Stable Isotope Ratios Research Articles

Authentication of premium Asian rice varieties: Stable isotope ratios and multi-elemental content for the identification of geographic fingerprints

Over 90 percent of the world's rice is produced and consumed in the Asia-Pacific region. Varieties such as Thai Jasmine rice and Paw San (or “Myanmar pearl rice”) are globally recognised as premium, while more local high-grade varieties include the Indonesian Ciherang and Inpari. Being able to trace the origin of these products has become necessary, since they are marketed at relatively higher prices compared to other cultivars, and they often become the target of fraudulent activities. In this work, we aimed to identify variables that could distinguish the premium-producing regions within each country, by Isotope Ratio Mass Spectrometry (IRMS) and Inductively Coupled Plasma- Mass Spectrometry (ICP-MS). Low-Level Data Fusion (LLDF) followed the analysis of more than 300 authentic samples, and (O)PLS-DA models yielded very high accuracy values. The most important geo-differentiating variables (VIP>1.4) were identified as: δ13C, δ18O, δ2H, δ34S, Co, Rb, Cu, Ba and Zn.

One place, many worlds – nutrition strategies of human groups inhabiting the site 3 in Miechów (southern Poland) since the Neolithic until the Iron Age

Abstract Studies on the ratios of stable isotopes of carbon and nitrogen constitute a research tool commonly applied in bioarchaeology to reconstruct human diets, including the origins of proteins consumed, the relationship between plant and animal foods, weaning processes, and parameters of the environment from which the food was obtained. Within the comprehensive analysis of the excavation results carried out at site 3 in Miechów (approximately 30 km north of Kraków), isotope analyses of δ13C and δ15N were performed on the human groups that inhabited the site from the Neolithic to the Iron Age. In total, 41 skeletons were investigated. The analyses aimed to hypothesise the nutritional strategies of communities of successive periods and to compare the knowledge obtained with current data and interpretations on food management in prehistoric communities of Central Europe. The results indicate a general predominance of a terrestrial diet, with plant-based foods prevailing, although not conspicuously. However, there are indications of slightly varying nutritional strategies among successive human groups. These differences are related to the contribution of animal protein and the relationship between C3 and C4 plants. For instance, in the Middle Neolithic (4th millennium BC), a greater consumption of meat and/or cereals from manured fields can be postulated compared to the Early Neolithic (late 6th and 5th millennia BC). On the other hand, the proportion of meat in the diet of Early Bronze Age inhabitants (2nd millennium BC) was possibly the lowest in the entire history of site occupation. This proportion returned to near-Neolithic levels in the developed Bronze Age and Iron Age (1st millennium BC). Regarding plant food, the results indicate greater variability in the plants consumed in the Bronze and Iron Ages. Levels of δ13C imply some contribution from C4 plants, that is, millet, during these periods. This aligns with recently formulated theories suggesting the post-Neolithic beginnings of millet cultivation and consumption in Central Europe.

An East Antarctic, sub-annual resolution water isotope record from the Mount Brown South Ice core

We report high resolution measurements of the stable water isotope ratios (δ18O, δD) from the Mount Brown South ice core (MBS, 69.11° S 86.31° E). The record covers the period 873 - 2009 CE with sub-annual temporal resolution. Preliminary analyses of surface cores have shown the Mount Brown South site has relatively high annual snowfall accumulation (0.3 metres ice equivalent) with a seasonal bias toward lower snowfall during austral summer. Precipitation at the site is frequently related to intense, short term synoptic scale events from the mid-latitudes of the southern Indian Ocean. Higher snowfall regimes are associated with easterly winds, while lower snowfall regimes are associated with south-easterly winds. Isotope ratios are measured with Infra-Red Cavity Ring Down Spectroscopy, calibrated on the VSMOW/SLAP scale and reported on the MBS2023 time scale interpolated accordingly. We provide estimates for measurement precision and internal accuracy for δ18O and δD.

The effects of fingerprinting agents on the stable isotope ratios of polyethylene films

Traditional forensic chemical comparisons of polymeric materials are often affected by fingerprinting agents that enhance and visualise finger-marks. This can inhibit detailed analysis used to provide an association or discrimination between two samples. In this study, we have demonstrated that the method for polymer comparisons using isotope ratio mass spectrometry analysis is not affected by fingerprinting matter on the surface in contrast to other forensic instrumental tests. A selection of resealable bags was analysed for carbon and hydrogen isotope ratio values of bags that had been subject to various fingerprinting agents and compared to values of untreated bags. The results showed no significant difference between samples that had been fingerprinted from those that were untreated.

