Dissolved Organic Carbon Fluxes Research Articles

Icelandic glacial dissolved organic carbon fluxes, composition and variability - relevance for the global glacial carbon budget

Despite their relatively large size, organic carbon (OC) fluxes from Icelandic glaciers have not been explicitly considered in current global glacial OC flux calculations. Most global glacial OC estimates are based on limited individual flux estimates, which show considerable spatial differences, are often based on melt season fluxes, and rarely account for seasonal and diurnal variability of glacial dissolved organic matter (DOM). Using an annual dataset of 25 Icelandic glaciers (and their glacial streams) we investigate DOM concentration and composition, calculating an estimate for downstream OC fluxes from Icelandic glaciers, considering diurnal and seasonal variability. DOM source and composition distinctly changed from a terrestrial character toward a more proteinaceous character as melt increased, both on a seasonal and diurnal basis, likely reflecting the flow path of the meltwater. While DOC concentration did not change on a diurnal basis, DOM composition was more labile in the afternoons, possibly indicating photochemical or biological transformation processes. Overall, the glacial streams predominantly acted as CO2 sinks. However, higher DOC concentrations, along with contributions of more proteinaceous DOM in proglacial streams, led to a decrease in the uptake potential for CO2. Finally, we estimated an export flux of 0.0026 ± 0.0029 Gg C yr−1 km−2 of DOC, and 0.011 ± 0.007 Tg C yr−1 km−2 of POC, from Icelandic glaciers. We reveal larger than previously assumed DOC and POC fluxes from Icelandic glaciers, with higher-than-global-average areal fluxes (~3 % and 9 % of global glacial C flux respectively). Our findings underscore the importance of revising current global estimates to include the not-fully-accounted-for contribution of Icelandic, and other glaciers. This is particularly important considering ongoing climatic changes will likely affect glacial meltwater discharge and sources, leading to altered DOM composition and DOC concentration, having potentially considerable consequences for glacial OC export and CO2 uptake potentials of glacial streams.

Rising CO2 and land use change amplify the increase in terrestrial and riverine export of dissolved organic carbon over the past four decades

The lateral transport of dissolved organic carbon (DOC) from land to rivers and oceans is a significant but overlooked component of the global carbon cycle. However, there are still large uncertainties in the magnitude and trend of global DOC export fluxes, as well as their response to environmental change. In this study, several simulations were conducted using a developed land surface model that considered riverine DOC transport and anthropogenic disturbance to investigate the terrestrial DOC loading and riverine DOC export, and to quantify the relative contributions of natural and anthropogenic factors over the past four decades (1981–2016). These factors include climate change, nitrogen deposition, land use change, atmospheric CO2 concentration, anthropogenic water regulation, and fertilizer and manure application. Results showed that the average global annual terrestrial DOC loading was about 432.30 ± 53.59 Tg C yr−1, and rivers exported about 209.73 ± 36.58 Tg C yr−1 to oceans over the past four decades. Simultaneously, a significant increase in terrestrial DOC loading and riverine DOC export fluxes (3.36 Tg C yr−2 and 2.99 Tg Cyr−2, p < 0.01) was found, which increased by 26.88 % and 47.02 %, respectively. According to our factorial analysis, the interannual variability in DOC fluxes in most regions was mainly attributed to climate change and contributed more than 60 % of the long-term increase. In addition, rising atmospheric CO2 and land use change amplified the increase in terrestrial DOC loading, with the area dominated by the two factors expanding from 7.94 % in the 1980s to 23.84 % in the 2010s, and riverine DOC export showed a similar pattern, which may be related to the increased soil DOC sources. Anthropogenic water regulation and nitrogen addition have led to a slight increase in DOC fluxes, which should not be ignored, otherwise carbon fluxes may be underestimated.

