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    Pleistocene climate variability in eastern Africa influenced hominin evolution

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    Respiratory loss during late-growing season determines the net carbon dioxide sink in northern permafrost regions

    We focused on the Northern High Latitudes (NHL, latitude > 50°N, excluding Greenland) due to their importance for carbon (CO2-C, the same hereafter)-climate feedbacks in the Earth system. To minimize the potential human influence on the CO2 cycle, we excluded areas under agricultural management (croplands, cropland/natural vegetation mosaic, and urban types), and considered only pixels of natural vegetation defined from the MODIS MCD12Q1 (v006) based IGBP land cover classification. Our main focus was the NHL permafrost region because permafrost plays a critical role in the ecology, environment, and society in the NHL. Permafrost, or permanently frozen ground, is defined as ground (soil, sediment, or rock) that remains at or below 0 °C for at least two consecutive years. The occurrence of permafrost is primarily controlled by temperature and has a strong effect on hydrology, soils, and vegetation composition and structure. Based on the categorical permafrost map from the International Permafrost Association58, the permafrost region (excluding permanent snow/ice and barren land), including sporadic (10–50%), discontinuous (50–90%), and continuous ( >90%) permafrost, encompasses about 15.7 × 106 km2, accounts for 57% of the NHL study dominion, and is dominated by tundra (shrubland and grass) and deciduous needleleaf (i.e., larch) forest that is regionally abundant in Siberia. The NHL non-permafrost region covers about 11.9 × 106 km2 and is dominated by mixed and evergreen needleleaf boreal forests (Fig. S1).Atmospheric CO2 inversions (ACIs)ACIs provide regionally-integrated estimates of surface-to-atmosphere net ecosystem CO2 exchange (NEEACI) fluxes by utilizing atmospheric CO2 concentration measurements and atmospheric transport models59. ACIs differ from each other mainly in their underlying atmospheric observations, transport models, spatial and temporal flux resolutions, land surface models used to predict prior fluxes, observation uncertainty and prior error assignment, and inversion methods. We used an ensemble mean of six different ACI products, each providing monthly gridded NEEACI at 1-degree spatial resolution, including Carbon‐Tracker 2019B (2000-2019, CT2019)60, Carbon‐Tracker Europe 2020 (2000–2019, CTE2020)61, Copernicus Atmosphere Monitoring Service (1979–2019, CAMS)62, Jena CarboScope (versions s76_v4.2 1976–2017, and s85_v4.2 1985-2017)63,64, and JAMSTEC (1996–2017)65. The monthly gridded ensemble mean NEEACI at 1-degree spatial resolution was calculated using the available ACIs from 1980-2017. Monthly ACI ensemble mean NEEACI data were summed to seasonal and annual values, and used to calculate the spatial and temporal trends of net CO2 uptake, and to investigate its relationship to climate and environmental controls.Productivity datasetDirect observations of vegetation productivity do not exist at a circumpolar scale. We therefore used two long-term gridded satellite-based estimates of vegetation productivity, including gross primary production (GPP) derived using a light use efficiency (LUE) approach (LUE GPP, 1982–1985)21,66 and satellite observations of Normalized Difference Vegetation Index (NDVI) from the Global Inventory Modeling and Mapping Studies (GIMMS NDVI, 1982–1985)67. LUE GPP (monthly, 0.5° spatial resolution, 1982–2015) is calculated from satellite observations of NDVI from the Advanced Very High-Resolution Radiometer (AVHRR; 1982 to 2015) combined with meteorological data, using the MOD17 LUE approach. LUE GPP has been extensively validated with a global array of eddy-flux tower sites68,69,70 and tends to provide better estimates in ecosystems with greater seasonal variability at high latitudes. Following66,71, we used the ensemble mean of GPP estimates from three of the most commonly used meteorological data sets: National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis; NASA Global Modeling and Assimilation Office (GMAO) Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2); and European Center for Medium-Range Weather Forecasting (ECMWF). GIMMS NDVI (bimonthly, 1/12 spatial resolution, 1982–2015) provides the longest satellite observations of vegetation “greenness”, and is widely used in studies of phenology, productivity, biomass, and disturbance monitoring as it has proven to be an effective surrogate of vegetation photosynthetic activity72.The gridded GPP data were resampled to 1-degree resolution at monthly time scales, to be consistent with NEEACI, and used to test (H1) whether greater temperature sensitivity of vegetation productivity explains the different trends in net CO2 uptake across the NHL. LUE GPP was also used to calculate monthly total ecosystem respiration (TER) as the difference between GPP and NEEACI (i.e., TERresidual =  GPP– NEEACI) from 1982-2015, as global observations of respiration do not exist. The NEEACI, GPP and TERresidual were used as observation-constrained top-down CO2 fluxes to investigate mechanisms underlying the seasonal CO2 dynamics in the structural equation modeling and additional decision tree-based analysis.Eddy