Pretreatment method for oxygen stable isotope ratio analysis of the sugar-rich fraction in fruit juice via isotope ratio mass spectrometry.

The oxygen stable isotope ratio (δ18O) of the sugar-rich fraction of fruit juice is important as a tracer of the geographical origin of raw material. This study sought to minimize the inter-day variation of δ18O attributable to the influence of water to accurately monitor geographical origin labeling. Two drying devices (freeze dryer and vacuum oven) were compared. Then, two humidity levels (normal and low humidity) at which the samples were placed after drying were compared. The low-humidity environment was constructed using a glove bag and pure argon gas. δ18O was measured using thermal conversion elemental analyzer/isotope ratio mass spectrometry. Improvements were made to the measurement method based on aforementioned analyses results, and the performance of the initial and improved methods was compared. δ18O of juice dried in a vacuum oven was 3.30‰ lower than that of juice dried in a freeze dryer. Moreover, δ18O of juice samples exposed to normal humidity was 3.74‰ lower than that of samples exposed to low humidity. The combined inter-day and intra-day standard deviation was reduced from 1.20‰ in the initial method to 0.42‰ in the improved method. This study describes a pretreatment method for δ18O measurement in the sugar-rich fraction of fruit juice with less inter-day variation, and it will be useful for monitoring geographical origin labeling.

Variations of dissolved trace elements in precipitation and stream water in Japanese forest area: additional evidence of changing air pollution in the region

Trace elements released into the atmosphere by human activities, such as fossil fuel combustion, flow into forest ecosystems via wet and dry deposition and can flow out via mountainous stream water. The Kajikawa catchment site in Niigata Prefecture, located on the Sea of Japan side in central Japan, suffers from large amounts of acidic substance deposition due to its geographical conditions and meteorological seasonality and is affected by transboundary air pollution originating from the Asian continent due to northwesterly seasonal winds in winter. This study determined the concentrations of trace elements dissolved in precipitation and stream water to comprehensively evaluate the effects of transboundary air pollution on forest ecosystems. The results showed that the concentrations of trace elements and major inorganic ions in precipitation tended to be high in winter and low in summer. The fluxes of many trace elements also increased in winter, reflecting high precipitation amount. Except for Sr, the enrichment factors of the highly enriched trace elements did not show clear seasonality. Therefore, they were continuously influenced by anthropogenic activities. Furthermore, the stable Pb isotope ratio changed significantly during the observation period; however, this was not explained by seasonal changes. This study revealed that trace elements are transported to the Sea of Japan side in central Japan, especially in winter; however, their quantity and content change in response to changes in local and transboundary air pollution.Graphical

Shelf-to-basin shuttle of highly fractionated chromium isotopes in the Arctic Ocean

The oceanic chromium (Cr) cycle is mainly governed by the interconversion and the distribution of Cr(VI) and Cr(III) species and their stable isotopic ratios (δ53Cr) in the water column. As a result, the Cr cycle generates a strong correlation between the natural logarithm of its dissolved concentration and δ53Cr regardless of the location of sampling. A few studies have reported the Cr composition of certain regions falling off the global Cr array, highlighting the local prevalence of underlying mechanisms participating in the Cr cycle in the oceans. In an effort to better constrain the global Cr array, this study presents an extensive dataset for total dissolved Cr concentration ([Cr]T) and δ53Cr in the Arctic Ocean in regions meeting the environmental conditions where Cr was observed to fall off the global Cr array (e.g. continental shelves, restricted water circulation, sea ice melting). We find that more than 70% of the Arctic seawater collected plot below the global Cr array due to a small addition of highly fractionated Cr (−2.8 ‰ to −1.1 ‰) and its transport across all the Arctic regions sampled. We identify the Chukchi Shelf as the region where highly fractionated Cr is produced, from where a Cr shuttle could work in tandem with the Arctic Fe and Mn shuttles to explain the production and widespread export of isotopically light Cr in the Arctic waters. We identify a second non-reductive release of highly fractionated Cr in the Canadian Arctic Archipelago, Baffin Bay and potentially the Labrador Sea via sediment resuspension, alongside addition of isotopically light Cr originating from crustal rocks. These findings demonstrate that the Arctic-modified outflow signature of Cr isotopes modify the Cr isotopic signature of the North Atlantic waters, and that the North Atlantic waters may deviate from the global Cr array depending on whether the isotopically light Cr added to the Arctic Ocean is Cr(III) that has not been scavenged or Cr(III) that has oxidized to Cr(VI).

