A special issue preface: Radiocarbon in the Anthropocene.

The Anthropocene is defined by marked acceleration in human-induced perturbations to the Earth system. Anthropogenic emissions of CO2 and other greenhouse gases to the atmosphere and attendant changes to the global carbon cycle are among the most profound and pervasive of these perturbations. Determining the magnitude, nature and pace of these carbon cycle changes is crucial for understanding the future climate that ecosystems and humanity will experience and need to respond to. This special issue illustrates the value of radiocarbon as a tool to shed important light on the nature, magnitude and pace of carbon cycle change. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Making the case for an International Decade of Radiocarbon.

Radiocarbon (14C) is a critical tool for understanding the global carbon cycle. During the Anthropocene, two new processes influenced 14C in atmospheric, land and ocean carbon reservoirs. First, 14C-free carbon derived from fossil fuel burning has diluted 14C, at rates that have accelerated with time. Second, 'bomb' 14C produced by atmospheric nuclear weapon tests in the mid-twentieth century provided a global isotope tracer that is used to constrain rates of air-sea gas exchange, carbon turnover, large-scale atmospheric and ocean transport, and other key C cycle processes. As we write, the 14C/12C ratio of atmospheric CO2 is dropping below pre-industrial levels, and the rate of decline in the future will depend on global fossil fuel use and net exchange of bomb 14C between the atmosphere, ocean and land. This milestone coincides with a rapid increase in 14C measurement capacity worldwide. Leveraging future 14C measurements to understand processes and test models requires coordinated international effort-a 'decade of radiocarbon' with multiple goals: (i) filling observational gaps using archives, (ii) building and sustaining observation networks to increase measurement density across carbon reservoirs, (iii) developing databases, synthesis and modelling tools and (iv) establishing metrics for identifying and verifying changes in carbon sources and sinks. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Microbial activity contributes to spatial heterogeneity of wetland methane fluxes.

The emission of methane from wetlands is spatially heterogeneous, as concurrently measured surface fluxes can vary by orders of magnitude within the span of a few meters. Despite extensive study and the climatic significance of these emissions, it remains unclear what drives large, within-site variations. While geophysical factors (e.g., soil temperature) are known to correlate with methane (CH4) flux, measurable variance in these parameters often declines as spatial and temporal scales become finer. As methane emitted from wetlands is the direct, net product of microbial metabolisms which both produce and degrade CH4, it stands to reason that characterizing the spatial variability of microbial communities within a wetland-both horizontally and vertically-may help explain observed variances in flux. To that end, we surveyed microbial communities to a depth of 1 m across an ombrotrophic peat bog in Maine, USA using amplicon sequencing and gene expression techniques. Surface methane fluxes and geophysical factors were concurrently measured. Across the first meter of peat at the site, we observed significant changes in the abundance and composition of methanogenic taxa at every depth sampled, with variance in methanogen abundance explaining 70% of flux heterogeneity at a subset of plots. Among measured environmental factors, only peat depth emerged as correlated with flux, and had significant impact on the abundance and composition of methane-cycling communities. These conclusions suggest that a heightened awareness of how microbial communities are structured and spatially distributed within wetlands could offer improved insights into predicting CH4 flux dynamics. IMPORTANCE Globally, wetlands are one of the largest sources of methane (CH4), a greenhouse gas with a warming impact significantly greater than CO2. Methane produced in wetlands is the byproduct of a group of microorganisms which convert organic carbon into CH4. Despite our knowledge of how this process works, it is still unclear what drives dramatic, localized (<10 m) variance in emission rates from the surface of wetlands. While environmental conditions, like soil temperature or water table depth, correlate with methane flux when variance in these factors is large (e.g., spring vs fall), the explanatory power of these variables decline when spatial and temporal scales become smaller. As methane fluxes are the direct product of microbial activity, we profiled how the microbial community varied, both horizontally and vertically, across a peat bog in Maine, USA, finding that variance in microbial communities was likely contributing to much of the observed variance in flux.

Global methane emissions from rivers and streams.