Capturing the Dynamics of Dissolved Organic Carbon (DOC) in Tidal Saltmarsh Estuaries Using Remote‐Sensing‐Informed Models

AbstractThe fluxes of dissolved organic carbon (DOC) through tidal marsh‐influenced estuaries remain poorly quantified and have been identified as a missing component in carbon‐cycle models. The extreme variability inherent to these ecosystems of the land‐ocean interface challenge our ability to capture DOC‐concentration dynamics and to calculate accurate DOC fluxes. In situ discrete and continuous measurements provide high‐quality estimates of DOC concentration, but these strategies are constrained spatially and temporally and can be costly to operate. Here, field measurements and high‐spatial‐resolution remote sensing were used to train and validate a predictive model of DOC‐concentration distributions in the Plum Island Estuary (PIE), a mesotidal saltmarsh‐influenced estuary in Massachusetts. A large set of field measurements collected between 2017 and 2023 was used to develop and validate an empirical algorithm to retrieve DOC concentration with a ±15% uncertainty from Sentinel‐2 imagery. Implementation on 141 useable images produced a 6‐year time series (2017–2023) of DOC distributions along the thalweg. Analysis of the time series helped identify river discharge, tidal water level (WL), and a marsh enhanced vegetation index 2 as predictors of DOC distribution in the estuary, and facilitated the training and validation of a simple model estimating the distribution. This simple model was able to predict DOC along the PIE thalweg within ±16% of the in situ measurements. Implementation for three years (2020–2022) illustrated how this type of remote‐sensing‐informed models can be coupled with the outputs hydrodynamic models to calculate DOC fluxes in tidal marsh‐influenced estuaries and estimate DOC export to the coastal ocean.

Qualitative variability of dissolved organic matter in the Baltic Sea sediments apparent from fluxes and optical properties

IntroductionThe release of dissolved organic matter (DOM) from sediments serves as an important part of the carbon cycle.MethodsHere, we address pore water DOM quality and its release from shallow sediments (0–10 cm) of the central and southern Baltic Sea - Gdansk, Bornholm, and Eastern Gotland Basins - using excitation–emission matrix spectroscopy and size-exclusion chromatography.ResultsDOM release from sediments displayed spatial variability, with diffusive DOC fluxes ranging from 0.02 to 1.06 mmol m−2 d−1, and basin-averaged fluxes increased in the order Gotland &amp;lt; Bornholm &amp;lt; Gdansk. DOM qualitative characteristics also varied among investigated basins. In the oxygen-limited study sites from the Gdansk Basin, we observed elevated abundances of low apparent molecular weight DOM fraction and proteinaceous-like fluorescent DOM, while in the Bornholm Basin, pore water DOM was generally more humic-like and of higher apparent molecular weight. Pore waters from the deepest study sites in the Gotland Basin were qualitatively very similar to those of the pore waters from the upper sediment layers (0–4 cm) from all other investigated sites, suggesting little organic matter reworking at depth at those stations.DiscussionOur results suggest that the spatial variability in the magnitude of DOM release may be linked to the qualitative differences of DOM in sediments.

Disentangling the effects of applying pig slurry or its digestate to winter wheat or a catch crop on dissolved C fluxes

The anaerobic digestion industry, which is still developing, generates biogas from organic waste products. A co-product of this process, digestate, is increasingly produced and can be recycled on agricultural land as an alternative to mineral fertilizers. Biogas digestate is a recent product whose chemical composition differs from that of its source material, and additional data still need to be acquired on its effects on dissolved carbon fluxes. The objectives of this study were to assess (i) the effects of applying biogas digestate on dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) fluxes with different winter crops, (ii) the dynamics of DOC and DIC concentrations during the drainage season, and (iii) the annual dynamics of DOC and DIC fluxes along the soil profile. The study examined effects of applying biogas digestate, pig slurry, or a mineral fertilizer to winter wheat and two catch crops (mustard and a multispecies crop) on DOC and DIC fluxes in the soil. Lysimeters at 40 cm (topsoil) and 90 cm (subsoil) depths were monitored from 2014 to 2023, from November to March (i.e., 9 winter drainage seasons). During the drainage season, the DOC concentration was highest with digestate, and its timing depended on development of the cover crop: from the beginning of the drainage season for mustard and the multispecies crop and around February for wheat. Applying digestate increased the topsoil DOC fluxes (mean of 35.7 ± 13.7 kg.ha−1 with digestate vs. 21.0 ± 6.7 kg.ha−1 with the other treatments), particularly under mustard. Topsoil DIC fluxes were highest with pig slurry due to higher mineralization than that with digestate (mean of 59.1 ± 22.8 kg.ha−1 with pig slurry vs. 46.2 ± 16.3 kg.ha−1 with the other treatments). In the subsoil, DOC fluxes were low (6.2 ± 4.1 kg.ha−1) and DIC fluxes were high (80.0 ± 45.7 kg.ha−1), with no difference among treatments.

