Compound-Specific Radiocarbon Analysis by Elemental Analyzer–Accelerator Mass Spectrometry: Precision and Limitations

[EN]We examine instrumental and methodological capabilities for microscale (10−50μg of C) radiocarbon analysisof individual compounds in the context of paleoclimate and paleoceanography applications, for which relatively high-precisionmeasurements are required. An extensive suite of data for14C-free and modern reference materials processed using differentmethods and acquired using an elemental-analyzer−accelerator-mass-spectrometry (EA-AMS) instrumental setup at ETHZurich was compiled to assess the reproducibility of specific isolation procedures. In order to determine the precision, accuracy,and reproducibility of measurements on processed compounds, we explore the results of both reference materials and threeclasses of compounds (fatty acids, alkenones, and amino acids) extracted from sediment samples. We utilize a MATLAB codedeveloped to systematically evaluate constant-contamination-model parameters, which in turn can be applied to measurementsof unknown process samples. This approach is computationally reliable and can be used for any blank assessment of small-sizeradiocarbon samples. Our results show that a conservative lower estimate of the sample sizes required to produce relativelyhigh-precision14C data (i.e., with acceptable errors of 0.5, a precision of 2% can be achieved for alkenone and fatty acid samples containing≥15 and 10μg of C, respectivel

An Abrupt Aging of Dissolved Organic Carbon in Large Arctic Rivers

Permafrost thaw in Arctic watersheds threatens to mobilize hitherto sequestered carbon. We examine the radiocarbon activity (F14C) of dissolved organic carbon (DOC) in the northern Mackenzie River basin. From 2003‐2017, DOC‐F14C signatures (1.00 ± 0.04; n = 39) tracked atmospheric 14CO2, indicating export of “modern” carbon. This trend was interrupted in June 2018 by the widespread release of aged DOC (0.85 ± 0.16, n = 28) measured across three separate catchment areas. Increased nitrate concentrations in June 2018 lead us to attribute this pulse of 14C‐depleted DOC to mobilization of previously frozen soil organic matter. We propose export through lateral perennial thaw zones occurred at the base of the active layer weakened by preceding warm summer and winter seasons. Although we are not yet able to ascertain the broader significance of this “anomalous” mobilization event, it highlights the potential for rapid and large‐scale release of aged carbon from permafrost

Environmental and hydrologic controls on sediment and organic carbon export from a subalpine catchment: insights from a time series

Studies engaging in tracking headwater carbon signatures downstream remain sparse, despite their importance for constraining transfer and transformation pathways of organic carbon (OC) and developing regional-scale perspectives on mechanisms influencing the balance between remineralization and carbon export. Based on a 40-month time series, we investigate the dependence of hydrology and seasonality on the discharge of sediment and OC in a small (350 km2) Swiss subalpine watershed (Sihl River basin). We analyze concentrations and isotopic compositions (δ13C, F14C) of particulate OC and use dual-isotope mixing and machine learning frameworks to characterize and estimate source contributions, transport pathways, and export fluxes. The majority of transferred OC is sourced from plant biomass and soil material. The relative amount of bedrock-derived (petrogenic) OC, abundant in headwater streams, progressively decreases downstream in response to a lack of source material and efficient overprinting with biospheric OC, illustrating rapid organic matter alteration over short distances. Large variations in OC isotopic compositions observed during baseflow conditions converge and form a homogenous mixture enriched in OC and characterized by higher POC-F14C values following precipitation-driven events. Particulate OC isotopic data and model results suggest that storms facilitate surface runoff and the inundation of riparian zones, resulting in the entrainment of loose plant-derived debris and surficial soil material. Although particle transport in the Sihl River basin is mainly driven by hydrology, subtle changes in bedrock erosivity, slope angle, and floodplain extent likely have profound effects on the POC composition, age, and export yields.</p

Abrupt intrinsic and extrinsic responses of southwestern Iberian vegetation to millennial-scale variability over the past 28 ka

We present new high-resolution pollen records combined with palaeoceanographic proxies from the same samples in deep-sea cores SHAK06-5K and MD01-2444 on the southwestern Iberian Margin, documenting regional vegetation responses to orbital and millennial-scale climate changes over the last 28 ka. The chronology of these records is based on high-resolution radiocarbon dates of monospecific samples of the planktonic foraminifera Globigerina bulloides, measured from SHAK06-5K and MD01-2444 and aligned using an automated stratigraphical alignment method. Changes in temperate and steppe vegetation during Marine Isotope Stage 2 are closely coupled with sea surface temperature (SST) and global ice-volume changes. The peak expansion of thermophilous woodland between ~10.1 and 8.4 cal ka bp lags behind the boreal summer insolation maximum by ~2 ka, possibly arising from residual high-latitude ice-sheets into the Holocene. Rapid changes in pollen percentages are coeval with abrupt transitions in SSTs, precipitation and winter temperature at the onset and end of Heinrich Stadial 2, the ice-rafted debris event and end of Heinrich Stadial 1, and the onset of the Younger Dryas, suggesting extrinsically forced southwestern Iberian ecosystem changes by abrupt North Atlantic climate events. In contrast, the abrupt decline in thermophilous elements at ~7.8 cal ka bp indicates an intrinsically mediated abrupt vegetation response to the gradually declining boreal insolation, potentially resulting from the crossing of a seasonality of precipitation threshold