Methane (CH4) is a potent greenhouse gas and its concentrations have tripled in the atmosphere since the industrial revolution. There is evidence that global warming has increased CH4 emissions from freshwater ecosystems1,2, providing positive feedback to the global climate. Yet for rivers and streams, the controls and the magnitude of CH4 emissions remain highly uncertain3,4. Here we report a spatially explicit global estimate of CH4 emissions from running waters, accounting for 27.9 (16.7-39.7) Tg CH4 per year and roughly equal in magnitude to those of other freshwater systems5,6. Riverine CH4 emissions are not strongly temperature dependent, with low average activation energy (EM = 0.14 eV) compared with that of lakes and wetlands (EM = 0.96 eV)1. By contrast, global patterns of emissions are characterized by large fluxes in high- and low-latitude settings as well as in human-dominated environments. These patterns are explained by edaphic and climate features that are linked to anoxia in and near fluvial habitats, including a high supply of organic matter and water saturation in hydrologically connected soils. Our results highlight the importance of land-water connections in regulating CH4 supply to running waters, which is vulnerable not only to direct human modifications but also to several climate change responses on land.

Aquatic biomass is a major source to particulate organic matter export in large Arctic rivers.

Arctic rivers provide an integrated signature of the changing landscape and transmit signals of change to the ocean. Here, we use a decade of particulate organic matter (POM) compositional data to deconvolute multiple allochthonous and autochthonous pan-Arctic and watershed-specific sources. Constraints from carbon-to-nitrogen ratios (C:N), δ13C, and Δ14C signatures reveal a large, hitherto overlooked contribution from aquatic biomass. Separation in Δ14C age is enhanced by splitting soil sources into shallow and deep pools (mean ± SD: -228 ± 211 vs. -492 ± 173‰) rather than traditional active layer and permafrost pools (-300 ± 236 vs. -441 ± 215‰) that do not represent permafrost-free Arctic regions. We estimate that 39 to 60% (5 to 95% credible interval) of the annual pan-Arctic POM flux (averaging 4,391 Gg/y particulate organic carbon from 2012 to 2019) comes from aquatic biomass. The remainder is sourced from yedoma, deep soils, shallow soils, petrogenic inputs, and fresh terrestrial production. Climate change-induced warming and increasing CO2 concentrations may enhance both soil destabilization and Arctic river aquatic biomass production, increasing fluxes of POM to the ocean. Younger, autochthonous, and older soil-derived POM likely have different destinies (preferential microbial uptake and processing vs. significant sediment burial, respectively). A small (~7%) increase in aquatic biomass POM flux with warming would be equivalent to a ~30% increase in deep soil POM flux. There is a clear need to better quantify how the balance of endmember fluxes may shift with different ramifications for different endmembers and how this will impact the Arctic system.

River ecosystem metabolism and carbon biogeochemistry in a changing world.

River networks represent the largest biogeochemical nexus between the continents, ocean and atmosphere. Our current understanding of the role of rivers in the global carbon cycle remains limited, which makes it difficult to predict how global change may alter the timing and spatial distribution of riverine carbon sequestration and greenhouse gas emissions. Here we review the state of river ecosystem metabolism research and synthesize the current best available estimates of river ecosystem metabolism. We quantify the organic and inorganic carbon flux from land to global rivers and show that their net ecosystem production and carbon dioxide emissions shift the organic to inorganic carbon balance en route from land to the coastal ocean. Furthermore, we discuss how global change may affect river ecosystem metabolism and related carbon fluxes and identify research directions that can help to develop better predictions of the effects of global change on riverine ecosystem processes. We argue that a global river observing system will play a key role in understanding river networks and their future evolution in the context of the global carbon budget.

A DNA barcode reference library for the native woody seed plants of Japan.

DNA barcode databases are increasingly available for a range of organisms, facilitating the wide application of DNA barcode-based studies. Here we announce the development of a comprehensive DNA barcode reference library of Japanese native woody seed plants representing 43 orders, 99 families, 303 genera and 834 species, and comprising 77.3% of the genera and 72.2% of the species of native woody seed plants in Japan. A total of 6216 plant specimens were collected from 223 sites across the subtropical, temperate, boreal and alpine biomes in Japan with most species represented by multiple accessions. This reference library utilized three chloroplast DNA regions (rbcL, trnH-psbA and matK) and consists of 14,403 barcode sequences. Individual regions varied in their identification rates, with species-level and genus-level rates for rbcL, trnH-psbA and matK based on blast being 57.4%/96.2%, 78.5%/99.1% and 67.8%/98.1%, respectively. Identification rates were higher using region combinations, with total species-level rates for two region combinations (rbcL & trnH-psbA, rbcL & matK and trnH-psbA & matK) ranging between 90.6% and 95.8%, and for all three regions being equal to 98.6%. Genus-level identification rates were even higher, ranging between 99.7% and 100% for two region combinations and being 100% for the three regions. These results indicate that this DNA barcode reference library is an effective resource for investigations of native woody seed plants in Japan using DNA barcodes and provides a useful template for the development of libraries for other components of the Japanese flora.

