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Introduction: Accurate and precise delineation of the globus pallidus pars interna (GPi) and subthalamic nucleus (STN) is critical for the clinical treatment and research of Parkinson’s disease (PD). Automated segmentation is a developing technology which addresses limitations of visualizing deep nuclei on MR imaging and standardizing their definition in research applications. We sought to compare manual segmentation with three workflows for template-to-patient nonlinear registration providing atlas-based automatic segmentation of deep nuclei. Methods: Bilateral GPi, STN, and red nucleus (RN) were segmented for 20 PD and 20 healthy control (HC) subjects using 3T MRIs acquired for clinical purposes. The automated workflows used were an option available in clinical practice and two common research protocols. Quality control (QC) was performed on registered templates via visual inspection of readily discernible brain structures. Manual segmentation using T1, proton density, and T2 sequences was used as “ground truth” data for comparison. Dice similarity coefficient (DSC) was used to assess agreement between segmented nuclei. Further analysis was done to compare the influences of disease state and QC classifications on DSC. Results: Automated segmentation workflows (CIT-S, CRV-AB, and DIST-S) had the highest DSC for the RN and lowest for the STN. Manual segmentations outperformed automated segmentation for all workflows and nuclei; however, for 3/9 workflows (CIT-S STN, CRV-AB STN, and CRV-AB GPi) the differences were not statically significant. HC and PD only showed significant differences in 1/9 comparisons (DIST-S GPi). QC classification only demonstrated significantly higher DSC in 2/9 comparisons (CRV-AB RN and GPi). Conclusion: Manual segmentations generally performed better than automated segmentations. Disease state does not appear to have a significant effect on the quality of automated segmentations via nonlinear template-to-patient registration. Notably, visual inspection of template registration is a poor indicator of the accuracy of deep nuclei segmentation. As automatic segmentation methods continue to evolve, efficient and reliable QC methods will be necessary to support safe and effective integration into clinical workflows.

Compared to discharge into waterways, land application of treated municipal effluent (TME) can reduce the need for both inorganic fertilizers and irrigation. However, TME irrigation may result in the accumulation of phosphorus (P) or trace elements in soil, and increased salinity and sodicity, which could damage soil structure and reduce infiltration. TME irrigation can also result in groundwater contamination through nitrate leaching or surface water contamination through runoff. This study aimed to evaluate the effects of increasing TME irrigation rates on quantity and quality of leachate and pasture growth in a lysimeter experiment using a Fluvial Recent soil and a Fragic Pallic soil. Pasture growth in the lysimeters was up to 2.5-fold higher in the TME treatments compared to the non-irrigated treatments. There were no signs of toxicity or accumulation of B, Al, Cd, Cu, Fe, Mn, As, and Zn. TME significantly increased the concentration of P and Na in the pasture. Nitrogen leaching from the lysimeters was negligible (

Sources of dissolved and particulate carbon to the Fraser River system vary significantly in space and time. Tributaries in the northern interior of the basin consistently deliver higher concentrations of dissolved organic carbon (DOC) to the main stem than other tributaries. Based on samples collected near the Fraser River mouth throughout 2013, the radiocarbon age of DOC exported from the Fraser River does not change significantly across seasons despite a spike in DOC concentration during the freshet, suggesting modulation of heterogeneous upstream chemical and isotopic signals during transit through the river basin. Dissolved inorganic carbon (DIC) concentrations are highest in the Rocky Mountain headwater region where carbonate weathering is evident, but also in tributaries with high DOC concentrations, suggesting that DOC respiration may be responsible for a significant portion of DIC in this basin. Using an isotope and major ion mass balance approach to constrain the contributions of carbonate and silicate weathering and DOC respiration, we estimate that up to 33 +/- 11% of DIC is derived from DOC respiration in some parts of the Fraser River basin. Overall, these results indicate close coupling between the cycling of DOC and DIC, and that carbon is actively processed and transformed during transport through the river network., Biogeochemistry, 164 (1), ISSN:0168-2563, ISSN:1573-515X

Two sediment cores collected in the shelf off Rio de Janeiro (RJ13-01B: 10.8 cal kyr BP, and RJ13-02B: 4.7 cal kyr BP) were investigated in high-resolution to evaluate changes in sedimentary processes and paleoclimatic and paleoceanographic variability during the Holocene in the Southeastern Brazil. Information from inorganic proxies of continental input (Al/Ca and Fe/Ca), redox-sensitive elements (Fe/Al, V/Al and Mn/Al), paleoproductivity (Sr/Al, Cd/Al and Ba/Al), as well as data for grain size, geophysical properties (p-wave velocity, gamma-ray density, acoustic impedance, magnetic susceptibility and porosity), Si, total organic carbon and calcium carbonate were considered. The data revealed three main periods of sediment accumulation: (i) from 10.8 cal kyr BP to 7.6 cal kyr BP the sediment was coarse, Si content was high (27%), the magnetic susceptibility was low and the presence of shell fragments all suggest a period of low continental input and the deposition site was shallow (i.e, lower sea level); (ii) from 7.5 cal kyr BP to 4.6 cal kyr BP the elevated ratios of Al/Ca (0.69 ± 0.08), Fe/Ca (0.27 ± 0.04), Sr/Al (31.57 ± 4.47) ×10−4, Cd/Al (0.09 ± 0.03) ×10−5 and Ba/Al (0.70 ± 0.16) ×10−4 are consistent with a period of maximum sea transgression and elevated influence of the nutrient-rich South Atlantic Central Water (SACW); (iii) from 4.5 cal kyr BP to the present, events of higher fluxes of TOC, Ni, Cu and Zn were observed from ca 3.2 cal kyr BP to 3.4 cal kyr BP, in both cores, related to humid climate. Overall, the multi-proxy approach shed light on the effects of climate and oceanographic variability on sediment input and accumulation in a less-studied portion of the Brazilian shelf, which are consistent with other shelf areas and with changes in regional climate systems like the Intertropical Convergence Zone (ITCZ), South American Monsoon Systems (SAMS) and South Atlantic Convergence Zone (SACZ).