An Increase in Stream Water DOC Concentrations May Not Necessarily Imply an Increase in DOC Fluxes in Areas Affected by Acid Deposition and Climate Change—An Example from Central European Catchments

Over a period of 30 years (1993–2022), headwater catchments in the Slavkov Forest (Czech Republic) exhibited a robust increase in stream water DOC (dissolved organic carbon) concentrations following a significant reduction in acidic atmospheric deposition. Sulfur deposition decreased from 34 kg ha−1 yr−1 in 1993 to 2.6 kg ha−1 yr−1 in 2022. Three Norway-spruce-dominated research sites—Černý Potok (CEP), a 15.2 ha peatbog catchment, Lysina (LYS), a 27.3 ha granitic catchment, and Pluhův Bor (PLB), a 21.6 ha serpentinite catchment, were investigated. The three–year average DOC concentration increased from 48.2 mg L−1 (1993–1995) to 68.3 mg L−1 (2020–2022) at CEP (0.69 mg L−1 yr−1). LYS showed an increase from 16.9 mg L−1 to 25.4 mg L−1 (0.30 mg L−1 yr−1 annually). The largest increase was recorded at PLB, with an increase from 15.7 mg L−1 to 36.7 mg L−1 (0.89 mg L−1 yr−1). A decline in ionic strength was identified as the main driver of the DOC increase. The annual runoff declined significantly at CEP and LYS from 465 mm to 331 mm as a result of rising air temperatures and reduced precipitation between 2014 and 2022. PLB (average of 266 mm) did not show a statistically significant decline. Recently, PLB experienced significant deforestation that likely lowered transpiration and thus increased catchment runoff. As a result, DOC fluxes did not change significantly at CEP (average 210 kg ha−1 yr−1) and LYS (90 kg ha −1 yr−1). However, PLB’s DOC flux more than doubled, increasing from 44 to 106 kg ha−1 yr−1. Drivers connected with global change, such as increasing temperatures, or potential chemical drivers, such as reductions in Al concentrations and pH changes, were not able to explain the observed changes in DOC concentra tions and fluxes.

Dissolved organic carbon (DOC) and labile organic compounds' spatial and temporal variations in coastal Indian groundwater: their bioavailability and transfer to neighboring coastal waters of India.

Submarine groundwater drainage (SGD) changes the elemental composition of the neighboring coastal ocean and impacts the biogeochemical cycles. To examine the seasonal and spatial variability in dissolved organic carbon (DOC) and labile organic compound biochemical compounds like dissolved carbohydrates (TDCHO), dissolved proteins (TDPRO), and dissolved free amino acid (TDFAA) concentrations during the dry and wet periods, groundwater samples were taken at 90 locations (180 samples) along the Indian coast. The mean DOC contents in Indian coastal groundwaters were more significant than the global mean values. DOC, TDCHO, TDPRO, and TDFAA concentrations are higher during wet than dry periods. The DOC and labile organic compound showed a substantial positive association with soil organic carbon, and respective labile compounds in soil, population, and land usage and poor relation with woodland territories, implying that soil organic compounds leaching is a source of DOC and other labile organic compounds into the groundwater. DOC and other labile compounds concentrations were linearly associated with population density, land usage, and sewage production, demonstrating that anthropogenic activities tightly regulate the formation of DOC in groundwater. During the wet and dry periods, total labile organic compounds (TDCHO, TDFAA, and TDPRO) constituted 21% and 10.5% of DOC, respectively. Compared to the wet time, more aromatic compounds accumulated during the dry season but were less bioavailable. SGD DOC flux contributed 2-7% of riverine DOC flux to the coastal ocean. The SGD flux from the Indian subcontinent to the nearby northern Indian Ocean accounts for approximately 2% of the worldwide SGD flux. The effect of DOC flux via SGD on coastal bacterial activity, the plankton food web, and the oxygen minimum zone must be studied.