The importance of hydrology in routing terrestrial carbon to the atmosphere via global streams and rivers.

SignificanceStream/river carbon dioxide (CO2) emission has significant spatial and seasonal variations critical for understanding its macroecosystem controls and plumbing of the terrestrial carbon budget. We relied on direct fluvial CO2 partial pressure measurements and seasonally varying gas transfer velocity and river network surface area estimates to resolve reach-level seasonal variations of the flux at the global scale. The percentage of terrestrial primary production (GPP) shunted into rivers that ultimately contributes to CO2 evasion increases with discharge across regions, due to a stronger response in fluvial CO2 evasion to discharge than GPP. This highlights the importance of hydrology, in particular water throughput, in terrestrial-fluvial carbon transfers and the need to account for this effect in plumbing the terrestrial carbon budget.

Regional trends and drivers of the global methane budget.

The ongoing development of the Global Carbon Project (GCP) global methane (CH4 ) budget shows a continuation of increasing CH4 emissions and CH4 accumulation in the atmosphere during 2000-2017. Here, we decompose the global budget into 19 regions (18 land and 1 oceanic) and five key source sectors to spatially attribute the observed global trends. A comparison of top-down (TD) (atmospheric and transport model-based) and bottom-up (BU) (inventory- and process model-based) CH4 emission estimates demonstrates robust temporal trends with CH4 emissions increasing in 16 of the 19 regions. Five regions-China, Southeast Asia, USA, South Asia, and Brazil-account for >40% of the global total emissions (their anthropogenic and natural sources together totaling >270 Tg CH4  yr-1 in 2008-2017). Two of these regions, China and South Asia, emit predominantly anthropogenic emissions (>75%) and together emit more than 25% of global anthropogenic emissions. China and the Middle East show the largest increases in total emission rates over the 2000 to 2017 period with regional emissions increasing by >20%. In contrast, Europe and Korea and Japan show a steady decline in CH4 emission rates, with total emissions decreasing by ~10% between 2000 and 2017. Coal mining, waste (predominantly solid waste disposal) and livestock (especially enteric fermentation) are dominant drivers of observed emissions increases while declines appear driven by a combination of waste and fossil emission reductions. As such, together these sectors present the greatest risks of further increasing the atmospheric CH4 burden and the greatest opportunities for greenhouse gas abatement.

Substantial accumulation of mercury in the deepest parts of the ocean and implications for the environmental mercury cycle.

Anthropogenic activities have led to widespread contamination with mercury (Hg), a potent neurotoxin that bioaccumulates through food webs. Recent models estimated that, presently, 200 to 600 t of Hg is sequestered annually in deep-sea sediments, approximately doubling since industrialization. However, most studies did not extend to the hadal zone (6,000- to 11,000-m depth), the deepest ocean realm. Here, we report on measurements of Hg and related parameters in sediment cores from four trench regions (1,560 to 10,840 m), showing that the world's deepest ocean realm is accumulating Hg at remarkably high rates (depth-integrated minimum-maximum: 24 to 220 µg ⋅ m-2 ⋅ y-1) greater than the global deep-sea average by a factor of up to 400, with most Hg in these trenches being derived from the surface ocean. Furthermore, vertical profiles of Hg concentrations in trench cores show notable increasing trends from pre-1900 [average 51 ± 14 (1σ) ng ⋅ g-1] to post-1950 (81 ± 32 ng ⋅ g-1). This increase cannot be explained by changes in the delivery rate of organic carbon alone but also need increasing Hg delivery from anthropogenic sources. This evidence, along with recent findings on the high abundance of methylmercury in hadal biota [R. Sun et al, Nat. Commun. 11, 3389 (2020); J. D. Blum et al, Proc. Natl. Acad. Sci. U. S. A. 117, 29292-29298 (2020)], leads us to propose that hadal trenches are a large marine sink for Hg and may play an important role in the regulation of the global biogeochemical cycle of Hg.

Empirical estimates of regional carbon budgets imply reduced global soil heterotrophic respiration.