Constraints on timescales of lateral transport of sedimentary organic carbon (OC) over continental shelves and associated influences on the distribution and abundance of OC remain sparse. Preferential degradation of labile, young OC during lateral transport results in apparent “diagenetic aging” of OC. Additionally, sediment translocation can also result in “transport time-associated aging” of associated organic matter (OM) as a function of the lateral transport time (LTT). Here, we use a coupled thermal decomposition and radiocarbon (14C) approach to constrain timescales of lateral transport and concomitant loss of OC associated with different grain size fractions of sediments collected from two locations ∼275 km apart along a dispersal pathway on the inner shelf of the East China Sea. The 14C age contrasts between corresponding thermal fractions are used to distinguish these two components of sedimentary OM “aging”. To minimize interferences from hydrodynamic sorting and diagenetic aging of OC accompanying lateral transport, we assess 14C age differences of decomposition products from the most thermally-refractory OC components associated with specific grain size fractions between locations. We show that LTTs vary among different grain size fractions, and examine relationships between LTTs and sedimentary OC loss in order to assess the decomposition of OC as a consequence of lateral transport. We suggest that the decomposition of OC associated with protracted lateral transport exerts a strong influence on OC burial efficiency, with broad implications for carbon cycling over continental shelves., Organic Geochemistry, 128, ISSN:0146-6380

Inland waters play a major role in the global carbon cycle, with particulate organic carbon (POC) burial in terrestrial wetlands surpassing that in ocean sediments. Lake Constance, the second largest lake at the periphery of the European Alps, receives POC sourced from both aquatic and terrestrial productivity as well as petrogenic OC (OCpetro) from bedrock erosion. Distinguishing POC inputs to lake sediments is key to assessing carbon flux and fate as reworked OCpetro represents neither a net sink of atmospheric CO2 nor source of O2. New stable and radiocarbon isotopic data indicate that 11 (9–12) Gg/yr of OCpetro is buried in Lake Constance with underlying sediments on average containing 0.3 (0.25–0.33) wt% OCpetro. Extrapolation of these results suggests that 27 TgOCpetro/yr (12–54 TgOC/yr) could be subject to temporary geological storage in lakes globally, which is comparable to estimates of 43−25+61 TgOCpetro/yr delivered to the ocean by rivers (Galy et al., 2015). More studies are needed to quantify OCpetro burial in inland sedimentary reservoirs in order to accurately account for atmospheric carbon sequestration in terrestrial basins. ISSN:0009-2541 ISSN:1872-6836

Relatively little is known about the amount of time that lapses between the photosynthetic fixation of carbon by vascular land plants and its incorporation into the marine sedimentary record, yet the dynamics of terrestrial carbon sequestration have important implications for the carbon cycle. Vascular plant carbon may encounter multiple potential intermediate storage pools and transport trajectories, and the age of vascular plant carbon accumulating in marine sediments will reflect these different pre-depositional histories. Here, we examine down-core 14C profiles of higher plant leaf wax-derived fatty acids isolated from high fidelity sedimentary sequences spanning the so-called “bomb-spike” and encompassing a ca. 60-degree latitudinal gradient from tropical (Cariaco Basin), temperate (Saanich Inlet), and polar (Mackenzie Delta) watersheds to constrain integrated vascular plant carbon storage/transport times (“residence times”). Using a modeling framework, we find that, in addition to a “young” (conditionally defined as < 50 y) carbon pool, an old pool of compounds comprises 49 to 78 % of the fractional contribution of organic carbon (OC) and exhibits variable ages reflective of the environmental setting. For the Mackenzie Delta sediments, we find a mean age of the old pool of 28 ky (±9.4, standard deviation), indicating extensive pre-aging in permafrost soils, whereas the old pools in Saanich Inlet and Cariaco Basin sediments are younger, 7.9 (±5.0) and 2.4 (±0.50) to 3.2 (±0.54) ky, respectively, indicating less protracted storage in terrestrial reservoirs. The “young” pool showed clear annual contributions for Saanich Inlet and Mackenzie Delta sediments (comprising 24% and 16% of this pool, respectively), likely reflecting episodic transport of OC from steep hillside slopes surrounding Saanich Inlet and annual spring flood deposition in the Mackenzie Delta, respectively. Contributions of 5–10 year old OC to the Cariaco Basin show a short delay of OC inflow, potentially related to transport time to the offshore basin. Modeling results also indicate that the Mackenzie Delta has an influx of young but decadal material (20–30 years of age), pointing to the presence of an intermediate reservoir. Overall, these results show that a significant fraction of vascular plant C undergoes pre-aging in terrestrial reservoirs prior to accumulation in deltaic and marine sediments. The age distribution, reflecting both storage and transport times, likely depends on landscape-specific factors such as local topography, hydrographic characteristics, and mean annual temperature of the catchment, all of which affect the degree of soil buildup and preservation. We show that catchment-specific carbon residence times across landscapes can vary by an order of magnitude, with important implications both for carbon cycle studies and for the interpretation of molecular terrestrial paleoclimate records preserved in sedimentary sequences.