Nutrient enrichment and herbivory alter carbon balance in temperate seagrass communities

Large nutrient levels and herbivory stress, particularly when acting together, drive a variety of responses in seagrass communities that ultimately may weaken their carbon balance. An in situ three-months experiment was carried out in two contrasting seasons to address the effects of two levels of nutrient load and three levels of artificial clipping on Cymodocea nodosa plants. Nutrient enrichment shifted the community from autotrophic to heterotrophic and reduced DOC fluxes in winter, whereas enhanced community carbon metabolism and DOC fluxes in summer. Herbivory stress decreased the net primary production in both seasons, whereas net DOC release increased in winter but decreased in summer. A reduction of seagrass food-web structure was observed under both disturbances evidencing impacts on the seagrass ecosystems services by altering the carbon transfer process and the loss of superficial OC, which may finally weaken the blue carbon storage capacity of these communities.

Carbon export from submarine groundwater discharge in a semi-enclosed bay: Impact for the buffering capacity against coastal ocean acidification

Submarine groundwater discharge (SGD) serves as an important pathway for the transport of dissolved carbon from land to ocean, significantly affecting the coastal biogeochemical cycles. However, the impact of SGD-derived dissolved carbon on the coastal carbon budget remains poorly understood. This study first quantified SGD and associated dissolved organic carbon (DOC), dissolved inorganic carbon (DIC) and total alkalinity (TA) fluxes in Daya Bay using mass balance models based on radium isotopes (223Ra, 224Ra, 226Ra and 228Ra). We then constructed carbon mass balance models to evaluate the impact of SGD-derived carbon on the buffering capacity against coastal ocean acidification. The estimated SGD fluxes ranged from 0.80 × 107 to 2.64 × 107 m3d−1. The DIC, DOC and TA fluxes from SGD were 17.90–36.44 mmol m−2d−1, 0.93–2.13 mmol m−2d−1, and 21.19–28.47 mmol m−2d−1, respectively. Based on carbon mass balances, the DIC flux from SGD was 19–39 times the riverine input, accounting for 27.16 % ∼ 37.64 % of the total carbon source. These results suggest that SGD is a major contributor to DIC, significantly affecting the coastal carbon budget. Furthermore, the average TA:DIC ratio of groundwater discharging into Daya Bay was approximately 1.13. High TA exports enhance the buffering capacity of the coastal ocean and contribute bicarbonate to the ocean, playing a significant role in the ocean carbon sequestration process. This study demonstrates the importance of SGD-derived dissolved carbon in the assessment of coastal carbon budgets.

Chemodiversity of dissolved organic matter exports from subtropical humid catchment driven by hydrological connectivity

The quantity and quality of dissolved organic matter (DOM) exported from source areas are closely related to hydrological linkage between source areas and streams, that is hydrological connectivity. However, understanding of how hydrological connectivity regulates the export of catchment DOM components remains inadequate. In this study, high-frequency monitoring of groundwater and runoff from subtropical humid catchment was conducted for 20 months, and hydrological connectivity was quantitatively characterized by considering both surface and subsurface hydrological processes. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was utilized to investigate the DOM molecular composition. Results showed that over half of the areas in the catchment could not persistently establish hydrological connectivity with the stream during the rainfall. The average proportion of lignin was the highest in DOM components, followed by tannin and proteins. Additionally, both modified aromaticity index and double bond equivalence reached maximums at peak discharge, reflecting terrestrial materials could increase DOM aromaticity and unsaturated degree. Partial least square-structural equation modeling revealed significantly direct effects of rainfall, antecedent conditions, and hydrological connectivity on dissolved organic carbon (DOC) export. Furthermore, nonlinear relationships were observed between hydrological connectivity and DOC, tannin, and condensed aromatics. Specifically, the instantaneous DOC flux increased dramatically when the hydrological connectivity strength exceeded 0.14; tannin and condensed aromatics exhibited a rapid increase with rising connectivity strength, but remained stable at connectivity strength above 0.25. However, hydrological connectivity showed no significant correlation with unstable components (such as lipids, protein, amino sugars, and carbohydrates). These results provide new insights into hydrological controls on the quantity and quality of DOM export and contribute to developing appropriate catchment management strategies for carbon storage.

