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Biogeochemical analysis of a chronosequence of secondary forest succession in lowland Central Africa suggests that calcium becomes an increasingly scarce and potentially limiting resource with stand age and ecosystem calcium storage shifts from soil to woody biomass. Secondary forests constitute an increasingly important component of tropical forests worldwide. Although cycling of essential nutrients affects recovery trajectories of secondary forests, the effect of nutrient limitation on forest regrowth is poorly constrained. Here we use three lines of evidence from secondary forest succession sequences in central Africa to identify potential nutrient limitation in regrowing forests. First, we show that atmospheric phosphorus supply exceeds demand along forest succession, whereas forests rely on soil stocks to meet their base cation demands. Second, soil nutrient metrics indicate that available phosphorus increases along the succession, whereas available cations decrease. Finally, fine root, foliar and litter stoichiometry show that tissue calcium concentrations decline relative to those of nitrogen and phosphorus during succession. Taken together, these observations suggest that calcium becomes an increasingly scarce resource in central African forests during secondary succession. Furthermore, ecosystem calcium storage shifts from soil to woody biomass over succession, making it a vulnerable nutrient in the wake of land-use change scenarios that involve woody biomass export. Our results thus call for a broadened focus on elements other than nitrogen and phosphorus regarding tropical forest biogeochemical cycles and identify calcium as a scarce and potentially limiting nutrient in an increasingly disturbed and dynamic tropical forest landscape.

Anthropogenic activities, particularly fertilisation, have resulted in significant increases in reactive nitrogen (rN) in soils globally, leading to eutrophication, acidification, poor air quality, and emissions of the important greenhouse gas N2O. Understanding the partitioning of rN losses into different environmental compartments is critical to mitigate negative impacts, however, loss pathways are poorly quantified, and potential changes driven by climate warming and societal shifts are highly uncertain. We present a coupled soil-atmosphere isotope model (IsoTONE; ISOtopic Tracing Of Nitrogen in the Environment) to partition rN losses into leaching, harvest, NH3 volatilization, and production of NO, N2 and N2O based on a global dataset of soil δ15N, as well as numerous other geoclimatic and experimental datasets. The model was optimized in a Bayesian framework using a time series of N2O mixing ratios and isotopic compositions since the preindustrial era, as well as a global dataset of N2O emission factors (EF). The posterior model results showed that the total anthropogenic flux in 2020 (7.8 Tg N2O-N a-1) was dominated by indirect emissions resulting from N deposition, while the growth rate and trend in anthropogenic N2O was driven by both direct N fertilisation and deposition inputs. In contrast, inputs from fixation N drive natural N2O emissions, and were responsible for subdecadal interannual variability in total emissions.Total N gas (N2O + NO + N2) production and N2O losses were strongly dependent on geoclimate and thus spatially variable, therefore the spatial pattern of N inputs strongly impacted resulting EFs and total N2O emissions. The area-weighted global EF for N2O was 1% of anthropogenic N inputs in 2020, similar to the current IPCC default of 1.4%, however the N input-weighted global EF was 4.3%. Shifts in fertilisation inputs from the temperate Northern hemisphere towards warmer regions with higher EFs such as India and China have led to accelerating N2O emissions (1.02±0.7 Tg N2O-N a-1). In addition, N2O emissions have increased over the past decades due to climate warming (0.76±0.4 Tg N2O-N a-1). Predicted increases in fertilisation in India and Africa in the coming decades could further accelerate N2O-driven climate warming, unless mitigation measures are implemented to increase fertiliser N use efficiency and reduce N2O emission factors.

Primary tropical forests generally exhibit large gaseous nitrogen (N) losses, occurring as nitric oxide (NO), nitrous oxide (N2O) or elemental nitrogen (N2). The release of N2O is of particular concern due to its high global warming potential and destruction of stratospheric ozone. Tropical forest soils are predicted to be among the largest natural sources of N2O; however, despite being the world’s second-largest rainforest, measurements of gaseous N-losses from forest soils of the Congo Basin are scarce. In addition, long-term studies investigating N2O fluxes from different forest ecosystem types (lowland and montane forests) are scarce. In this study we show that fluxes measured in the Congo Basin were lower than fluxes measured in the Neotropics, and in the tropical forests of Australia and South East Asia. In addition, we show that despite different climatic conditions, average annual N2O fluxes in the Congo Basin’s lowland forests (0.97 ± 0.53 kg N ha−1 year−1) were comparable to those in its montane forest (0.88 ± 0.97 kg N ha−1 year−1). Measurements of soil pore air N2O isotope data at multiple depths suggests that a microbial reduction of N2O to N2 within the soil may account for the observed low surface N2O fluxes and low soil pore N2O concentrations. The potential for microbial reduction is corroborated by a significant abundance and expression of the gene nosZ in soil samples from both study sites. Although isotopic and functional gene analyses indicate an enzymatic potential for complete denitrification, combined gaseous N-losses (N2O, N2) are unlikely to account for the missing N-sink in these forests. Other N-losses such as NO, N2 via Feammox or hydrological particulate organic nitrogen export could play an important role in soils of the Congo Basin and should be the focus of future research., The ISME Journal, 15, ISSN:1751-7362, ISSN:1751-7370