Significance Terrestrial organic-carbon reservoirs (vegetation, soils) currently consume more than a third of anthropogenic carbon emitted to the atmosphere, but the response of this “terrestrial sink” to future climate change is widely debated. Rivers export organic carbon sourced over their watersheds, offering an opportunity to assess controls on land carbon cycling on broad spatial scales. Using radiocarbon ages of biomolecular tracer compounds exported by rivers, we show that temperature and precipitation exert primary controls on biospheric-carbon turnover within river basins. These findings reveal large-scale climate control on soil carbon stocks, and they provide a framework to quantify responses of terrestrial organic-carbon reservoirs to past and future change., Terrestrial vegetation and soils hold three times more carbon than the atmosphere. Much debate concerns how anthropogenic activity will perturb these surface reservoirs, potentially exacerbating ongoing changes to the climate system. Uncertainties specifically persist in extrapolating point-source observations to ecosystem-scale budgets and fluxes, which require consideration of vertical and lateral processes on multiple temporal and spatial scales. To explore controls on organic carbon (OC) turnover at the river basin scale, we present radiocarbon (14C) ages on two groups of molecular tracers of plant-derived carbon—leaf-wax lipids and lignin phenols—from a globally distributed suite of rivers. We find significant negative relationships between the 14C age of these biomarkers and mean annual temperature and precipitation. Moreover, riverine biospheric-carbon ages scale proportionally with basin-wide soil carbon turnover times and soil 14C ages, implicating OC cycling within soils as a primary control on exported biomarker ages and revealing a broad distribution of soil OC reactivities. The ubiquitous occurrence of a long-lived soil OC pool suggests soil OC is globally vulnerable to perturbations by future temperature and precipitation increase. Scaling of riverine biospheric-carbon ages with soil OC turnover shows the former can constrain the sensitivity of carbon dynamics to environmental controls on broad spatial scales. Extracting this information from fluvially dominated sedimentary sequences may inform past variations in soil OC turnover in response to anthropogenic and/or climate perturbations. In turn, monitoring riverine OC composition may help detect future climate-change–induced perturbations of soil OC turnover and stocks.

Compound-specific radiocarbon (14C) dating often requires working with small samples of < 100 µg carbon (µgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 µgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis., Radiocarbon, 62 (1), ISSN:0033-8222

Ocean dynamics served an important role during past dramatic climate changes via impacts on deep-ocean carbon storage. Such changes are recorded in sedimentary proxies of hydrographic change on continental margins, which lie at the ocean–atmosphere–earth interface. However, interpretations of these records are challenging, given complex interplays among processes delivering particulate material to and from ocean margins. Here we report radiocarbon (14C) signatures measured for organic carbon in differing grain-size sediment fractions and foraminifera in a sediment core retrieved from the southwest Iberian margin, spanning the last ~25,000 yr. Variable differences of 0–5000 yr in radiocarbon age are apparent between organic carbon in differing grain-sizes and foraminifera of the same sediment layer. The magnitude of 14C differences co-varies with key paleoceanographic indices (e.g., proximal bottom-current density gradients), which we interpret as evidence of Atlantic–Mediterranean seawater exchange influencing grain-size specific carbon accumulation and translocation. These findings underscore an important link between regional hydrodynamics and interpretations of down-core sedimentary proxies., Marine sedimentary records and the proxies within play a central role in unlocking our understanding of past climates, yet interpreting the signals they contain can be complex. Here, the authors reveal and discuss the complex effects of hydrodynamics on carbon accumulation in the sediments off the Iberian margin.

Understanding the effects of hydrodynamic forcing on organic matter (OM) composition is important for assessment of organic carbon (OC) burial in marginal seas on regional and global scales. Here we examine the relationships between regional oceanographic conditions (bottom shear stress), and the physical characteristics (mineral surface area and grain size) and geochemical properties (OC content [OC%] and carbon isotope compositions [13C, 14C]) of a large suite of surface sediments from the Chinese marginal seas to assess the influence of hydrodynamic processes on the fate of OM on shallow continental shelves. Our results suggest that 14C content is primarily controlled by organo‐mineral interactions and hydrodynamically driven resuspension processes, highlighted by (i) positive correlations between 14C content and OC% (and surface area) and (ii) negative correlations between 14C content and grain size (and bottom shear stress). Hydrodynamic processes influence 14C content due to both OC aging during lateral transport and accompanying selective degradation of OM associated with sediment (re) mobilization, these effects being superimposed on the original 14C characteristics of carbon source. Our observations support the hypotheses of Blair and Aller (2012, https://doi.org/10.1146/annurev‐marine‐120709‐142717) and Leithold et al. (2016, https://doi.org/10.1016/j.earscirev.2015.10.011) that hydrodynamically driven sediment translocation results in greater OC 14C depletion in broad, shallow marginal seas common to passive margin settings than on active margins. On a global scale, this may influence the extent to which continental margins act as net carbon sources and sinks. Our findings thus suggest that hydrodynamic processes are important in shaping the nature, dynamics, and magnitude of OC export and burial in passive marginal seas.