The Distinct Composition and Transformation of Terrestrial Organic Carbon in the Yukon River Delta and Plume During the Mighty Spring Freshet

AbstractArctic amplification is leading to increased terrestrial organic carbon (terrOC) mobilization with downstream impacts on riverine and marine biogeochemistry. To improve quantification and characterization of terrOC discharged to the Arctic Ocean, Yukon River delta samples were collected during three stages of the annual hydrograph (ascending limb/peak freshet, descending limb, late summer) and across a land‐to‐ocean salinity gradient (0.08–29.06 ppt). All samples were analyzed for dissolved organic carbon (DOC) concentration and lignin phenols to determine seasonal variability in riverine terrOC and salinity‐induced transformation of highly aromatic terrestrial compounds. Additionally, the relationship between lignin and absorbance at 350 and 412 nm was assessed to determine the feasibility of using optical proxies for accurate quantification, both seasonally and across expansive salinity gradients. Lignin phenols were highest during the ascending limb/peak freshet (0.58–0.97 mg/100 mg OC) when riverine DOC was dominated by young vascular plant sources, whereas lignin phenols were lower (0.15–0.89 mg/100 mg OC) and riverine DOC more variable in terrestrial source and diagenetic state during the descending limb and late summer. Across the sampled salinity gradient, there was disproportionate depletion of lignin (up to 73%) compared to DOC (up to 22%). Finally, while optical proxies can be used to quantify lignin within seasonal or spatial contexts, increased uncertainty is likely when expanding linear correlations across Arctic land‐ocean continuums. Overall, results indicate seasonal, spatial, interannual, and climatic controls that are amplified during high‐flow conditions and important to constrain when investigating Arctic terrOC cycling and land‐ocean DOC flux.

Karst carbon sink mechanism and its contribution to carbon neutralization under land- use management

The chemical weathering process of carbonate rocks consumes a large quantity of CO2. This has great potential as a carbon sink, and it is one of a significant pathway for achieving carbon neutrality. However, the control mechanisms of karst carbon sink fluxes are unclear, and there is a lack of effective and accurate accounting. We took the Puding Shawan karst water‑carbon cycle test site in China, which has identical initial conditions but different land use types, as the research subject. We used controlled experiments over six years to evaluate the mechanisms for the differences in hydrology, water chemistry, concentrations and fluxes of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC). We found that the transition from rock to bare soil to grassland led to increases in the DIC concentration by 0.08–0.62 mmol⋅L−1. The inorganic carbon sink flux (CSF) increased by 3.01–5.26 t⋅C⋅km−2⋅a−1, an increase amplitude of 30–70 %. The flux of dissolved organic carbon (FDOC) increase by 0.28 to 0.52 t⋅C⋅km−2⋅a−1, an increase amplitude of 34–90 %. We also assessed the contribution of land use modifications to regional carbon neutrality, it indicate that positive land use modification can significantly regulate the karst carbon sink, with grassland having the greatest carbon sequestration ability. Moreover, in addition to DOC from soil organic matter degradation, DOC production by chemoautotrophic microorganisms utilizing DIC in groundwater may also be a potential source. Thus, coupled studies of the conversion of DIC to DOC processes in groundwater are an important step in assessing karst carbon sink fluxes.

