transitions into a seasonally ice-covered ocean when leads may be more abundant. To highlight the relevance of methane in-gassing at the air–ice interface as a potential but still unconsidered pathway, we include estimates of the occurrence and frequency of young lead ice from satellite observations of leads during MOSAiC.

Comparative nutrient drawdown capacities of farmed kelps and implications of metabolic strategy and nutrient source.

Seaweed aquaculture, particularly kelp farming, is a popular topic as a potential solution for mitigating anthropogenic pollutants and enhancing coastal drawdown of carbon and nitrogen. Using a common garden approach, this study evaluated nutrient drawdown capacities of Alaria marginata (ribbon kelp) and Saccharina latissima (sugar kelp) across four commercial kelp farms in Southeast and Southcentral Alaska. Our findings show that A. marginata exhibited ~30% more carbon and 21% more nitrogen content compared to S. latissima. These results demonstrate the potential for A. marginata to serve as a more efficient species for nutrient drawdown into farmed kelp tissues (per unit biomass) for consideration of potential mitigative actions. The efficacy of this drawdown is likely to be driven by the careful pairing of kelp species with farming environment. Temporally, there was a noted increase in carbon content and a decline in nitrogen content from March to May for both species, consistent with known seasonal nutrient dynamics in coastal waters. Notably, differences in the carbon stable isotope signatures (δ13C) between the kelps may hint at variations in metabolic pathways and nutrient sourcing, particularly concerning the preferential assimilation of CO2 versus , and highlight the need for further work on this topic for applied macroalgal research.

Using stable isotopes in deciphering climate changes from travertine deposits: the case of the Lapis Tiburtinus succession (Acque Albule Basin, Tivoli, Central Italy)

Quaternary stable isotope records of marine and lacustrine carbonate deposits as well as speleothems were extensively studied to reconstruct global and regional climatic evolution. This study demonstrates how stable isotope records of travertine provide fundamental information about climate and the consequences of its evolution on groundwater level fluctuations. The deposition of the Lapis Tiburtinus travertine succession occurred during the Late Pleistocene (150–30 ka), coeval with the last activity of the Colli Albani volcanic complex. Two boreholes (Sn1 and Sn2) were drilled into the Acque Albule Basin (23 km E of Rome), crossing the entire Lapis Tiburtinus succession. The Sn1 borehole in the central part of the basin crosscuts a travertine succession of 62.1 m in thickness, while the Sn2 borehole in the southern part of the basin is characterized by a travertine succession 36.3 m in thickness. Carbon and oxygen stable isotope ratios were analysed on 118 samples (59 samples both for Sn1 and Sn2 boreholes) representative of the entire Lapis Tiburtinus travertine succession crossed by the boreholes. Values, measured and correlated in the two drilled boreholes, permitted determination of the sensitivity of the travertine depositional system to glacial and interglacial cycles, unravelling the complex oxygen and carbon cycle dynamic recorded in such sedimentary succession. Moreover, the results obtained correlated with available pollen curves of the Mediterranean area (from the Castiglione crater, 25 km E of Rome). Regional and global oxygen isotope continental and marine curves, calibrated with the stratigraphy of the Acque Albule Basin, and available U/Th dating allow the identification of at least three phases of the last interglacial (Marine Isotope Stage 5-MIS5). The carbon isotope record, compared with CO2 flux reconstructed and associated with the volcanic activity of the Colli Albani volcanic complex, instead shows an influence from groundwater level changes. In particular, positive shifts that occurred during arid phases are associated with a lower groundwater level and increased CO2 degassing, inducing a major fractionation effect on carbon isotopes. Instead, the negative shifts occurring during more humid periods indicate the inhibition of CO2 degassing and increase in pressure, attesting to a rise in groundwater level. In this view, travertine deposits, frequently studied to define the tectonic setting and activity of the area where they develop, can thus also be used as a tool to understand climate changes and groundwater variations apparent in their stable oxygen and carbon isotope signature.