Worldwide tree species have been observed to be suffering from extended periods of water limitation, for example due to warmer climate that increases soil evaporation and plant transpiration. These conditions likely do not only affect the growth and vitality of trees but may also feed back on the cycling of carbon and nitrogen at the interface between roots and soils. In September 2019, we established a mesocosm experiment to mechanistically study on a seasonal basis how the interactions between plants and soil biotic and abiotic resources are altered during events of drought. The mesocosms feature young Scots pine (Pinus sylvestris L.) trees and soil collected from a drought-affected natural forest in the Rhone valley, Switzerland; and are treated with three different levels of water availability (control, sufficient water; intermediate drought, 40% reduction; severe drought, 75% reduction). One year after the start of the experiment an isotopic labelling campaign with 13CO2 was conducted to trace the natural pathway of photosynthetic assimilates into above- and belowground carbon pools and fluxes. During the first growing season of the experiment, severe drought more than doubled the growth of fine roots when compared to the control treatment. In turn, the mean diameter of the fine roots significantly decreased by 22%, and fewer ectomycorrhizal root tips were observed. These findings suggest that trees exposed to drought invest more in within-plant carbon maintenance and in the growth of root systems, rather than in the allocation of carbon to sustain the biology in the rhizosphere for nutrient acquisition. Moreover, post-label soil pore 13CO2 concentrations and total soil CO2 concentrations were lower under severe drought compared to intermediate and control treatments, indicating a generally reduced carbon metabolism. By tracking the fate of 13C assimilates into fine roots, soils and microbial communities over time we now investigate whether there is a threshold at which Scots pine trees stop investing in providing carbon to the rhizosphere and rather succumb to drought., EGUsphere

Due to regular influx of organic matter and nutrients, waste stabilization ponds (WSPs) can release considerable quantities of greenhouse gases (GHGs). To investigate the spatiotemporal variations of GHG emissions from WSPs with a focus on the effects of sludge accumulation and distribution, we conducted a bathymetry survey and two sampling campaigns in Ucubamba WSP (Cuenca, Ecuador). The results indicated that spatial variation of GHG emissions was strongly dependent on sludge distribution. Thick sludge layers in aerated ponds and facultative ponds caused substantial CO2 and CH4 emissions which accounted for 21.3% and 78.7% of the total emissions from the plant. Conversely, the prevalence of anoxic conditions stimulated the N2O consumption via complete denitrification leading to a net uptake from the atmosphere, i.e. up to 1.4±0.2 mg-N m-2 d-1. Double emission rates of CO2 were found in the facultative and maturation ponds during the day compared to night-time emissions, indicating the important role of algal respiration, while no diel variation of the CH4 and N2O emissions was found. Despite the uptake of N2O, the total GHG emissions of the WSP was higher than constructed wetlands and conventional centralized wastewater treatment facilities. Hence, it is recommended that sludge management with proper desludging regulation should be included as an important mitigation measure to reduce the carbon footprint of pond treatment facilities.

The isotopic composition of nitrous oxide (N2 O) provides useful information for evaluating N2 O sources and budgets. Due to the co-occurrence of multiple N2 O transformation pathways, it is, however, challenging to use isotopic information to quantify the contribution of distinct processes across variable spatiotemporal scales. Here, we present an overview of recent progress in N2 O isotopic studies and provide suggestions for future research, mainly focusing on: analytical techniques; production and consumption processes; and interpretation and modelling approaches. Comparing isotope-ratio mass spectrometry (IRMS) with laser absorption spectroscopy (LAS), we conclude that IRMS is a precise technique for laboratory analysis of N2 O isotopes, while LAS is more suitable for in situ/inline studies and offers advantages for site-specific analyses. When reviewing the link between the N2 O isotopic composition and underlying mechanisms/processes, we find that, at the molecular scale, the specific enzymes and mechanisms involved determine isotopic fractionation effects. In contrast, at plot-to-global scales, mixing of N2 O derived from different processes and their isotopic variability must be considered. We also find that dual isotope plots are effective for semi-quantitative attribution of co-occurring N2 O production and reduction processes. More recently, process-based N2 O isotopic models have been developed for natural abundance and 15 N-tracing studies, and have been shown to be effective, particularly for data with adequate temporal resolution. Despite the significant progress made over the last decade, there is still great need and potential for future work, including development of analytical techniques, reference materials and inter-laboratory comparisons, further exploration of N2 O formation and destruction mechanisms, more observations across scales, and design and validation of interpretation and modelling approaches. Synthesizing all these efforts, we are confident that the N2 O isotope community will continue to advance our understanding of N2 O transformation processes in all spheres of the Earth, and in turn to gain improved constraints on regional and global budgets.