Determining rainwater dissolved organic carbon to reveal atmospheric carbon deposition in China's karst city: Variations, origins, and deposition flux

A large amount of organic carbon (OC) in the atmosphere are transferred to the Earth's surface through dry (40%) and wet (60%) deposition. Therefore, wet deposition is an important physical pathway for the removal of atmospheric OC. Identifying the variations of DOC in wet deposition (rainwater) is essential for clarifying the earth-surface C balance. The present study detected the DOC content in 96 daily rainwater samples collected over an entire year in a karst city, with abundant rainfall in Southwest China. The DOC concentrations varied between 1.03–37.7 mg C L−1, while the VWM value stood at 2.76 mg C L−1, which is similar to the worldwide and Asian averages. The yearly DOC wet deposition flux was calculated as 2.88 g C m−2 yr−1. Both the VWM concentration and flux of rainwater DOC exhibit pronounced seasonal variations and regional differences, primarily controlled by precipitation and the external input of OC. The sources of rainwater DOC were multifaceted, including urban waste emission, agricultural activities, and fossil fuel combustion (especially coal combustion), while the contribution from natural sources was limited. Additionally, the C: N (2.08) ratio of rainwater is significantly lower than the Redfield ratio (6.625), indicating the importance of considering the impact of nutrient components in rainfall on the material cycling of surface water ecosystems. This work will benefit the knowledge of the present status of rainwater DOC and its deposition flux on the karst regional scale and further on a global scale, and contribute to a better understanding of the C geochemical cycle on the territorial system.

Carbon wet deposition flux and river carbon output in a forest watershed in permafrost region of the Da Xing'an Mountains.

Carbon wet deposition and river carbon output in river basins are important components of global carbon cycle. The assessment of both properties is of great significance for regional carbon budget. However, research on these topics in high-latitude permafrost regions in China is still lacking. We conducted dynamic monitoring of carbon wet deposition and carbon output in the river from May 28th to October 30th, 2022, in Laoyeling watershed, a typical forested watershed in the Da Xing'an Mountains permafrost region. We analyzed the variations of carbon component concentrations and fluxes in precipitation and river water, and estimated the contribution of carbon wet deposition to carbon output in the watershed. The results showed that wet deposition fluxes of dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), and total dissolved carbon (TDC) in the Laoyeling watershed were 1354.86, 684.59, and 2039.45 kg·km-2, respectively. The fluxes of DOC, DIC, TDC, particulate organic carbon (POC), particulate inorganic carbon (PIC), and total carbon (TC) in the river were 601.75, 1977.30, 2579.05, 125.13, 21.99, and 2726.17 kg·km-2, respectively. The contribution of TDC wet deposition to the river TDC output was 9941.89 kg, accounting for 17.6% of total output. The DIC concentration in the river showed significant seasonal differences, with increased runoff resulting from precipitation leading to a decrease in DIC concentration in the river and showing a clear dilution effect, while the concentrations of DOC, POC, and PIC increased, mainly due to erosion effect. In conclusion, carbon wet deposition flux in the Laoyeling watershed was mainly determined by precipitation, and its contribution to river carbon output was relatively small compared to other factor. Runoff was the dominant factor affecting river carbon output. The results would provide important insights into carbon cycling and carbon budget balance in permafrost regions under climate change.

Impacts of Hydrology and Extreme Events on Dissolved Organic Carbon Dynamics in a Heavily Urbanized Estuary and Its Major Tributaries: A View From Space

AbstractDissolved organic matter and its colored component, Colored Dissolved Organic Matter (CDOM), play a major role in global carbon budgets, and their fluxes provide an essential link between terrestrial and aquatic biogeochemical cycles. Satellite observations can uniquely capture the hydro‐biogeochemical connectivity of terrestrial and aquatic landscapes, across scales. Yet, accurate satellite retrievals of CDOM and dissolved organic carbon (DOC) dynamics remain challenging in urbanized estuaries and coasts. Here, we present an advanced unified algorithm for space‐based retrieval of coastal CDOM and DOC dynamics and its application in Long Island Sound—one of the world's most heavily urbanized estuaries that is becoming increasingly vulnerable to climate change stressors. A rich bio‐optical data set, encompassing a wide range of environmental conditions, was integrated into the algorithm training to retrieve DOC concentrations and CDOM spectral shape (i.e., spectral slope S275–295)—a proxy for DOC quality. The new algorithms were applied to full‐resolution satellite imagery from the Sentinel‐3 Ocean and Land Color Instrument (OLCI) after thoroughly evaluating the performance of six ocean color atmospheric correction approaches (ACOLITE, BAC, C2RCC, MUMM, l2gen, and Polymer). Evaluation of the algorithms yielded mean absolute percent differences of 28%, 12%, and 10% for aCDOM(300), S275–295, and DOC, respectively. Application of the algorithms to multi‐year satellite OLCI imagery captured, for the first time, the coupled impact of seasonal transitions, wind regimes, freshwater inputs, anthropogenic disturbances, and hydrological extremes (both intense precipitation and droughts) on DOC fluxes and CDOM quality at the ecosystem scale. Results have important implications for improved predictions of coastal biogeochemical fluxes in complex urban−estuary systems.