Stable carbon isotope ratios of pristine carbohydrates preserved within nannofossil calcite

The geochemical characterization of phytoplankton-derived organic compounds found in marine sediments has been widely used to reconstruct atmospheric pCO2 throughout the Cenozoic. This is possible owing to a well-established relationship between the carbon isotope ratios of phytoplankton biomass and CO2 concentration in the ambient seawater. An ideal molecular target for such proxy reconstructions would be degradation resistant on geologic timescales and unambiguously associated with known, experimentally tractable, organisms, so that species-specific models can be developed, calibrated, and applied to appropriate material. However, existing organic matter targets do not meet these criteria, primarily owing to ambiguity in the source species of recalcitrant compounds in deep time. Here we explore the potential of a novel organic carbon target for isotopic analysis: acidic polysaccharides extracted from the calcite plates (coccoliths) that are produced by all calcifying haptophytes. Carbohydrates are usually rapidly remineralized in sediments, but coccolith-associated polysaccharides (CAPs) are mechanically protected from diagenesis within the coccolith calcite lattice. Coccoliths can be taxonomically separated by size and identified, often to species level, prior to CAP extraction, providing a species-specific record. Coccolith morphology and composition are important additional sources of information, which are then unambiguously associated with the extracted CAPs. We found that carbon isotope ratios of CAPs changed in response to the environmental changes associated with a glacial cycle, which we attribute to temperature-driven changes in average growth rate. Once the underlying biosynthetic processes and the associated isotope effects are better understood, this archive of pristine organic matter has the potential to provide insight into phytoplankton growth rates and atmospheric pCO2 far beyond the Cenozoic, to when the first coccolithophores inhabited the surface ocean over 200 million years ago.

Reconstructing diet after the fall of the Wari Empire in the central Andean Highlands: A study of human dental calculus

Stable isotopes from bones and teeth have been used to reconstruct human lifeways in bioarchaeological research for over 30 years. Recently, there have been efforts to use less invasive methods of analysis that meet ethical standards and do not compromise the integrity of human skeletal remains. To that end, this study examines dental calculus from human teeth as a proxy for paleodietary reconstruction. This current work builds on a handful of studies that have tested the use of dental calculus for reconstructing diet, which have shown mixed results. This study contributes to those ongoing efforts to improve methods and capacities in paleodiet research. The sample is comprised of dental calculus from individuals from the Wari (600–1000 CE) and post-Wari periods (1000–1400 CE). Individuals from both time periods with stable carbon and nitrogen isotope data from the calculus are directly compared to the stable isotope results from human bone collagen, dental carbonates, and bone carbonates. Results from dental calculus show δ13C that range from -20.5 ‰ to −12.3 ‰, consistent with the use of C4 plants (maize) as a major component of the diet. The δ13C from calculus are isotopically lighter and more varied than those obtained from collagen, and this is likely explained by the distinct composition of calculus compared to that of bone collagen and apatite. The δ15N from calculus range from +8.9 ‰ to +18.8 ‰, which is heavier than expected for highland maize-based diets in the Peruvian Andes. This may be explained by 15N enrichment from aridity or crop fertilization (e.g., camelid dung), especially during the post Wari period, a time of social upheaval and severe drought. The differences in stable isotope values may also be partially explained by the diet-sourced isotopes in bone collagen (e.g., averaging the last 5–10 years of life) versus that of dental calculus (e.g., averaging the last few years of life). Documenting these differences in stable isotope ratios from distinct components may aid in richer understandings of past diets and provide additional ways to compare diet through time and space. Indeed, as more researchers begin analyzing the stable isotope ratios from dental calculus, we can minimize destructive techniques and make direct comparisons between studies that use dental calculus. We suggest that this is an important expansion of our analytical toolkit.

Stable potassium isotope ratios in human blood serum towards biomarker development in Alzheimer's disease.