International audience; Specific n-alkanes and n-alkanoic acids are commonly used as biomarkers in paleoenvironmental reconstruction, yet any individual homologue may originate from multiple biological sources. Here we improve source and age controls for these compounds in meromictic systems by measuring the radiocarbon (C-14) ages of specific homologues preserved in twentieth century Lake Pavin (France) sediments. In contrast to many studies, C-14 ages generally decreased with increasing carbon chain length, from 7.3 to 2.6 ka for the C-14-C-30 n-alkanoic acids and from 9.2 to 0.3 ka for the C-21-C-33 n-alkanes. Given a known hard water effect, these values suggest that aquatic microbial sources predominate and contributed to most of the homologues measured. Only the longest chain n-alkanes exclusively represent inputs of higher plant waxes, which were previously sequestered in soils over centennial to millennial timescales prior to transport and deposition. These findings suggest that biomarker source and age should be carefully established for lacustrine settings.

Sediments in deep ocean trenches may contain crucial information on past earthquake history and constitute important sites of carbon burial. Here we present 14C data on bulk organic carbon (OC) and its thermal decomposition fractions produced by ramped pyrolysis/oxidation for a core retrieved from the >7.5 km-deep Japan Trench. High-resolution 14C measurements, coupled with distinctive thermogram characteristics of OC, reveal hemipelagic sedimentation interrupted by episodic deposition of pre-aged OC in the trench. Low δ13C values and diverse 14C ages of thermal fractions imply that the latter material originates from the adjacent margin, and the co-occurrence of pre-aged OC with intervals corresponding to known earthquake events implies tectonically triggered, gravity-flow-driven supply. We show that 14C ages of thermal fractions can yield valuable chronological constraints on sedimentary sequences. Our findings shed new light on links between tectonically driven sedimentological processes and marine carbon cycling, with implications for carbon dynamics in hadal environments., Within sediments in deep ocean trenches an earthquake record may be observed. Here, the authors present 14C data on bulk organic carbon (OC) and thermal decomposition from a sediment core in the Japan Trench and match OC values with known earthquake events.

This study examines temporal variations of the abundance and carbon isotopic characteristics of particulate organic carbon (POC) and specific-source compounds in the context of hydrological variability in the Yellow River. The content and bulk carbon isotopic characteristics (13C and 14C) of POC were relatively uniform over the hydrologic (seasonal) cycle. We attribute these temporally invariant geochemical characteristics to the dominant contribution of loess material to the suspended particulate matter (SPM). In contrast, molecular-level signals revealed that hydrologic conditions exert a significant influence on the proportional contributions of petrogenic and especially fresh plant-derived OC, while pre-aged soil OC is mobilized via deeper erosion processes (e.g., gully erosion, mudslides) and is independent of hydrodynamics and surface runoff. A coupled biomarker-isotope mixing model was applied to estimate the time-varying supply of contemporary/modern biomass, pre-aged soil, and fossil OC components to Chinese marginal seas from the Yellow River. We found that natural (e.g., precipitation) and human-induced (e.g., water and sediment regulation) variations in hydrological regime strongly influence the flux with the magnitude of the corresponding annual fluxes of POC ranging between 0.343 ± 0.122 Mt yr−1 and 0.581 ± 0.213 Mt yr−1, but less strongly infleunce proportions of the different OC constituents. Inter-annual differences in pre-aged soil and fossil OC fluxes imply that extreme climate events (e.g., floods) modulate the exhumation and export of old carbon to the ocean, but the OC homogeneity in the pre-aged mineral soil-dominated watersheds facilitates robust predictions in terms of OC transport dynamics in the past (sediment cores) and in the future.

Humans have interacted with fire for thousands of years, yet the utilization of fossil fuels marked the beginning of a new era. Ubiquitous in the environment, pyrogenic carbon (PyC) arises from incomplete combustion of biomass and fossil fuels, forming a continuum of condensed aromatic structures. Here, we develop and evaluate 14C records for two complementary PyC molecular markers, benzene polycarboxylic acids (BPCAs) and polycyclic aromatic hydrocarbons (PAHs), preserved in aquatic sediments from a suburban and a remote catchment in the United States (U.S.) from the mid-1700s to 1998. Results show that the majority of PyC stems from local sources and is transferred to aquatic sedimentary archives on subdecadal to millennial time scales. Whereas a small portion stems from near-contemporaneous production and sedimentation, the majority of PyC (∼90%) experiences delayed transmission due to “preaging” on millennial time scales in catchment soils prior to its ultimate deposition. BPCAs (soot) and PAHs (precu...