Rivers act as a natural source of greenhouse gases (GHGs) that can be released from the metabolisms of aquatic organisms. Anthropogenic activities can largely alter the chemical composition and microbial communities of rivers, consequently affecting their GHG emissions. To investigate these impacts, we assessed the emissions of CO2, CH4, and N2O from Cuenca urban river system (Ecuador). High variation of the emissions was found among river tributaries that mainly depended on water quality and neighboring landscapes. By using Prati and Oregon Indexes, a clear pattern was observed between water quality and GHG emissions in which the more polluted the sites were, the higher were their emissions. When river water quality deteriorated from acceptable to very heavily polluted, their global warming potential (GWP) increased by ten times. Compared to the average estimated emissions from global streams, rivers with polluted water released almost double the estimated GWP while the proportion increased to ten times for very heavily polluted rivers. Conversely, the GWP of good-water-quality rivers was half of the estimated GWP. Furthermore, surrounding land-use types, i.e. urban, roads, and agriculture, significantly affected the river emissions. The GWP of the sites close to urban areas was four time higher than the GWP of the nature sites while this proportion for the sites close to roads or agricultural areas was triple and double, respectively. Lastly, by applying random forests, we identified dissolved oxygen, ammonium, and flow characteristics as the main important factors to the emissions. Conversely, low impact of organic matter and nitrate concentration suggested a higher role of nitrification than denitrification in producing N2O. These results highlighted the impacts of land-use types on the river emissions via water contamination by sewage discharges and surface runoff. Hence, to estimate of the emissions from global streams, both their quantity and water quality should be included.

Introductory Paragraph In the mostly pristine Congo Basin, agricultural land-use change has intensified in recent years. One potential and understudied consequence of this deforestation and conversion to agriculture is the mobilization and loss of organic matter from soils to rivers as dissolved organic matter. Here, we quantify and characterize dissolved organic matter sampled from 19 catchments of varying deforestation extent near Lake Kivu over a two-week period during the wet season. Dissolved organic carbon from deforested, agriculturally-dominated catchments was older (14C age: ~1.5kyr) and more biolabile than from pristine forest catchments. Ultrahigh-resolution mass spectrometry revealed that this aged organic matter from deforested catchments was energy-rich and chemodiverse, with higher proportions of nitrogen- and sulfur-containing formulae. Given the molecular composition and biolability, we suggest that organic matter from deforested landscapes is preferentially respired upon disturbance, resulting in elevated in-stream concentrations of carbon dioxide. We estimate that while deforestation reduces the overall flux of dissolved organic carbon by ~56%, it does not significantly change the yield of biolabile dissolved organic carbon. Ultimately, the exposure of deeper soil horizons through deforestation and agricultural expansion releases old, previously stable, and biolabile soil organic carbon into the modern carbon cycle via the aquatic pathway.

Since substrates for respiration are supplied mainly by recent photo-assimilates, there is a strong but time-lagged link between short-term above- and belowground carbon (C) cycling. However, regulation of this coupling by environmental variables is poorly understood. Whereas recent studies focussed on the effect of drought and shading on the link between above- and belowground short-term C cycling, the effect of temperature remains unclear. We used a 13CO2 pulse-chase labelling experiment to investigate the effect of a sudden temperature change from 25 to 10 °C on the short-term coupling between assimilatory C uptake and respiratory loss. The study was done in the laboratory using two-month-old perennial rye-grass plants (Lolium perenne L.). After label application, the δ13C signal of respired shoot and root samples was analysed at regular time intervals using laser spectroscopy. In addition, δ13C was analysed in bulk root and shoot samples. Cold temperature (10 °C) reduced the short-term coupling between shoot and roots by delaying belowground transfer of recent assimilates and its subsequent respiratory use, as indicated by the δ13C signal of root respiration (δ13CRR). That is, the time lag from the actual shoot labelling to the first appearance of the label in 13CRR was about 1.5 times longer under cold temperature. Moreover, analysis of bulk shoot and root material revealed that plants at cold temperature invest relatively more carbon into respiration compared to growth or storage. While the whole plant C turnover increased under cold temperature, the turnover time of the labile C pool decreased, probably because less 13C is used for growth and/or storage. That is, (almost) all recent C remained in the labile pool serving respiration under these conditions. Overall, our results highlight the importance of temperature as a driver of C transport and relative C allocation within the plant–soil system.