Dietary reconstruction and influencing factors of oysters cultured in a typical estuarine bay of South China

Blue carbon can be transferred from primary producers to primary consumers through oyster filter feeding. Understanding the carbon (food) sources is crucial for understanding coastal food webs and management of oyster aquaculture ecosystems. In the present study, Bayesian stable isotope mixing models (MixSIAR) were used to identify and quantify food composition within a cultured oyster ecosystem at six sites along a salinity gradient in the estuarine bay of Zhenhai (ZHB). The carbon stable isotope (δ13C) signatures of oyster Crassostrea hongkongensis ranged from −22.06 to −27.27‰, with significant spatial differences (p < 0.001), indicating variations in food resources along the salinity gradient. The primary food source for cultured oysters was suspended particle organic matter across ZHB (55.7–90.6%), with sedimentary organic matter contributing more in the mid-estuary (28.9–44.3%). Partial least squares regression (PLSR) was used to explore the effects of habitat environment and human disturbance on spatial variation in oyster diets. The results indicated that dissolved oxygen, sediment particle size, elevation, and mangrove-related landscape indices were the main factors influencing oyster diet in ZHB. The findings provide insights into the dietary composition of cultured oysters and the underlying factors in a typical shallow bay in southern China, with particular emphasis on the role of terrestrial landscape features. In addition, the findings validate PLSR as a reasonable tool for predicting the food composition of consumers in estuarine bays.

Ammonium enrichment, nitrate attenuation and nitrous oxide production along groundwater flow paths: Carbon isotopic and DOM optical evidence

Dissolved organic matter (DOM) plays a crucial role in the biogeochemical processing of reactive nitrogen in groundwater systems. However, the impacts of DOM on release of geogenic ammonium and transport and transformation of reactive nitrogen including nitrate attenuation under dynamics in groundwater level characteristic for floodplain environments remain unclear. In this study, we have identified the influence of riparian water level fluctuations on changes in the redox conditions, groundwater geochemical composition including the DOM mobilization in the piedmont recharge and the discharge area along groundwater flow paths. We have also evaluated the pivotal roles of DOM degradation in transport and transformation of nitrogen species including geogenic ammonium enrichment, nitrate attenuation, and dissolved nitrous oxide (N2O) production combining the stable carbon isotopic signatures and the optical characteristics of DOM. Along groundwater flow paths, the seasonal amplitudes of surface water levels were higher in the piedmont recharge area than those in the plain discharge area, and four DOM fluorescent components were identified through the parallel factor analysis (PARAFAC), with two terrestrial humic-like components (C1 and C2) in the piedmont recharge area, and two microbial humic-like components (C3 and C4) in the plain transition-discharge area. A positive correlation between stable dissolved inorganic carbon isotopic signatures (δ13C-DIC) and ammonium-nitrogen concentrations indicated that microbial degradation processes of DOM concomitantly promote the release of geogenic ammonium into groundwater. Ammonium enrichment and nitrate attenuation trend in groundwater was noted as one moved from the recharge area to the discharge area. Evidently, a clear correlation emerged where elevated dissolved N2O concentrations were linked to diminished ammonium-nitrogen levels and elevated nitrate-nitrogen levels. Additionally, groundwater exhibited higher dissolved N2O levels in the piedmont recharge area compared to the plain discharge area. These findings revealed that the impacts of groundwater DOM degradation on nitrate attenuation and dissolved N2O production in similar geogenic ammonium-affected Quaternary alluvial aquifers along groundwater flow paths, and established the theoretical basis for ensuring the security of local groundwater supply.

Stable isotope composition of pesticides in commercial formulations: The ISOTOPEST database

By assessing the changes in stable isotope compositions within individual pesticide molecules, Compound Specific Isotope Analysis (CSIA) holds the potential to identify and differentiate sources and quantify pesticide degradation in the environment. However, the environmental application of pesticide CSIA is limited by the general lack of knowledge regarding the initial isotopic composition of active substances in commercially available formulations used by farmers. To address this limitation, we established a database aimed at cataloguing and disseminating isotopic signatures in commercial formulations to expand the use of pesticide CSIA. Our study involved the collection of 25 analytical standards and 120 commercial pesticide formulations from 23 manufacturers. Subsequently, 59 commercial formulations and 25 standards were extracted, and each of their active substance was analyzed for both δ13C (n = 84) and δ15N CSIA (n = 43). The extraction of pesticides did not cause significant isotope fractionation (Δ13C and Δ15N < 1‰). Incorporating existing literature data, stable carbon and nitrogen isotope signatures varied in a relatively narrow range among pesticide formulations for different pesticides (Δ13C and Δ15N < 10‰) and within different formulations for a single substance (Δ13C and Δ15N < 2‰). Overall, this suggests that pesticide CSIA is more suited for identifying pesticide transformation processes rather than differentiating pesticide sources. Moreover, an inter-laboratory comparison showed similar δ13C (Δ13C ≤ 1.2 ‰) for the targeted substances albeit varying GC-IRMS instruments. Insignificant carbon isotopic fractionation (Δ13C < 0.5‰) was observed after 4 years of storing the same pesticide formulations, confirming their viability for long-term storage at 4 °C and future inter-laboratory comparison exercises. Altogether, the ISOTOPEST database, in open access for public use and additional contributions, marks a significant advancement in establishing an environmentally relevant pesticide CSIA approach.