Resolving regional carbon budgets is critical for informing land-based mitigation policy. For nine regions covering nearly the whole globe, we collected inventory estimates of carbon-stock changes complemented by satellite estimates of biomass changes where inventory data are missing. The net land-atmospheric carbon exchange (NEE) was calculated by taking the sum of the carbon-stock change and lateral carbon fluxes from crop and wood trade, and riverine-carbon export to the ocean. Summing up NEE from all regions, we obtained a global 'bottom-up' NEE for net land anthropogenic CO2 uptake of -2.2 ± 0.6 PgC yr-1 consistent with the independent top-down NEE from the global atmospheric carbon budget during 2000-2009. This estimate is so far the most comprehensive global bottom-up carbon budget accounting, which set up an important milestone for global carbon-cycle studies. By decomposing NEE into component fluxes, we found that global soil heterotrophic respiration amounts to a source of CO2 of 39 PgC yr-1 with an interquartile of 33-46 PgC yr-1-a much smaller portion of net primary productivity than previously reported.

Global riverine nitrous oxide emissions: The role of small streams and large rivers.

Nitrous oxide, N2O, is the leading cause of stratospheric ozone depletion and one of the most potent greenhouse gases (GHG). Its concentration in the atmosphere has been rapidly increasing since the green revolution in the 1950s and 1960s. Riverine systems have been suggested to be an important source of N2O, although their quantitative contribution has been estimated with poor precision, ranging between 32.2 and 2100 GgN2O - N/yr. Here, we quantify reach scale N2O emissions by integrating a data-driven machine learning model with a physically-based upscaling model. The application of this hybrid modeling approach reveals that small streams (those with widths less than 10 m) are the primary sources of riverine N2O emissions to the atmosphere. They contribute nearly 36 GgN2O - N/yr; almost 50% of the entire N2O emissions from riverine systems (72.8 Gg2O - N/yr), although they account for only 13% of the total riverine surface area worldwide. Large rivers (widths wider than 175 m), such as the main stems of the Amazon River (~ 6 GgN2O - N/yr), the Mississippi River (~ 2 GgN2O - N/yr), the Congo River (~ 1 GgN2O - N/yr) and the Yang Tze River (~ 0.7 GgN2O - N/yr), only contribute 26% of global N2O emissions, which primarily originate from their water column. This study identifies, for the first time, near-global N2O emission and NO3 removal hot spots within watersheds and thus can aid the development of local- to global-scale management and mitigation strategies for riverine systems with respect to N2O emissions. The presented framework can be extended to quantified biogeochemical, besides N2O emissions, processes at the global scale.

Groundwater as a limited carbon dioxide source in a large river (the Yangtze River).

Groundwater discharge to river networks makes up a major source of riverine CO2 emission, available evidence however comes mainly from headwater streams which are directly connected to terrestrial ecosystems and spatially limited in terms of system size. Here relying on coupled water and CO2 mass balances, we quantified the groundwater-mediated CO2 input to the Yangtze River mainstem on an annual basis, where the mass balance of water provided physical constraints on CO2 exchange between the river and groundwater. A landscape topographic control of the groundwater-river interaction was proposed where mountain reaches preferentially receive water and CO2 discharge from the groundwater while plain alluvial reaches predominantly lose water to the aquifers. Groundwater CO2 inputs were however small in magnitude on all reaches (0.3-14% of the total CO2 emission and transport by the river) and unable to account for the discrepancy between surface evasion and internal metabolism in the river. Minor direct groundwater discharge to the reaches in comparison to smaller streams (negative to < 3.5% of the surface water flows) was concluded to be the main reason for low groundwater-sourced CO2 in the large river reaches.

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 that 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.

A comprehensive quantification of global nitrous oxide sources and sinks.

Nitrous oxide (N2O), like carbon dioxide, is a long-lived greenhouse gas that accumulates in the atmosphere. Over the past 150 years, increasing atmospheric N2O concentrations have contributed to stratospheric ozone depletion1 and climate change2, with the current rate of increase estimated at 2 per cent per decade. Existing national inventories do not provide a full picture of N2O emissions, owing to their omission of natural sources and limitations in methodology for attributing anthropogenic sources. Here we present a global N2O inventory that incorporates both natural and anthropogenic sources and accounts for the interaction between nitrogen additions and the biochemical processes that control N2O emissions. We use bottom-up (inventory, statistical extrapolation of flux measurements, process-based land and ocean modelling) and top-down (atmospheric inversion) approaches to provide a comprehensive quantification of global N2O sources and sinks resulting from 21 natural and human sectors between 1980 and 2016. Global N2O emissions were 17.0 (minimum-maximum estimates: 12.2-23.5) teragrams of nitrogen per year (bottom-up) and 16.9 (15.9-17.7) teragrams of nitrogen per year (top-down) between 2007 and 2016. Global human-induced emissions, which are dominated by nitrogen additions to croplands, increased by 30% over the past four decades to 7.3 (4.2-11.4) teragrams of nitrogen per year. This increase was mainly responsible for the growth in the atmospheric burden. Our findings point to growing N2O emissions in emerging economies-particularly Brazil, China and India. Analysis of process-based model estimates reveals an emerging N2O-climate feedback resulting from interactions between nitrogen additions and climate change. The recent growth in N2O emissions exceeds some of the highest projected emission scenarios3,4, underscoring the urgency to mitigate N2O emissions.