Global Change Biology, 24 (5), ISSN:1354-1013, ISSN:1365-2486

Branch or shoot chamber measurements integrate over both foliar and woody tissue carbon dioxide (CO2) fluxes and their associated influences on the carbon isotopic composition of atmospheric/headspace CO2. Here, we quantified the bias introduced by woody tissue carbon isotope fluxes on apparent leaf (13)C discrimination (Δ(13)Capparent) estimates, using laser spectroscopy under controlled conditions. CO2 efflux from woody tissues of defoliated beech saplings in the dark was strongly related to temperature (R(2) = 0.78), which served as the basis to model light-dependent woody tissue photosynthesis (R(2) = 0.72). We then quantified the contributions of leaf and woody tissues to leaf Δ(13)Capparent of foliated beech saplings in the light. Unbiased foliar Δ(13)C was 1.1 to 4.9‰ lower than leaf Δ(13)Capparent, depending on photosynthetic rates of woody tissues. Therefore, we strongly recommend accounting for isotope-related bias due to woody tissues when estimating leaf Δ(13)Capparent based on branch or shoot chamber measurements.

Above- and belowground processes in plants are tightly coupled via carbon and water fluxes through the soil-plant-atmosphere system. The oxygen isotopic composition of atmospheric CO₂ and water vapour (H₂Ov) provides a valuable tool for investigating the transport and cycling of carbon and water within this system. However, detailed studies on the coupling between ecosystem components and environmental drivers are sparse. Therefore, we conducted a H2 (18)O-labelling experiment to investigate the effect of drought on the speed of the link between below- and aboveground processes and its subsequent effect on C(18)OO released by leaves and soils. A custom-made chamber system, separating shoot from soil compartments, allowed separate measurements of shoot- and soil-related processes under controlled conditions. Gas exchange of oxygen stable isotopes in CO₂ and H₂Ov served as the main tool of investigation and was monitored in real time on Fagus sylvatica saplings using laser spectroscopy. H₂(18)O-labelling showed that drought caused a slower transport of water molecules from soil to shoot, which was indicated by its direct derivation from independently measured concentrations and (18)O/(16)O ratios of CO₂ and H₂Ov, respectively. Furthermore, drought reduced the (18)O equilibrium between H₂O and CO₂ at the shoot level, resulting in less-enriched C(18)OO fluxes from leaf to atmosphere compared with control plants. Compared with the shoot, (18)O equilibrium was not instantaneous in the soil and no drought effect was apparent.

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier-transform infrared spectrometer (FTIR), measuring the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently-emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 60 % of days at one site and 77 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for one year at the unfertilised, winter-grazed site were 8.2 (± 0.91) nmol CH4 m−2 s−1 and 0.40 (± 0.018) nmol N2O m−2 s−1. During the same year, mean emission rates at the irrigated, fertilised and rotationally-grazed site were 7.0 (± 0.89) nmol CH4 m−2 s−1 and 0.57 (± 0.019) nmol N2O m−2 s−1. At this site, the N2O emissions amounted to 1.19 (± 0.15) % of the nitrogen inputs from animal excreta and fertiliser application.

Pulse labelling experiments provide a common tool to study short-term processes in the plant-soil system and investigate below-ground carbon allocation as well as the coupling of soil CO(2) efflux to photosynthesis. During the first hours after pulse labelling, the measured isotopic signal of soil CO(2) efflux is a combination of both physical tracer diffusion into and out of the soil as well as biological tracer release via root and microbial respiration. Neglecting physical back-diffusion can lead to misinterpretation regarding time lags between photosynthesis and soil CO(2) efflux in grassland or any ecosystem type where the above-ground plant parts cannot be labelled in gas-tight chambers separated from the soil. We studied the effects of physical (13)CO(2) tracer back-diffusion in pulse labelling experiments in grassland, focusing on the isotopic signature of soil CO(2) efflux. Having accounted for back-diffusion, the estimated time lag for first tracer appearance in soil CO(2) efflux changed from 0 to 1.81±0.56 h (mean±SD) and the time lag for maximum tracer appearance from 2.67±0.39 to 9.63±3.32 h (mean±SD). Thus, time lags were considerably longer when physical tracer diffusion was considered. Using these time lags after accounting for physical back-diffusion, high nocturnal soil CO(2) efflux rates could be related to daytime rates of gross primary productivity (R(2)=0.84). Moreover, pronounced diurnal patterns in the δ(13)C of soil CO(2) efflux were found during the decline of the tracer over 3 weeks. Possible mechanisms include diurnal changes in the relative contributions of autotrophic and heterotrophic soil respiration as well as their respective δ(13)C values. Thus, after accounting for physical back-diffusion, we were able to quantify biological time lags in the coupling of photosynthesis and soil CO(2) efflux in grassland at the diurnal time scale.