We present dissolved organic carbon (DOC) concentrations, particulate organic matter (POM) composition (δ13C, δ15N, ∆14C, N/C), and particulate glycerol dialkyl glycerol tetraether (GDGT) distributions from a 34-month time-series near the mouth of the Congo River. An end-member mixing model using δ13C and N/C indicates that exported POM is consistently dominated by C3 rainforest soil sources, with increasing contribution from C3 vegetation and decreasing contribution from phytoplankton at high discharge. Large C4 inputs are never observed despite covering ≈ 13% of the catchment. Low and variable ∆14C values during 2011 [annual mean = (− 148 ± 82) ‰], when discharge from left-bank tributaries located in the southern hemisphere reached record lows, likely reflect a bias toward pre-aged POM derived from the Cuvette Congolaise swamp forest. In contrast, ∆14C values were stable near − 50‰ between January and June 2013, when left-bank discharge was highest. We suggest that headwater POM is replaced and/or diluted by C3 vegetation and pre-aged soils during transit through the Cuvette Congolaise, whereas left-bank tributaries export significantly less pre-aged material. GDGT distributions provide further evidence for seasonal and inter-annual variability in soil provenance. The cyclization of branched tetraethers and the GDGT-0 to crenarchaeol ratio are positively correlated with discharge (r ≥ 0.70; p-value ≤ 4.3 × 10− 5) due to the incorporation of swamp-forest soils when discharge from right-bank tributaries located in the northern hemisphere is high. Both metrics reach record lows during 2013, supporting our interpretation of increased left-bank contribution at this time. We conclude that hydrologic variability is a major control of POM provenance in the Congo River Basin and that tropical wetlands can be a significant POM source despite their small geographic coverage.

Compound-specific radiocarbon analysis (CSRA) of benzene polycarboxylic acids (BPCAs) yields molecular-level, source-specific information necessary to constrain isotopic signatures of pyrogenic carbon. However, the purification of individual BPCAs requires a multistep procedure that typically results in only microgram quantities of the target analyte(s). Such small samples are highly susceptible to contamination by extraneous carbon, which needs to be minimized and carefully accounted for in order to yield accurate results. Here, we undertook comprehensive characterization and quantification of contamination associated with molecular radiocarbon (14C) BPCA analyses through systematic processing of multiple authentic standards with both fossil and modern 14C signatures at various concentrations. Using this approach, we precisely apportion the contribution of extraneous carbon with respect to the four implemented subprocedures. Assuming a constant source and quantity of extraneous carbon we correct and statistically evaluate uncertainties in resulting 14C data. Subsequently, we examine the results of triplicate analyses of reference materials representing four different environmental matrices (sediment, soil, aerosol, riverine natural organic matter) and apportion their BPCA sources in terms of carbon residues derived from biomass or fossil fuel combustion. This comprehensive approach to CSRA facilitates retrieval of robust 14C data, with application in environmental studies of the continuum of pyrogenic carbon.

Precisely-dated stalagmites are increasingly important archives for the reconstruction of terrestrial paleoclimate at very high temporal resolution. In-depth understanding of local conditions at the cave site and of the processes driving stalagmite deposition is of paramount importance for interpreting proxy signals incorporated in stalagmite carbonate. Here we present a sub-decadally resolved dead carbon fraction (DCF) record for a stalagmite from Yok Balum Cave (southern Belize). The record is coupled to parallel stable carbon isotope (delta C-13) and U/Ca measurements, as well as radiocarbon (C-14) measurements from soils overlying the cave system. Using a karst carbon cycle model we disentangle the importance of soil and karst processes on stalagmite DCF incorporation, revealing a dominant host rock dissolution control on total DCF. Covariation between DCF, delta C-13, and U/Ca indicates that karst processes are a common driver of all three parameters, suggesting possible use of delta C-13 and trace element ratios to independently quantify DCF variability. A statistically significant multi-decadal lag of variable length exists between DCF and reconstructed solar activity, suggesting that solar activity influenced regional precipitation in Mesoamerica over the past 1500 years, but that the relationship was non-static. Although the precise nature of the observed lag is unclear, solar-induced changes in North Atlantic oceanic and atmospheric dynamics may play a role. (C) 2016 Elsevier Ltd. All rights reserved.

Lignin is a key component of soil dissolved organic carbon (DOC) and is recently suggested to track 14C-young DOC components. However, direct evidence is still lacking to prove this hypothesis in the soil. Here, utilizing molecular radiocarbon dating, we present the first 14C dataset on dissolved lignin through a Podzol soil profile. Dissolved lignin and hydroxy phenols had similar 14C content as soil organic carbon (SOC) and DOC in the surface organic layer. However, in contrast to SOC, both DOC and dissolved lignin phenols exhibited consistent and higher Δ14C values in the mineral soils. Coupled with lignin phenol concentration data, our results suggest that dissolved lignin comprises a key DOC component throughout this Podzol profile and is mainly supplied by surface leachates with young 14C ages.