Estimating nitrogen and phosphorus concentrations in streams and rivers, within a machine learning framework.

Nitrogen (N) and Phosphorus (P) are essential nutritional elements for life processes in water bodies. However, in excessive quantities, they may represent a significant source of aquatic pollution. Eutrophication has become a widespread issue rising from a chemical nutrient imbalance and is largely attributed to anthropogenic activities. In view of this phenomenon, we present a new geo-dataset to estimate and map the concentrations of N and P in their various chemical forms at a spatial resolution of 30 arc-second (∼1 km) for the conterminous US. The models were built using Random Forest (RF), a machine learning algorithm that regressed the seasonally measured N and P concentrations collected at 62,495 stations across the US streams for the period of 1994-2018 onto a set of 47 in-house built environmental variables that are available at a near-global extent. The seasonal models were validated through internal and external validation procedures and the predictive powers measured by Pearson Coefficients reached approximately 0.66 on average.

Rivers across the Siberian Arctic unearth the patterns of carbon release from thawing permafrost.

Climate warming is expected to mobilize northern permafrost and peat organic carbon (PP-C), yet magnitudes and system specifics of even current releases are poorly constrained. While part of the PP-C will degrade at point of thaw to CO2 and CH4 to directly amplify global warming, another part will enter the fluvial network, potentially providing a window to observe large-scale PP-C remobilization patterns. Here, we employ a decade-long, high-temporal resolution record of 14C in dissolved and particulate organic carbon (DOC and POC, respectively) to deconvolute PP-C release in the large drainage basins of rivers across Siberia: Ob, Yenisey, Lena, and Kolyma. The 14C-constrained estimate of export specifically from PP-C corresponds to only 17 ± 8% of total fluvial organic carbon and serves as a benchmark for monitoring changes to fluvial PP-C remobilization in a warming Arctic. Whereas DOC was dominated by recent organic carbon and poorly traced PP-C (12 ± 8%), POC carried a much stronger signature of PP-C (63 ± 10%) and represents the best window to detect spatial and temporal dynamics of PP-C release. Distinct seasonal patterns suggest that while DOC primarily stems from gradual leaching of surface soils, POC reflects abrupt collapse of deeper deposits. Higher dissolved PP-C export by Ob and Yenisey aligns with discontinuous permafrost that facilitates leaching, whereas higher particulate PP-C export by Lena and Kolyma likely echoes the thermokarst-induced collapse of Pleistocene deposits. Quantitative 14C-based fingerprinting of fluvial organic carbon thus provides an opportunity to elucidate large-scale dynamics of PP-C remobilization in response to Arctic warming.

Immobilization of relic anthropogenic dissolved organic matter from alpine rivers in the Himalayan-Tibetan Plateau in winter.

The Tibetan Plateau is a critical ecosystem that sensitively responds to ongoing glacier shrinkage and permafrost thaw. Dissolved organic matter (DOM) in Tibetan Alpine rivers plays pivotal roles in the biogeochemical cycling of elements and nutrients at regional and even global scales, impacting water quality, downstream environments, and climate. However, little is known about the characteristics and dynamics of DOM in these watersheds. We investigated five major Himalayan rivers in the southern Tibetan Plateau, utilizing bulk dissolved organic carbon (DOC), optical properties, and molecular formulas. We found extremely low DOC and fluorescent DOM (FDOM) levels in the rivers (average DOC: 0.25-0.87 mg L-1, FDOM: 0.02-0.05 RU) with a highly degraded molecular signature, which was enriched with heteroatomic molecular formulas (S-containing: 58-72%, N-containing: 61-86%) and condensed aromatics (31-39% vs. ∼11% in world major rivers). Further, 81-99% of the condensed aromatics was identified as dissolved black nitrogen (DBN) with multiple nitrogen atoms, typical for grassy biomass combustion. The findings highlighted potentially fast DOM remineralization leading to the release of CO2 and enriched apparently anthropogenic condensed aromatics and heteroatomic formulas in what have been considered pristine Tibetan rivers. These findings should be considered in future biogeochemical models and ecosystem management.