The Alzheimer's disease (AD)-affected brain purges K with concurrently increasing serum K, suggesting brain-blood K transferal. Here, natural stable K isotope ratios-δ41K-of human serum samples were characterized in an AD biomarker pilot study (plus two paired Li-heparin and potassium ethylenediaminetetraacetic acid [K-EDTA] plasma samples). AD serum was found to have a significantly lower mean δ41K relative to controls. To mechanistically explore this change, novel ab initio calculations (density functional theory) of relative K isotope compositions between hydrated K+ and organically bound K were performed, identifying hydrated K+ as isotopically light (lower δ41K) compared to organically bound K. Taken together with literature, serum δ41K and density functional theory results are consistent with efflux of hydrated K+ from the brain to the bloodstream, manifesting a measurable decrease in serum δ41K. These data introduce serum δ41K for further investigation as a minimally invasive AD biomarker, with cost, scalability, and stability advantages over current techniques.

Elemental and stable isotopic signatures for dynamic traceability of genuine and "bathing" cultured Yangcheng Eriocheir sinensis crabs

This study examines whether the "bathing" culture of Chinese mitten crabs Eriocheir sinensis outside the Yangcheng Lake area converges with the origin characteristics of crabs from Yangcheng Lake and Kunshan Ponds. Inductively coupled plasma mass spectrometry (ICP-MS) and stable isotope ratio mass spectrometry (IRMS) were used to analyze mineral elements and stable isotopes in crabs at various stages of "bathing". The results indicated a dynamic transformation in the origin characteristics of "bathed" crabs; however, full convergence with genuine crabs was not achieved. Notably, disparities persisted between genuine crabs and "bathed" crabs. The combination of mineral elements and stable isotopes exhibited a discrimination accuracy of 95 % and 81.3 % between genuine crabs and "bathed crabs" from Kunshan Ponds and the Yangcheng Lake during each period of “bathing", respectively, which was higher than that using either method alone. This suggests limitations in altering original characteristics through "bathing". The combination of mineral elements and stable isotopes provides promising avenues for origin identification and understanding changes in crab characteristics during the "bathing" process. These findings highlight the complexities of crab culture practices and have implications for quality control and origin authentication in the crab industry.

Elemental and isotopic analysis of leaves predicts nitrogen-fixing phenotypes

Nitrogen (N)-fixing symbiosis is critical to terrestrial ecosystems, yet possession of this trait is known for few plant species. Broader presence of the symbiosis is often indirectly determined by phylogenetic relatedness to taxa investigated via manipulative experiments. This data gap may ultimately underestimate phylogenetic, spatial, and temporal variation in N-fixing symbiosis. Still needed are simpler field or collections-based approaches for inferring symbiotic status. N-fixing plants differ from non-N-fixing plants in elemental and isotopic composition, but previous investigations have not tested predictive accuracy using such proxies. Here we develop a regional field study and demonstrate a simple classification model for fixer status using nitrogen and carbon content measurements, and stable isotope ratios (δ15N and δ13C), from field-collected leaves. We used mixed models and classification approaches to demonstrate that N-fixing phenotypes can be used to predict symbiotic status; the best model required all predictors and was 80–94% accurate. Predictions were robust to environmental context variation, but we identified significant variation due to native vs. non-native (exotic) status and phylogenetic affinity. Surprisingly, N content—not δ15N—was the strongest predictor, suggesting that future efforts combine elemental and isotopic information. These results are valuable for understudied taxa and ecosystems, potentially allowing higher-throughput field-based N-fixer assessments.

Deciphering the transfer of hydroclimate signals to tree-ring δ18O using a proxy system model in East Asia's Meiyu region

The stable oxygen isotope ratios of whole tree-ring α-cellulose (δ18OWR) have been interpreted as an indicator of early summer hydroclimate in the Meiyu region of East Asia. However, the underlying physical mechanism often remains unclear. Here we provide a mechanistic understanding through intra-annual tree-ring oxygen isotope analysis and process-based δ18OWR modelling over the period 1979–2006. The selected tree species for analysis is Pinus taiwanensis, whose δ18OWR exhibit the strongest linear relationship with relative humidity (RH) in June. The results indicated that the June RH signal is predominantly contained in tree-ring earlywood rather than latewood. The strong response of δ18OWR to June RH is not due to the legacy effect. Using the proxy system model (PSM) of δ18OWR, we obtained a modeled δ18OWR time series that is significantly positively correlated with the measured δ18OWR time series. The modeled and measured δ18OWR series show similar relationships with monthly RH. Sensitivity experiments with PSM revealed that the June RH signal is originated from the oxygen isotopes of source water and leaf water. Rapid cellulose formation in June plays a role in enhancing the June RH signal. Our study demonstrates how δ18OWR record early summer hydroclimate signals from a process perspective, and that the PSM is effective in modelling the interannual δ18OWR variability in the Meiyu region.

