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As climate mitigation efforts lag, dependence on anthropogenic CO₂removal increases. Enhanced rock weathering (ERW) is a rapidly growing CO₂removal approach. In terrestrial ERW, crushed rocks are spread on land where they react with CO₂and water, forming dissolved inorganic carbon (DIC) and alkalinity. For long-term sequestration, these products must travel through rivers to oceans, where carbon remains stored for over 10,000 years. Carbon and alkalinity can be lost during river transport, reducing ERW efficacy. However, the ability of biological processes, such as aquatic photosynthesis, to affect the fate of DIC and alkalinity within rivers has been overlooked. Our analysis indicates that within a stream-order segment, aquatic photosynthesis uptakes 1%–30% of DIC delivered by flow for most locations. The effect of this uptake on ERW efficacy, however, depends on the cell-membrane transport mechanism and the fate of photosynthetic carbon. Different pathways can decrease just DIC, DIC and alkalinity, or just alkalinity, and the relative importance of each is unknown. Further, data show that expected river chemistry changes from ERW may stimulate photosynthesis, amplifying the importance of these biological processes. We argue that estimating ERW’s carbon sequestration potential requires consideration and better understanding of biological processes in rivers. 

Abstract Inland waters receive large quantities of dissolved organic carbon (DOC) from soils and act as conduits for the lateral transport of this terrestrially derived carbon, ultimately storing, mineralizing, or delivering it to oceans. The lateral DOC flux plays a crucial role in the global carbon cycle, and numerous models have been developed to estimate the DOC export from different landscapes. We reviewed 34 published models and compared their characteristics to identify challenges in model applications and opportunities for future model development. We classified these models into three types: indicator-driven, hydrology-forced, and process-based DOC export simulation models. They differ mainly in their environmental inputs, simulation approaches for soil DOC production, leaching from soils to inland waters, and transit through inland waters. It is essential to consider landscape characteristics, climate conditions, available data, and research questions when selecting the most appropriate model. Given the substantial assumptions associated with these models, sufficient measurements are required to benchmark estimates. Accurate accounting of terrestrially derived DOC export to oceans requires incorporating the DOC produced in aquatic ecosystems and deposited with rainwater; otherwise, global export estimates may be overestimated by 40.7%. Additionally, improving the representation of mineralization and burial processes in inland waters allows for more accurate accounting of carbon sequestration through land ecosystems. When all the inland water processes are ignored or assuming DOC leaching is equivalent to DOC export, the loss of soil carbon through this lateral flux could be underestimated by 43.9%. 

Abstract In this Perspective, we put forward an integrative framework to improve estimates of land-atmosphere carbon exchange based on the accumulation of carbon in the landscape as constrained by its lateral export through rivers. The framework uses the watershed as the fundamental spatial unit and integrates all terrestrial and aquatic ecosystems as well as their hydrologic carbon exchanges. Application of the framework should help bridge the existing gap between land and atmosphere-based approaches and offers a platform to increase communication and synergy among the terrestrial, aquatic, and atmospheric research communities that is paramount to advance landscape carbon budget assessments. 

The magnitude of stream and river carbon dioxide (CO 2 ) emission is affected by seasonal changes in watershed biogeochemistry and hydrology. Global estimates of this flux are, however, uncertain, relying on calculated values for CO 2 and lacking spatial accuracy or seasonal variations critical for understanding macroecosystem controls of the flux. Here, we compiled 5,910 direct measurements of fluvial CO 2 partial pressure and modeled them against watershed properties to resolve reach-scale monthly variations of the flux. The direct measurements were then combined with seasonally resolved gas transfer velocity and river surface area estimates from a recent global hydrography dataset to constrain the flux at the monthly scale. Globally, fluvial CO 2 emission varies between 112 and 209 Tg of carbon per month. The monthly flux varies much more in Arctic and northern temperate rivers than in tropical and southern temperate rivers (coefficient of variation: 46 to 95 vs. 6 to 12%). Annual fluvial CO 2 emission to terrestrial gross primary production (GPP) ratio is highly variable across regions, ranging from negligible (<0.2%) to 18%. Nonlinear regressions suggest a saturating increase in GPP and a nonsaturating, steeper increase in fluvial CO 2 emission with discharge across regions, which leads to higher percentages of GPP being shunted into rivers for evasion in wetter regions. This highlights the importance of hydrology, in particular water throughput, in routing terrestrial carbon to the atmosphere via the global drainage networks. Our results suggest the need to account for the differential hydrological responses of terrestrial–atmospheric vs. fluvial–atmospheric carbon exchanges in plumbing the terrestrial carbon budget. 