Temperature and moisture are minor drivers of regional-scale soil organic carbon dynamics

Storing large amounts of organic carbon, soils are a key but uncertain component of the global carbon cycle, and accordingly, of Earth System Models (ESMs). Soil organic carbon (SOC) dynamics are regulated by a complex interplay of drivers. Climate, generally represented by temperature and moisture, is regarded as one of the fundamental controls. Here, we use 54 forest sites in Switzerland, systematically selected to span near-independent gradients in temperature and moisture, to disentangle the effects of climate, soil properties, and landform on SOC dynamics. We estimated two SOC turnover times, based on bulk soil 14C measurements (τ14C) and on a 6-month laboratory soil incubation (τi). In addition, upon incubation, we measured the 14C signature of the CO2 evolved and quantified the cumulated production of dissolved organic carbon (DOC). Our results demonstrate that τi and τ14C capture the dynamics of contrasting fractions of the SOC continuum. The 14C-based τ14C primarily reflects the dynamics of an older, stabilised pool, whereas the incubation-based τi mainly captures fresh readily available SOC. Mean site temperature did not raise as a critical driver of SOC dynamics, and site moisture was only significant for τi. However, soil pH emerged as a key control of both turnover times. The production of DOC was independent of τi and not driven by climate, but primarily by the content of clay and, secondarily by the slope of the site. At the regional scale, soil physicochemical properties and landform appear to override the effect of climate on SOC dynamics

Seasonal particulate organic carbon dynamics of the Kolyma River tributaries, Siberia

Arctic warming is causing permafrost thaw and release of organic carbon (OC) to fluvial systems. Permafrost-derived OC can be transported downstream and degraded into greenhouse gases that may enhance climate warming. Susceptibility of OC to decomposition depends largely upon its source and composition, which vary throughout the seasonally distinct hydrograph. Most studies on carbon dynamics to date have focused on larger Arctic rivers, yet little is known about carbon cycling in lower-order rivers and streams. Here, we characterize the composition and sources of OC, focusing on less studied particulate OC (POC), in smaller waterways within the Kolyma River watershed. Additionally, we examine how watershed characteristics control carbon concentrations. In lower-order systems, we find rapid initiation of primary production in response to warm water temperatures during spring freshet, shown by decreasing δ13C-POC, in contrast to larger rivers. This results in CO2 uptake by primary producers and microbial degradation of mainly autochthonous OC. However, if terrestrially derived inorganic carbon is assimilated by primary producers, part of it is returned via CO2 emissions if the autochthonous OC pool is simultaneously degraded. As Arctic warming and hydrologic changes may increase OC transfer from smaller waterways to larger river networks, understanding carbon dynamics in smaller waterways is crucial.</p

Fluvial organic carbon composition regulated by seasonal variability in lowland river migration and water discharge

Identifying drivers of seasonal variations in fluvial particulate organic carbon (POC) composition can aid sediment provenance and biogeochemical cycling studies. We evaluate seasonal changes in POC composition in the Río Bermejo, Argentina, a lowland river running ∼1,270 km without tributaries. Weekly POC concentration and isotopic composition from 2016 to 2018 show that during the wet season, increased lateral channel migration generates an influx of 13C-enriched and 14C-enriched floodplain-sourced material, overprinting the 13C-depleted and 14C-depleted headwater signature that is observed during the dry season. These findings demonstrate how channel morphodynamics can drive variability of POC composition in lowland rivers, and may modulate the composition of POC preserved in sedimentary archives

Diverse soil carbon dynamics expressed at the molecular level

The stability and potential vulnerability of soil organic matter (SOM) to global change remains incompletely understood due to the complex processes involved in its formation and turnover. Here we combine compound-specific radiocarbon analysis with fraction-specific and bulk-level radiocarbon measurements in order to further elucidate controls on SOM dynamics in a temperate and sub-alpine forested ecosystem. Radiocarbon contents of individual organic compounds isolated from the same soil interval generally exhibit greater variation than those among corresponding operationally-defined fractions. Notably, markedly older ages of long-chain plant leaf wax lipids (n-alkanoic acids) imply that they reflect a highly stable carbon pool. Furthermore, marked 14C variations among shorter- and longer-chain n-alkanoic acid homologues suggest that they track different SOM pools. Extremes in SOM dynamics thus manifest themselves within a single compound class. This exploratory study highlights the potential of compound-specific radiocarbon analysis for understanding SOM dynamics in ecosystems potentially vulnerable to global change