Speleothem organic matter can be a powerful tracer for past environmental conditions and karst processes. Carbon isotope measurements (δ13C and 14C) in particular can provide crucial information on the provenance and age of speleothem organic matter, but are challenging due to low concentrations of organic matter in stalagmites. Here, we present a method development study on extraction and isotopic characterization of speleothem organic matter using a rapid procedure with low laboratory contamination risk. An extensive blank assessment allowed us to quantify possible sources of contamination through the entire method. Although blank contamination is consistently low (1.7 ± 0.34 – 4.3 ± 0.86 μg C for the entire procedure), incomplete sample decarbonation poses a still unresolved problem of the method, but can be detected when considering both δ13C and 14C values. We test the method on five stalagmites, showing reproducible results on samples as small as 7 μg C for δ13C and 20 μg C for 14C. Furthermore, we find consistently lower non-purgeable organic carbon (NPOC) 14C values compared to the carbonate 14C over the bomb spike interval in two stalagmites from Yok Balum Cave, Belize, suggesting overprint of a pre-aged or even fossil source of carbon on the organic fraction incorporated by these stalagmites.

Highlights • Continental margin-scale spatial variability in C values among grain size fractions is presented. • Two different hydrodynamic modes influencing in 14C heterogeneity are identified. • A new index (H14 index) is defined to describe overall 14C heterogeneity within marine surface sedimentary OC. Abstract The deposition and long-term burial of sedimentary organic matter (OM) on continental margins comprises a fundamental component of the global carbon cycle. A key unknown in interpretation of carbon isotope records of sedimentary OM is the extent to which OM accumulating in continental shelf and slope sediments is influenced by dispersal and redistribution processes. Here, we present results from an extensive survey of organic carbon (OC) characteristics of grain size fractions (ranging from

Substances enriched with radiocarbon can easily contaminate samples and laboratories used for natural abundance measurements. We have developed a new method using wet chemical oxidation for swabbing laboratories and equipment to test for 14C contamination. Here, we report the findings of 18 months’ work and more than 800 tests covering studies at multiple locations. Evidence of past and current use of enriched 14C was found at all but one location and a program of testing and communication was used to mitigate its effects. Remediation was attempted with mixed success and depended on the complexity and level of the contamination. We describe four cases from different situations.

Studies using carbon isotopes to understand the global carbon cycle are critical to identify and quantify sources, sinks, and processes and how humans may impact them. 13C and 14C are routinely measured individually; however, there is a need to develop instrumentation that can perform concurrent online analyses that can generate rich data sets conveniently and efficiently. To satisfy these requirements, we coupled an elemental analyzer to a stable isotope mass spectrometer and an accelerator mass spectrometer system fitted with a gas ion source. We first tested the system with standard materials and then reanalyzed a sediment core from the Bay of Bengal that had been analyzed for 14C by conventional methods. The system was able to produce %C, 13C, and 14C data that were accurate and precise, and suitable for the purposes of our biogeochemistry group. The system was compact and convenient and is appropriate for use in a range of fields of research.

Marginal seas are estimated to account for up to 90% of organic carbon (OC) burial in marine sediments, and thus play an important role in global carbon cycle. However, comprehensive assessments of carbon budgets for marginal sea systems are challenging due to their inherent complexity, with spatial and temporal variability in carbon inputs and dispersal processes. We examine the Bohai Sea and Yellow Sea (BS–YS) in order to further our understanding of sedimentary OC delivery, translocation and accumulation in a shallow marginal sea system. Bulk properties and the content and isotopic compositions (Δ14C, δ13C) of source-specific plant wax n-alkyl lipid biomarkers were determined for a suite of surficial sediment samples. Variable δ13C values (−25.1‰ to −28.5‰) and contemporary radiocarbon ages of short-chain n-fatty acids (FAs; C16, C18) reflect modern autochthonous marine and/or fresh terrestrial plant input. In contrast, extremely depleted Δ14C values (−932‰ to −979‰) of short-chain n-alkanes (C16, C18) suggest a predominant input from sedimentary rocks (petrogenic OC) or petroleum. Abundance-weighted average δ13C and Δ14C values of long-chain leaf wax lipids (C26+28+30 n-FAs, C24+26+28 n-alkanols, C27+29+31 n-alkanes) are −29.1 ± 1.1‰ to −30.2 ± 0.3‰, and −286 ± 150‰ to −442 ± 119‰, respectively, illustrating that terrestrial OC delivery is dominated by pre-aged (∼3000–5000 14C yrs) C3 vegetation sources. A coupled carbon-isotopic mixing model, based on the bulk and compound-specific biomarker δ13C and Δ14C values, is used to partition the BS–YS sedimentary OC into three components that reflect both origins and transport processes. For all sampling sites, 31–64% is modern/contemporary OC, 24–49% is pre-aged terrestrial OC, and 7–26% is fossil OC, the latter likely derived from both physical erosion of ancient sedimentary rocks and fossil fuel sources. Pre-aged soil OC is most prominent in front of the modern and old Huanghe (Yellow River) delta (48% and 49%), and fossil OC is most significant north of the old Huanghe mouth (26%). Significant pre-aged soil contributions (33%) are also evident for sites further offshore, where transport and deposition of eolian dust supply may be important. For the three major deposition areas of the BS–YS system (Bohai Basin, sub-aqueous Huanghe delta and central south YS basin), we estimate that about 3.02 Mt/yr of refractory, plant-derived pre-aged soil OC and 0.98 Mt/yr of 14C-depleted fossil OC accumulates in surface sediments, corresponding to 35% and 11% of sediment TOC, respectively. Compared with estimates for fluxes from corresponding sources, the burial efficiency is close to 100% for pre-aged soil OC and 70% for fossil OC, implying efficient OC burial in delta and shelf environments. Re-burial of these two pools of terrigenous OC only affects carbon cycling on millennial and longer timescales respectively, and exerts little influence on the modern carbon cycle (