Characterization of atmospheric methane release in the outer Mackenzie River delta from biogenic and thermogenic sources

Abstract. The Mackenzie River delta is the second largest Arctic river delta in the world. Thin and destabilizing permafrost coupled with vast natural gas reserves at depth, high organic-content soils, and a high proportion of wetlands create a unique ecosystem conducive to high rates of methane (CH4) emission from biogenic and thermogenic sources. Hotspots are known to have a significant contribution to summertime CH4 emissions in the region. Still, little research has been done to determine how often geologic or biogenic CH4 contributes to hotspots in the Mackenzie River delta. In the present study, stable carbon isotope analysis was used to identify the source of CH4 at several aquatic and terrestrial sites thought to be hotspots of CH4 flux to the atmosphere. Walking transects and point samples of atmospheric CH4 and CO2 concentrations were measured. Source stable carbon isotope (δ13C-CH4) signatures were derived from keeling plots of point samples and ranged from −42 ‰ to −88 ‰ δ13C-CH4, identifying both biogenic and thermogenic sources. A CH4 source was determined for eight hotspots, two of which were thermogenic in origin (−42.5 ‰, −44.7 ‰), four of which were biogenic in origin (−71.9 ‰ to −88.3 ‰), and two of which may have been produced by the oxidation of biogenic CH4 (−53.0 ‰, −63.6 ‰), as evidenced by δ13C-CH4 signatures. This indicates that the largest hotspots of CH4 production in the Mackenzie River delta are caused by a variety of sources.

Methane emissions from subglacial meltwater of three alpine glaciers in Yukon, Canada

ABSTRACT Subglacial meltwater of land-terminating glaciers in Greenland and Iceland are sources of methane (CH4) to the atmosphere, but sparse empirical data exist about the spatial distribution of subglacial CH4 production and emission from glaciers in other regions of the world. This study presents the first measurements of CH4 emissions from the subglacial meltwater of three outlet glaciers of the St. Elias Mountains in Yukon, Canada. Dissolved CH4 concentrations were highly elevated at 45, 135, and 250 times compared to the atmospheric equilibrium concentration in the meltwater of Dusty, Kluane, and Donjek glaciers, respectively. Dissolved CO2 concentrations were depleted relative to the atmospheric equilibrium. This points to the meltwater being a source of CH4 and a sink of CO2. Stable carbon (13C) and hydrogen (2H) isotopic signatures of the subglacial CH4 were depleted compared to atmospheric CH4 at all sites, indicating both biotic and abiotic sources and possible alteration from bacterial CH4 oxidation in the meltwater. No relation was found between CH4 concentrations in the meltwater and the meltwater chemistry or the size of the glaciers in this study. These findings suggest that CH4 emissions from subglacial environments under alpine glaciers may be a more common phenomenon than previously thought.

Quantitative wood anatomy and stable carbon isotopes indicate pronounced drought exposure of Scots pine when growing at the forest edge