A long-term study of stable isotope ratios of fingernail keratin and amino acids in a mother-infant dyad.

To evaluate the potential of compound-specific isotope analysis of amino acids (CSIA-AA) for investigating infant feeding practices, we conducted a long-term study that compared infant and maternal amino acid (AA) nitrogen isotope ratios. Fingernail samples were collected from a single mother-infant dyad over 19 months postpartum. Carbon and nitrogen stable isotope ratios were measured in the bulk keratin of the fingernail samples. Selected samples were then hydrolyzed and derivatized for compound-specific nitrogen isotope analysis of keratin AAs. As in previous studies, infant bulk keratin nitrogen isotope values increased during exclusive breastfeeding and fell with the introduction of complementary foods and eventual cessation of breastfeeding. Infant trophic AAs had elevated nitrogen isotope values relative to the mother, while the source AAs were similar between the mother and infant. Proline and threonine appeared to track the presence of human milk in the infant's diet as the isotopic composition of these AAs remained offset from maternal isotope values until the cessation of breastfeeding. Although CSIA-AA is costly and labor intensive, it appears to hold potential for estimating the duration of breastfeeding, even after the introduction of complementary foods. Through the analysis of a full suite of AAs, it may also yield insights into infant physiology and AA synthesis.

Soil organic carbon pools as influenced by 21 years of conservation agriculture management practices in Saskatchewan

Soil organic carbon (SOC) content is a key metric of soil quality and limited work has been done to examine the effect of long-term conservation agriculture management practices (CAMP) on SOC pools within western Canadian soils. We assessed the nature and permanence of sequestered SOC within 90 diverse Saskatchewan surface (0–10 cm) agricultural soils before and after 21 years of CAMP. Comparisons were made of total SOC, labile and dynamic SOC fractions (light fraction, water-extractable, and microbial biomass), respirable CO2–C during a 6-week incubation, along with spectroscopic characterization using 13C/12C stable isotope ratio and ATR-FTIR. Among soil climatic zones, the SOC content increased in the semi-arid Brown and Dark Brown soils, ranging from 2.4 to 3.7 Mg C ha−1 (111.4–187.7 kg C ha−1 year−1), but did not change in the subhumid Black, Dark Gray, and Gray soils. Overall, soils having the smallest initial SOC level were most responsive to CAMP and accumulated more SOC. According to the δ13C data, CAMP appeared to reduce annual crop moisture stress, especially within the Brown soil zone. Decreased light fraction and water-extractable SOC contents in Black, Dark Gray, and Gray soils could reflect more intense decomposition and greater surface stratification of crop residues. Brown soils experienced the largest increase in microbial biomass-C content. The CO2–C emissions from the Brown, Dark Brown, and Gray soils under CAMP suggest greater SOC stability in 2018 compared with 1996. The ATR-FTIR data pointed to enhanced SOC persistence, via more stabilized SOC forms and mineral-associated organic C fractions.

Hydrogen isotope fractionation in plants with C3, C4, and CAM CO2 fixation.

Measurements of stable isotope ratios in organic compounds are widely used tools for plant ecophysiological studies. However, the complexity of the processes involved in shaping hydrogen isotope values (δ2H) in plant carbohydrates has limited its broader application. To investigate the underlying biochemical processes responsible for 2H fractionation among water, sugars, and cellulose in leaves, we studied the three main CO2 fixation pathways (C3, C4, and CAM) and their response to changes in temperature and vapor pressure deficit (VPD). We show significant differences in autotrophic 2H fractionation (εA) from water to sugar among the pathways and their response to changes in air temperature and VPD. The strong 2H depleting εA in C3 plants is likely driven by the photosynthetic H+ production within the thylakoids, a reaction that is spatially separated in C4 and strongly reduced in CAM plants, leading to the absence of 2H depletion in the latter two types. By contrast, we found that the heterotrophic 2H-fractionation (εH) from sugar to cellulose was very similar among the three pathways and is likely driven by the plant's metabolism, rather than by isotopic exchange with leaf water. Our study offers new insights into the biochemical drivers of 2H fractionation in plant carbohydrates.