Robust chronologies are crucial for the correct interpretation of climate proxy records and for detailed reconstructions of palaeoclimate. Stalagmites have garnered strong interest as recorders of past climate in part due to their amenability to U-series dating. However, many stalagmites are not dateable using this technique due to low 238U and/or high detrital Th concentrations (e.g., many tropical cave systems (Adkins et al., 2013)), and occasionally these issues affect stalagmites across wide geographical regions (e.g., large parts of Australia (Green et al. 2013)) complicating the use of stalagmites in these areas. Radiocarbon (14C) offers an alternative method of dating stalagmites, but issues associated with the ‘dead carbon fraction’ (DCF) have historically hindered this approach. Here, a novel 14C-based method for dating stalagmites is presented and discussed. The technique calculates a best-fit growth rate between a time-series of stalagmite 14C data and known atmospheric 14C variability. The new method produces excellent results for stalagmites that satisfy four requirements: i) the absence of long-term secular variability in DCF (i.e., stalagmite DCF varies around a mean value with no long-term trend), ii) stalagmite growth rate does not vary significantly (the technique identifies stalagmites with substantial growth rate variability), iii) the stalagmite record is long enough that measurable 14C decay has occurred, and iv) one ‘anchor’ point exists where the calendar age is known. The model produces good results for a previously U–Th dated stalagmite from Heshang Cave, China, and is then applied to an undated stalagmite from southern Poland. The new method will not replace high-precision U–Th measurements, because the precision of the technique is difficult to quantify. However, it provides a means for dating certain stalagmites undateable by conventional U–Th methods and for refining coarse U–Th chronologies.

Radiocarbon measurements in tree rings can be used to estimate atmospheric 14C concentration and thereby used to create a 14C calibration curve. When wood is discovered in construction sites, rivers, buildings, and lake sediments, it is unclear if the wood could fill gaps in the 14C calibration curve or if the wood is of historical interest until the age is determined by dendrochronology or 14C dating. However, dendrochronological dating is subjected to many requirements and 14C dating is costly and time consuming, both of which can be frivolous endeavors if the samples are not in the age range of interest. A simplified 14C dating technique, called Speed Dating, was thus developed. It can be used to quickly obtain 14C ages as wood samples are neither chemically treated nor graphitized. Instead, wood is combusted in an elemental analyzer (EA) and the CO2 produced is carried into an accelerator mass spectrometer (AMS) with a gas ion source. Within a day, 75 samples can be measured with uncertainties between 0.5–2% depending on the age, preservation, and contaminants on the material and Speed Dating costs about one-third of conventional AMS dates.

The occurrence of pre-aged organic carbon (OC) in continental margin surface sediments is a commonly observed phenomenon, yet the nature, sources, and causes of this aged OC remain largely undetermined for many continental shelf settings. Here we present the results of an extensive survey of the abundance and radiocarbon content of OC in surface sediments from the northern Chinese marginal seas. Pre-aged OC is associated with both coarser (>63 µm) and finer (

The radiocarbon content of dissolved organic carbon (DOC) in rivers, lakes, and other non-saline waters can provide valuable information on carbon cycling dynamics in the environment. DOC is typically prepared for 14C analysis by accelerator mass spectrometry (AMS) either by ultraviolet (UV) oxidation or by freeze-drying and sealed tube combustion. We present here a new method for the rapid analysis of 14C of DOC using wet chemical oxidation (WCO) and automated headspace sampling of CO2. The approach is an adaption of recently developed methods using aqueous persulfate oxidant to determine the δ13C of DOC in non-saline water samples and the 14C content of volatile organic acids. One advantage of the current method over UV oxidation is higher throughput: 22 samples and 10 processing standards can be prepared in one day and analyzed in a second day, allowing a full suite of 14C processing standards and blanks to be run in conjunction with samples. A second advantage is that there is less potential for cross-contamination between samples.

The New Zealand fjords are located at a latitude where distinct oceanic and atmospheric fronts separate carbon reservoirs of varying residence time. The marine radiocarbon reservoir age in this region is likely to deviate from the global average reservoir age over space and time as frontal boundaries migrate north and south. Here we present new estimates of modern radiocarbon reservoir age using the radiocarbon content of bivalve shells collected live before 1950. Multiple measurements from hydrographically distinct sites support the use of a ΔR, defined as the regional offset between measured and modeled marine radiocarbon reservoir age, of 59 ± 35 years for the New Zealand fjords. We also assess the radiocarbon content of bulk surface sediments throughout the fjord region. Sediment with a higher proportion of marine organic carbon has relatively less radiocarbon than more terrestrial sediment, suggesting a short residence time of organic carbon on land before deposition in the fjords. Additionally, we constrain reservoir age variability throughout the Holocene using coeval terrestrial and marine macrofossils. Although our modern results suggest spatial consistency in ΔR throughout the fjords, large deviations from the global average marine radiocarbon reservoir age exist in the paleo record. We find four ancient ΔR values, extending back to ∼10.2 cal kyr BP, to be negative or near zero. A likely cause of younger radiocarbon reservoir ages at select intervals throughout the Holocene is the increased influence of the Southern Hemisphere westerly winds, which cause extreme precipitation in the region that delivers terrestrial carbon, enriched in radiocarbon, to fjord basins. However, bivalve depth habitat may also influence radiocarbon content due to a stratified water column containing distinct carbon pools. This work highlights the need for thorough assessment of local radiocarbon cycling in similar regions of dynamic ocean/atmosphere frontal zones, especially fjords and other semi-restricted estuaries.