Exploring hydrological controls on dissolved organic carbon export dynamics in a typical flash flood catchment using a process-based model

The dynamics of dissolved organic carbon (DOC) export from headwater catchments are of critical importance for the global carbon balance and are driven by complex runoff processes. Most previous studies have used statistical relationships between runoff and DOC concentration to estimate DOC export dynamics. Thus, the coupling mechanisms between runoff generation and DOC export dynamics at the process level were obscured in the fitting parameters and have rarely been addressed. In this study, high-frequency (hourly) discharge and DOC export from a typical flash flood experimental headwater catchment with an area of 1.8 km2 were simulated using a process-based model (INCA-C). The results showed that the INCA-C model successfully captured the hourly dynamics of both discharge and DOC concentrations with a Nash–Sutcliffe efficiency (NSE) of 0.47–0.81 and 0.28–0.70 among moderate events and 0.81–0.85 and 0.19–0.90 among extreme events, respectively. The DOC was exported with distinct concentration dynamics, fluxes, and contributions from the four flow pathways under different storm intensities. At higher intensities, the DOC fluxes were exported by subsurface flows, particularly from shallow organic soil, with greater peaks and shorter time-to-peaks. Exported DOC is primarily sourced from subsurface runoff from the mineral layer (73 %–77 %) during moderate events, whereas it is primarily sourced from subsurface runoff from the organic layer (61 %–79 %) during extreme events. The two contrasting contributions suggest that hydrological pathway controls and DOC dynamic patterns can shift owing to runoff generation influenced by storm intensity. The distinct and variable controls of different flow pathways on DOC export highlight the need to explain the role of hydrology in regulating DOC storm exports through process-based modelling.

Degradation of ice-wedge polygons leads to increased fluxes of water and DOC

Ice-wedge polygon landscapes make up a substantial part of high-latitude permafrost landscapes. The hydrological conditions shape how these landscapes store and release organic carbon. However, their coupled water‑carbon dynamics are poorly understood as field measurements are sparse in smaller catchments and coupled hydrology-dissolved organic carbon (DOC) models are not tailored for these landscapes. Here we present a model that simulates the hydrology and associated DOC export of high-centered and low-centered ice-wedge polygons and apply the model to a small catchment with abundant polygon coverage along the Yukon Coast, Canada. The modeled seasonal pattern of water and carbon fluxes aligns with sparse field data. These modeled seasonal patterns indicate that early-season runoff is mostly surficial and generated by low-centered polygons and snow trapped in troughs of high-centered polygons. High-centered polygons show potential for deeper subsurface flow under future climate conditions. This suggests that high-centered polygons will be responsible for an increasing proportion of annual DOC export compared to low-centered polygons. Warming likely shifts low-centered polygons to high-centered polygons, and our model shows that this shift will cause a deepening of the active layer and a lengthening of the thawing season. This, in turn, intensifies seasonal runoff and DOC flux, mainly through its duration. Our model provides a physical hypothesis that can be used to further quantify and refine our understanding of hydrology and DOC export of arctic ice-wedge polygon terrain.