Climate change poses a major threat to global forest ecosystems. In particular, rising temperatures and prolonged drought spells have led to increased rates of forest decline and dieback in recent decades. Under this framework, forest edges are particularly prone to drought-induced decline since they are characterized by warmer and drier micro-climatic conditions amplifying impacts of drought on tree growth and survival. Previous research indicated that forest-edge Scots pine trees have a higher growth sensitivity to water availability compared to the forest interior with consequent reduction of canopy greenness (remotely sensed NDVI) and higher mortality rates. Yet, the underlying physiological mechanisms remain largely unknown. Here, we address this knowledge gap by comparing stable carbon isotope signatures and wood anatomical traits in annual rings of trees growing at the forest edge vs. the forest interior and between trees that either survived or died during the extreme drought of 2015. Our analyses suggest that the exposure to drought of forest-edge Scots pine likely results in a reduction of stomatal conductance, as reflected by a higher δ13C of stem wood, thinner cell walls, and lower mean ring density. Moreover, we found dead trees to feature larger mean hydraulic lumen diameters and a lower cell-wall reinforcement, indicating a higher risk to suffer from cavitation. In conclusion, the typically drier micro-climatic conditions at the forest edge seem to have triggered a larger reduction of stomatal conductance of Scots pine trees, resulting in a lower carbon availability and significantly altered wood anatomical properties under an increasingly drier climate.

High urinary oxidative DNA damage in wild chimpanzees ranging in proximity of agricultural fields in Sebitoli area, Uganda.

Agriculture expansion is a major cause of habitat loss and exposure to phytochemical pollution for non-human primates. In addition to endocrine disruption, exposure to pesticides may have other sublethal physiological consequences for animals, such as generation of oxidative damage to macromolecules. In this study, we analyzed the pesticides contained in the river water across the home range of wild chimpanzees (Pan troglodytes) in Sebitoli area located on the Northern part of Kibale National Park (Uganda). We tested whether levels of three urinary markers of oxidative damage vary among individuals in relation to their ranging patterns, as a proxy for pesticide exposure intensity. To better characterize the foraging habitat use, the trophic level, and the energetic status of study individuals, we also quantified urinary levels of carbon and nitrogen stable isotope signatures and of C-peptide. Among the 511 pesticides screened, 18 compounds including herbicides, insecticides, and fungicides were found in the water sampled in the Western part of the home range of chimpanzees. In this area, chimpanzees used to feed on maize crops. By contrast, in the Eastern part where crop feeding was never observed, we found only seven pesticides. According to their ranging patterns and thus crop feeding frequency, the 139 urine samples collected from 43 Sebitoli chimpanzees were categorized as belonging to low, medium, and high exposure level. Chimpanzees from the high exposure zone had higher oxidative DNA damage (8-OHdG) than chimpanzees from both the low and medium exposure groups, who had similar levels of oxidative DNA damage. In addition, individuals with higher C-peptide tended to have significantly higher oxidative DNA damage and lipid peroxides. The three exposure groups had similar levels of urinary 8-isoprostanes and of urinary lipid peroxides. These results were robust for any potential confounding effect of other variables because neither age category nor sex or isotope levels were significantly associated with markers of oxidative damage. Our study points to genotoxic effects as one potential sublethal consequence of ranging in proximity of agricultural fields owing to exposure to pesticides or other unidentified sources of stress. Given our phylogenetic proximity, this information is relevant for the conservation of this species which is endangered and also sentinel for human health.

Sequential loss-on-ignition as a simple method for evaluating the stability of soil organic matter under actual environmental conditions

Soil organic matter (SOM) is one of the largest carbon (C) reservoirs on Earth, and therefore its stability attracts a great deal of interest from the perspective of the global C cycle. This study examined the applicability of loss-on-ignition with a stepwise increase in temperature (SIT-LOI) of soil to evaluate the stability of SOM using soil samples having different organic matter (OM) and mineral contents and different mean residence times (MRTs) for SOM. The responses of SOM to the SIT-LOI varied depending on the samples but were all successfully approximated by a liner regression model as a function of the temperature of LOI. The slope value in the liner model that determines the residual potential of carbon during the SIT-LOI highly correlated with MRT of SOM, suggesting that this value reflects the overall stability of SOM over a range of soil properties. This hypothesis was consistent with the observation that Δ14C values of SOM decreased with increasing LOI temperature and thus, older, slower-cycling SOM was preferentially left in the soil samples by SIT-LOI. Additionally, the hypothesis was also supported by the significant correlations (p < 0.01) between the slope value and OM and mineral contents in the samples because these components are considered to regulate SOM stability. In addition to the regression analysis of the SIT-LOI data, changes in carbon to nitrogen (C/N) and carbon to hydrogen (C/H) ratios and stable carbon isotope signatures (δ13C) of the samples were investigated. The results suggest that the mineral association of SOM is an important factor characterizing the response of SOM to LOI. Hence, it was concluded that SIT-LOI is a simple and useful method for evaluating the stability of SOM under actual environmental conditions.