The mobilization of glacial permafrost carbon during the last glacial–interglacial transition has been suggested by indirect evidence to be an additional and significant source of greenhouse gases to the atmosphere, especially at times of rapid sea-level rise. Here we present the first direct evidence for the release of ancient carbon from degrading permafrost in East Asia during the last 17 kyrs, using biomarkers and radiocarbon dating of terrigenous material found in two sediment cores from the Okhotsk Sea. Upscaling our results to the whole Arctic shelf area, we show by carbon cycle simulations that deglacial permafrost-carbon release through sea-level rise likely contributed significantly to the changes in atmospheric CO2 around 14.6 and 11.5 kyrs BP., Permafrost-derived carbon (C) may have been an additional source of greenhouse gases during the last glacial-interglacial transition. Here the authors show that ancient C from degrading permafrost was mobilised during phases of rapid sea-level rise, partially explaining changes in atmospheric CO2 and ∆14C.

Quantitative constraints on soil organic matter (SOM) dynamics are essential for comprehensive understanding of the terrestrial carbon cycle. Deep soil carbon is of particular interest, as it represents large stocks and its turnover rates remain highly uncertain. In this study, SOM dynamics in both the top and deep soil across a climatic (average temperature ~ 1–9 °C) gradient are determined using time-series (~ 20 years) 14C data from bulk soil and water-extractable organic carbon (WEOC). Analytical measurements reveal enrichment of bomb-derived radiocarbon in the deep soil layers on the bulk level during the last two decades. The WEOC pool is strongly enriched in bomb-derived carbon, indicating that it is a dynamic pool. We used a numerical model to determine turnover time of the bulk, slow and dynamic pool as well as the size of the dynamic pool. The presence of bomb-derived carbon in the deep soil, as well as the rapidly turning over WEOC pool and sizeable dynamic fraction at depth across the climatic gradient implies that there likely is a dynamic component of carbon in the deep soil. Precipitation appears to exert a stronger influence on soil C dynamics than temperature. Overall, geology seems to impact the carbon cycling in three key ways: (1) bedrock-derived (petrogenic) carbon can comprise an important component of the soil carbon pool even at relatively shallow depths (< 1 m). (2) Bedrock type influences water logging either by its porosity or by determining texture, and (3) rock and soil mineralogy controls C stabilization.

Organic carbon (OC) radiocarbon (14C) signatures in marine surface sediments are highly variable and the causes of this heterogeneity remain ambiguous. Here, we present results from a detailed 14C-based investigation of an Arabian Sea sediment, including measurements on organic matter (OM) in bulk sediment, specific grain size fractions, and OC decomposition products from ramped-pyrolysis-oxidation (RPO). Our results show that 14C ages of OM increase with increasing grain size, suggesting that grain size is an important factor controlling the 14C heterogeneity in marine sediments. Analysis of RPO decomposition products from different grain size fractions reveals an overall increase in age of corresponding thermal fractions from finer to coarser fractions. We suggest that hydrodynamic properties of sediment grains exert the important control on the 14C age distribution of OM among grain size fractions. We propose a conceptual model to account for this dimensionality in 14C variability that invokes two predominant modes of OM preservation within different grain size fractions of Arabian Sea sediment: finer (14C ages, whereas OM preserved in coarser (>63 µm) fractions includes materials encapsulated within microfossils and/or entrained fossil (14C-depleted) OC hosted in detrital mineral grains. Our findings highlight the value of RPO for assessment of 14C age variability in sedimentary OC, and for assessing mechanisms of OM preservation in aquatic sediments.

Inland water bodies contain significant amounts of carbon in the form of dissolved inorganic carbon (DIC) derived from a mixture of modern atmospheric and pre-aged sources, which needs to be considered in radiocarbon-based dating and natural isotope tracer studies. While reservoir effects in hardwater lakes are generally considered to be constant through time, a comparison of recent and historical DI14C data from 2013 and 1969 for Lake Constance reveals that this is not a valid assumption. We hypothesize that changes in atmospheric carbon contributions to lake water DIC have taken place due to anthropogenically forced eutrophication in the 20th century. A return to more oligotrophic conditions in the lake led to reoxygenation and enhanced terrigenous organic matter remineralization, contributing to lake water DIC. Such comparisons using DI14C measurements from different points in time enable nonlinear changes in lake water DIC source and signature to be disentangled from concurrent anthropogenically induced changes in atmospheric 14C. In the future, coeval changes in lake dynamics due to climate change are expected to further perturb these balances. Depending on the scenario, Lake Constance DI14C is projected to decrease from the 2013 measured value of 0.856 Fm to 0.54–0.62 Fm by the end of the century., Radiocarbon, 60 (3), ISSN:0033-8222