Bioarchaeological Perspectives on Late Antiquity in Dalmatia: Paleogenetic, Dietary, and Population Studies of the Hvar—Radošević burial site

Late Antiquity Dalmatia was a time and place of political unrest in the Roman Empire that influenced the lives of those in that region. The Late Antique burial site of Hvar – Radošević, spanning the 3rd to 5th centuries CE, is located on the Croatian Dalmatian island of Hvar. Given the time frame and location on a busy marine trade route, the study of this burial site offers us a glimpse into the lives of the Late Antique population living on this island. It comprises 33 individuals, with 17 buried within a confined grave tomb and the remaining individuals buried in separate locations in the tomb's proximity. The study aims to provide a new perspective on the lives of people on the island during those times by studying ancestry, population structure, possible differences within the buried population, dietary habits, and general health. The genetic analysis of the ancestral origins of the individuals buried at Hvar – Radošević revealed a diverse population reflective of the era's genetic variability. The identification of genetic outliers suggests a range of ancestries from distinct regions of the Roman Empire, possibly linked to trade routes associated with the Late Antique port in ancient Hvar. Stable isotope ratio analysis (δ13C and δ15N) indicated a diet mainly consisting of C3 plants, with minimal consumption of marine foods. High childhood mortality rates, physiological stress markers, and dental diseases suggest a low quality of life in the population. Assessment of kinship and dietary patterns revealed no discernible distinctions between individuals buried within the tomb and those buried outside, indicative of an absence of differential burial practices based on social status and familial ties among this specific buried population.

Relationship between fish traits and the methane‐derived carbon contribution to fish in a shallow lake

Abstract Although the transfer of methane‐derived carbon (MDC) to benthic macroinvertebrates such as chironomid larvae and oligochaetes has been well documented, knowledge of the transfer of MDC to fish is limited. We investigated the MDC contribution to 28 fish species through their growth stages and examined the relationship between fish traits including body size, and MDC contribution to fish within species in Lake Kasumigaura, Japan. We used carbon stable isotope ratios and a two‐source mixing model (methane‐oxidation bacteria [MOB] and particulate organic matter) to estimate the MDC contribution to fish. The MDC contribution to individual fish ranged from 0% to 21.5%. Anguilla japonica showed the highest MDC contribution (mean 3.8%). Fish species were classified into four groups according to two criteria: (a) whether the correlation between the MDC contribution and fish size (within species) was significantly negative (negative vs. not significant; ns); and (b) whether the 90th percentile of MDC contribution was 0% or not. The mean MDC contribution was highest (2.18% ± 2.93%, 12 species) for the group with (a)ns/(b)>0%, including the high contribution species such as Abbottina rivularis (mean 5.5%) and Biwia zezera (mean 9.8%). This group (12 species) included relatively high numbers of benthic habitat use (eight species) and omnivores (nine species). The mean MDC contributions were almost zero for the group with (a)ns/(b)=0% (seven species), which included only two species of benthic habitat use and one species of omnivores. The mean MDC contributions were intermediate for the other groups with (a)negative/(b)>0% (1.30% ± 1.17%, seven species) and (a)negative/(b)=0% (0.10%, two species). The negative correlation between fish size within species and MDC contribution in groups with (a)negative/(b)>0% and (a)negative/(b)=0% indicated that ontogenetic habitat and dietary shifts induced changes in MDC transfer. Our results suggest that 21 out of 28 fish species were involved in the MDC transfer in a shallow lake, but variation in MDC transfer could be explained by fish traits (trophic guild and habitat use). Although the mean MDC contribution to all fish species was low (0.61% ± 1.97%), the roughly estimated annual consumption rate of fish on MOB corresponded to approximately 10% of the MOB production in the sediment, suggesting that fish contribute to methane dynamics from the perspective of biogeochemical cycles.