Isotopic evidence for the effects of earthworm and straw amendment on root carbon uptake of upland rice and maize

The role of earthworms in the direct transfer of dissolved soil organic carbon to plants is poorly understood. We quantified this effect by examining the root uptake of carbon from 13C-labeled rice straw in a greenhouse experiment with three non-flooded Philippine soils that greatly differed in texture (from light sandy to loam). Measurements of carbon stable isotope signatures of aerobic rice and maize over a two-month period revealed that earthworms positively affected 13C transfer from rice straw to rice plants but not to maize plants. However, this effect was significant only in loamy and not in sandy soils. Although the direct uptake of dissolved carbon from soil had no impact on rice production, it indicated a widely ignored option to mitigate carbon loss from crop residue decomposition and associated climate risks. Its enhancement by earthworms confirms the important role of this taxon as soil engineers.

New insights on black carbon in pelagic Atlantic sediments

Black carbon (BC) is ubiquitous in pelagic sediments and presumed to have an older radiocarbon age due to long ocean residence times and pre-aging in terrestrial soils. Here, we analyzed sediments from five regions in the subtropical Atlantic Ocean to quantify the black carbon fraction of the total organic carbon pool. Black carbon, derived from the chemothermal oxidation method, comprised between 17 ± 6% of the sedimentary organic carbon in the Northwest Argentina Basin and 65 ± 18% in the Amazon Delta. Black carbon sediment accumulation rates were six times greater in the Sierra Leone Rise (8.4 ± 4.1 mg cm−2 kyr−1) compared to the remote Northwest Argentina Basin (1.3 ± 0.4 mg cm−2 kyr−1), possibly due to enhanced regional atmospheric deposition from annual African grassland fires. The radiocarbon age for BC from subtropical Atlantic sediments were more modern compared to the bulk total organic carbon, and BC source was apportioned as biomass burning byproducts from their stable carbon isotopic signatures and characteristic ratios of polycyclic aromatic hydrocarbons. This study demonstrated that subtropical Atlantic Ocean sediments serve as an important sink for young BC.

Seasonal cycles of biogeochemical fluxes in the Scotia Sea, Southern Ocean: a stable isotope approach

Abstract. The biological carbon pump is responsible for much of the decadal variability in the ocean carbon dioxide (CO2) sink, driving the transfer of carbon from the atmosphere to the deep ocean. A mechanistic understanding of the ecological drivers of particulate organic carbon (POC) flux is key both to the assessment of the magnitude of the ocean CO2 sink and for accurate predictions as to how this will change with changing climate. This is particularly important in the Southern Ocean, a key region for the uptake of CO2 and the supply of nutrients to the global thermocline. In this study we examine sediment-trap-derived particle fluxes and stable isotope signatures of carbon (C), nitrogen (N), and biogenic silica (BSi) at a study site in the biologically productive waters of the northern Scotia Sea in the Southern Ocean. Both deep (2000 m) and shallow (400 m) sediment traps exhibited two main peaks in POC, particulate N, and BSi flux: one in austral spring and one in summer, reflecting periods of high surface productivity. Particulate fluxes and isotopic compositions were similar in both deep and shallow sediment traps, highlighting that most remineralisation occurred in the upper 400 m of the water column. Differences in the seasonal cycles of isotopic compositions of C, N, and Si provide insights into the degree of coupling of these key nutrients. We measured increasing isotopic enrichment of POC and BSi in spring, consistent with fractionation during biological uptake. Since we observed isotopically light particulate material in the traps in summer, we suggest physically mediated replenishment of lighter isotopes of key nutrients from depth, enabling the full expression of the isotopic fractionation associated with biological uptake. The change in the nutrient and remineralisation regimes, indicated by the different isotopic compositions of the spring and summer productive periods, suggests a change in the source region of material reaching the traps and associated shifts in phytoplankton community structure. This, combined with the occurrence of advective inputs at certain times of the year, highlights the need to make synchronous measurements of physical processes to improve our ability to track changes in the source regions of sinking particulate material. We also highlight the need to conduct particle-specific (e.g. faecal pellets, phytoplankton detritus, zooplankton moults) isotopic analysis to improve the use of this tool in assessing particle composition of the sinking material and to develop our understanding of the drivers of biogeochemical fluxes.