The impacts of water-sediment regulation on organic carbon in the Yellow River

The Yellow River water-sediment regulation (WSR) is a unique hydraulic engineering project that involves the resuspension and rapid discharge of sediment downstream under the influence of density currents. This process leads to short-term high-intensity sediment scouring, which in turn increases the output of organic carbon. The impact of WSR on the biogeochemical cycling of organic carbon in rivers has not been adequately explored. In this study, we applied stable isotope and 3-D fluorescence analyses to investigate the impact of WSR at the Xiaolangdi (XLD) Reservoir on the sources and fluxes of dissolved organic carbon (DOC) and particulate organic carbon (POC) in the Yellow River. The POC and DOC fluxes during WSR (∼51 days) accounted for 95.5 % and 28.3 % of the annual fluxes. According to the Bayesian model used in the study, the fluxes of POC from sediment, terrestrial plants, and sewage increased by 23.2, 13.36, and 56.55 times, respectively, during the WSR period. On the other hand, the flux from various sources of DOC decreased by ∼0.7 times during the WSR process. The three-dimensional fluorescence index (specific UV absorbance [SUVA254], humification index [HIX], biological index [BIX], and fluorescence index [FI]) further reveals that in the WSR process, more DOC comes from sediment and upstream water. This study provides quantitative insights into the effects of WSR on river organic carbon export dynamics and the driving mechanisms behind them. It also has important implications for understanding the impact of anthropogenic disturbance on the global carbon cycle.

Dissolved organic matter composition and characteristics during extreme flood events in the Yangtze River Estuary

Understanding the molecular composition and fate of dissolved organic matter (DOM) during transport in estuaries is essential for gaining a comprehensive understanding of its role within the global biogeochemical cycle. In 2020, a catastrophic flood occurred in the Yangtze River basin. It is currently unknown whether differences in hydrologic conditions due to extreme flooding will significantly impact the estuarine to oceanic DOM cycle. We determined the DOM composition in the Yangtze River estuary (YRE) to the East China Sea by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) during the high discharge and the flood period (monthly average discharge was 1.2 times higher) on the same trajectory. Our study found that the composition of DOM is more diverse, and more DOM molecules were introduced to the YRE during the flood, especially in the freshwater end member. The result revealed that the DOM was significantly labile and unstable during the flood period. A total of 1840 unique molecular formulas were identified during the flood period, most of which were CHON, CHONS, and CHOS compounds, most likely resulting from anthropogenic inputs from upstream. Only 194 of these molecules were detected in the seawater end member after transporting to the sea, suggesting that the YRE served as a ‘filter’ of DOM. However, the flood enhances the transport of a group of terrigenous DOM, that is resistant to photodegradation and biodegradation. As a result, YRE experienced ~1.6 times higher terrigenous DOC flux than high discharge period. Considering the increased frequency of future floods, our study provides a preliminary basis for further research on how floods affect the composition and characteristics of estuarine DOM. With the help of the FT-ICR MS technique, we can now better understand the dynamic of DOM composition and characteristics in large river estuaries.

Benzenepoly(carboxylic acid)s as Exclusive Intrinsic Markers to Assess Riverine Export of Dissolved Black Carbon.

Landscape fires annually generate large quantities of black carbon. The water-soluble fraction of black carbon (i.e., dissolved black carbon/DBC) is an important constituent of the dissolved organic carbon (DOC) pool, playing a crucial role in the global budget of refractory carbon and climate change. A key challenge in constraining the flux and fate of riverine DBC is to develop targeted and accurate quantification methods. Herein, we report that benzenepentacarboxylic acid (B5CA) intrinsically present in DBC can be used as an exclusive and holistic marker (representing both condensed aromatics and less-/nonaromatic fractions) for DBC quantification. B5CA was universally detected in water extractions of biochar and fire-affected soils with relatively large abundance but not produced by nonthermogenic processes. It has good mobility in the environment as it is not readily precipitated by cations or adsorbed by common geosorbents. B5CA also represents the recalcitrant components of DBC with excellent stability against photodegradation and biodegradation. Applying B5CA as the DBC marker in surface waters of the Changjiang River (i.e., the third largest river in the world), we calculate the DBC concentration in the downstream Changjiang River to be 4.8 ± 5.5% of the DOC flux. Our work provides a simple and reliable approach for the accurate quantification and source tracking of DBC in the soil and aquatic carbon pools.