Abstract Climate change is thawing and potentially mobilizing vast quantities of organic carbon (OC) previously stored for millennia in permafrost soils of northern circumpolar landscapes. Climate‐driven increases in fire and thermokarst may play a key role in OC mobilization by thawing permafrost and promoting transport of OC. Yet, the extent of OC mobilization and mechanisms controlling terrestrial‐aquatic transfer are unclear. We demonstrate that hydrologic transport of soil dissolved OC (DOC) from the active layer and thawing permafrost to headwater streams is extremely heterogeneous and regulated by the interactions of soils, seasonal thaw, fire, and thermokarst. Repeated sampling of streams in eight headwater catchments of interior Alaska showed that the mean age of DOC for each stream ranges widely from modern to ∼2,000 years B.P. Together, an endmember mixing model and nonlinear, generalized additive models demonstrated that Δ¹⁴C‐DOC signature (and mean age) increased from spring to fall, and was proportional to hydrologic contributions from a solute‐rich water source, related to presumed deeper flow paths found predominantly in silty catchments. This relationship was correlated with and mediated by catchment properties. Mean DOC ages were older in catchments with >50% burned area, indicating that fire is also an important explanatory variable. These observations underscore the high heterogeneity in aged C export and difficulty of extrapolating estimates of permafrost‐derived DOC export from watersheds to larger scales. Our results provide the foundation for developing a conceptual model of permafrost DOC export necessary for advancing understanding and prediction of land‐water C exchange in changing boreal landscapes. 

Abstract Dissolved organic matter (DOM) is recognized for its importance in freshwater ecosystems, but historical reliance on DOM quantity rather than indicators of DOM composition has led to an incomplete understanding of DOM and an underestimation of its role and importance in biogeochemical processes. A single sample of DOM can be composed of tens of thousands of distinct molecules. Each of these unique DOM molecules has their own chemical properties and reactivity or role in the environment. Human activities can modify DOM composition and recent research has uncovered distinct DOM pools laced with human markers and footprints. Here we review how land use change, climate change, nutrient pollution, browning, wildfires, and dams can change DOM composition which in turn will affect internal processing of freshwater DOM. We then describe how human-modified DOM can affect biogeochemical processes. Drought, wildfires, cultivated land use, eutrophication, climate change driven permafrost thaw, and other human stressors can shift the composition of DOM in freshwater ecosystems increasing the relative contribution of microbial-like and aliphatic components. In contrast, increases in precipitation may shift DOM towards more relatively humic-rich, allochthonous forms of DOM. These shifts in DOM pools will likely have highly contrasting effects on carbon outgassing and burial, nutrient cycles, ecosystem metabolism, metal toxicity, and the treatments needed to produce clean drinking water. A deeper understanding of the links between the chemical properties of DOM and biogeochemical dynamics can help to address important future environmental issues, such as the transfer of organic contaminants through food webs, alterations to nitrogen cycling, impacts on drinking water quality, and biogeochemical effects of global climate change. 

Abstract Headwater stream networks contribute substantially to the global carbon dioxide terrestrial flux because of high turbulence and coupling with terrestrial environments. Heterogeneity within headwater stream networks, both spatially and temporally, makes measuring and upscaling these emissions challenging because measurements of carbon dioxide in streams are often limited to a few monitoring points. We modified a stream network model to reflect real measurements made under base flow and high flow conditions at Martha Creek in Stabler, WA in the US Pacific Northwest. We found that under high flow conditions, the stream network had much greater total carbon emissions than during low flow conditions (1.22 Mg C day⁻¹vs. 0.034 Mg C day⁻¹). We attribute this increase to a larger overall stream network area (0.04 vs. 0.01 km²) and discharge (1.9 m³ s⁻¹vs. 0.005 m³ s⁻¹) in November versus August. Our results demonstrate the need to understand the nonperennial stream reaches when calculating carbon emissions. We compared the stream network emissions with the terrestrial net ecosystem exchange (NEE) estimated by local eddy covariance measurements per watershed area (−5.5 Mg C day⁻¹in August and −2.2 Mg C day⁻¹in November). Daily stream emissions in November accounted for a much larger percentage of NEE than in August (54% vs. 0.62%). We concluded that the stream network can emit a large percentage of the forest NEE in the winter months, and annual estimates of stream network emissions must consider the flow regime throughout the year.