Sourcing and long-range transport of particulate organic matter in river bedload: Río Bermejo, Argentina

Abstract. Fluvial transport of organic carbon from the terrestrial biosphere to the oceans is an important term in the global carbon cycle. Traditionally, the long-term burial flux of fluvial particulate organic carbon (POC) is estimated using river suspended sediment flux; however, organic carbon can also travel in river bedload as coarse particulate organic matter (POMBed). Estimates of fluvial POC export to the ocean are highly uncertain because few studies document POMbed sources, flux, and evolution during long-range fluvial transport from uplands to ocean basins. This knowledge gap limits our ability to determine the global terrestrial organic carbon burial flux. In this study we investigate the flux, sources, and transformations of POMBed during fluvial transport over a ∼1300 km long reach of the Río Bermejo, Argentina, which has no tributary inputs. To constrain sourcing of POMBed, we analyzed the composition and stable hydrogen and carbon isotope ratios (δ2H, δ13C) of plant wax biomarkers from POMBed at six locations along the Río Bermejo and compared this to samples of suspended sediment, soil, leaf litter, and floating organic debris (POMfloat) from both the lowland and headwater river system. Across all samples, we found no discernible differences in n-alkane average chain length or nC29 δ13C, indicting a common origin for all sampled POMBed. Leaf litter and POMfloat nC29 δ2H values decrease with elevation, making it a useful proxy for POMBed source elevation. Biomarker δ2H values suggest that POMBed is a mix of distally derived headwater and locally recruited floodplain sources at all sampling locations. These results indicate that POMBed can be preserved during transport through lowland rivers for hundreds of kilometers. However, the POMBed flux decreases with increasing transport distance, suggesting mechanical comminution of these coarse organic particles and progressive transfer into the suspended load. Our provisional estimates suggest that the carbon flux from POMBed comprises less than 1 % of the suspended load POC flux in the Río Bermejo. While this represents a small portion of the river POC flux, this coarse, high-density material likely has a higher probability of deposition and burial in sedimentary basins, potentially allowing it to be more effective in long-term CO2 drawdown relative to fine suspended particles. Because the rate and ratio of POMBed transport versus comminution likely vary across tectonic and climatic settings, additional research is needed to determine the importance of POMBed in the global carbon cycle.

Cryogenic vacuum distillation vs Cavitron methods in ecohydrology: Extraction protocol effects on plant water isotopic values

Stable isotope ratios of hydrogen and oxygen in plant water are widely used for water tracing in ecohydrology studies. In this approach, plant water is extracted for isotopic analysis of δ2H and δ18O. Among the extraction methods, cryogenic vacuum distillation (CVD) has been the most popular, but its impact on the isotopic composition of plant water is currently under debate. Newer Cavitron method have been proposed to replace CVD method for xylem water extraction. These recommendations have been largely based on comparisons between Cavitron-xylem water with low temperatures CVD-xylem water. However, the CVD protocol (extraction temperature and time) varies widely across laboratories, and no direct, systematic comparison has yet been made between extraction temperature and time protocols vs. the Cavitron approach. Here we compared the isotopic values of xylem water from the same tree obtained through CVD extraction at 60 °C (60, 120, 240, 360 min), 100 °C (30, 60, 120, 240 min), 140 °C (15, 30, 60, 120, 240 min), and 200 °C (15, 30 min). Subsequently, we compared the results of CVD-xylem water with Cavitron-xylem water. Our data show that isotopic values for CVD-xylem water became more positive with increasing extraction time under the same extraction temperature. Such extractions also became more isotopically positive with increasing extraction temperature for the same extraction time. When total extraction efficiency exceeded 98 %, there was no δ18O difference in CVD-xylem water among any of the different protocols (p > 0.05). However, lower extraction temperatures resulted in more negative δ2H when compared to higher temperature extraction (p < 0.05). Cavitron-xylem water was close to CVD-xylem water (average difference of 3 ‰ for δ2H and 0.5 ‰ for δ18O, n = 79) when total extraction efficiency for CVD was below 98 %. But for extraction efficiencies beyond 98 %, the Cavitron-xylem water was more negative in δ2H (17.3 ‰, n = 70) and δ18O (1.7 ‰, n = 70) than CVD-xylem water. Compared to Cavitron-xylem water, CVD-xylem water at 200 °C with extraction efficiency > 98 % was closer to the soil water. Further study is necessary to conduct a complete cross-comparison between Cavitron and CVD at different temperatures with different species at various water and salt stress conditions. But our results suggest that abandoning CVD for plant water maybe premature until such complete comparison work is done.