Covariance (EC) measurements of bottom-up CO2 fluxesA total of 48 sites with at least three years of data representing the major NHL ecosystems were obtained from the FLUXNET2015 database (Table S1 and Fig. S1). EC measurements provide direct observations of net ecosystem CO2 exchange (NEE) and estimate the GPP and TER flux components of NEE using other climate variables. Daily GPP and TER were estimated as the mean value from both the nighttime partitioning method73 and the light response curve method74. More details on the flux partitioning and gap-filling methods used are provided by75. Daily fluxes were summed into seasonal and annual values and used to compare with trends from ACIs (Fig. S7), to estimate the climate and environmental controls on the CO2 cycle in the pathway analysis (Fig. 5), and to calculate the net CO2 uptake sensitivity to spring temperature (Fig. S14).Ensemble of dynamic global vegetation models (TRENDY simulations)The TRENDY intercomparison project compiles simulations from state-of-the-art dynamic global vegetation models (DGVMs) to evaluate terrestrial energy, water, and net CO2 exchanges76. The DGVMs provide a bottom-up approach to evaluate terrestrial CO2 fluxes (e.g., net biome production [NBP]) and allow deeper insight into the mechanisms driving changes in carbon stocks and fluxes. We used monthly NBP, GPP, and TER (autotrophic + heterotrophic respiration; Ra + Rh) from ten TRENDY v7 DGVMs76, including CABLE-POP, CLM5.0, OCN, ORCHIDEE, ORCHIDEE-CNP, VISIT, DLEM, LPJ, LPJ-GUESS, and LPX. We analyzed the “S3” simulations that include time-varying atmospheric CO2 concentrations, climate, and land use. All simulations were based on climate forcing from the CRU-NCEPv4 climate variables at 6-hour resolution. CO2 flux outputs were summarized monthly at 1-degree spatial resolution from 1980 to 2017. Monthly ensemble mean NBP, GPP, and TER were summed to seasonal and annual values, and then used to compare with observation-constrained ACI top-down CO2 fluxes (Figs. 4 and 5).Satellite data-driven carbon flux estimates (SMAP L4C)We also used a much finer spatio-temporal simulation of carbon fluxes from the NASA Soil Moisture Active Passive (SMAP) mission Level 4 Carbon product (L4C) to quantify the temperature and moisture sensitivity of NHL CO2 exchange77. The SMAP L4C provides global operational daily estimates of NEE and component CO2 fluxes for GPP and TER at 9 km resolution since 2015; whereas, an offline version of the L4C model provides a similar Nature Run (NR) carbon flux record over a longer period (2000-present), but without the influence of SMAP observational inputs. The L4C model has been calibrated against FLUXNET tower CO2 flux measurements and shows favorable performance and accuracy in high latitude regions4,77. In this analysis, daily gridded CO2 fluxes at 9-km resolution from the L4C NR record were summed to seasonal and annual values, and used to calculate the sensitivity of net C uptake in response to spring temperature (Fig. S14).CO2 fluxes in this analysis are defined with respect to the biosphere so that a positive value indicates the biosphere is a net sink of CO2 absorbed from the atmosphere. The different data products described above use different terminology (e.g., NEE, NBP) with slightly different meanings; however, they all provide estimates of net land-atmosphere CO2 exchange78.Climate, tree cover, permafrost, and soil moisture dataMonthly gridded air temperatures at 0.5-degree spatial resolution from 1980 to 2017 were obtained from the Climate Research Unit (CRU TS v4.02) at the University of East Anglia79. Air temperature was summarized at seasonal and annual scales to calculate temperature sensitivities of net CO2 uptake and to investigate the mechanism underlying the seasonal CO2 dynamics.Percent tree cover (%TC) at 0.05-degree spatial resolution was averaged over a 35-year (1982-2016) period using annual %TC layers derived from the Advanced Very High-Resolution Radiometer (AVHRR) (Fig. 1a)42. %TC was binned using 5% TC intervals to assess its relation to net CO2 uptake, or aggregated at a regional scale (e.g., TC  > 50% or TC  90%), discontinuous permafrost (DisconP, 10% < P  90%), discontinuous (DisconP, 10% < P  0.05 indicate a good fitting model), Bentler’s comparative fit index (CFI, where CFI ≈ 1 indicates a good fitting model), and the root mean square error of approximation (RMSEA; where RMSEA ≤ 0.05 and p  > 0.1 indicate a good fitting model). The standardized regression coefficient can be interpreted as the relative influences of exogenous (independent) variables. The R2 indicates the total variation in an endogenous (dependent) variable explained by all exogenous (independent) variables.Direct and legacy effects of temperature on seasonal net CO2 uptakeBecause landscape thawing and snow conditions regulate the onset of vegetation growth and influence the seasonal and annual CO2 cycles in the NHL24,84, we also analyzed the legacy effects of spring (May–Jun) temperature on seasonal net CO2 uptake. We regressed seasonal and annual net CO2 uptake from the site-level EC observations, regional-level ACI ensemble, and the TRENDY NBP ensemble against spring (May-June) air temperature. For EC observations, net CO2 uptake (i.e., NEE) and air temperature were summarized from site-level measurements. For the ACIs and TRENDY ensemble, net CO2 uptake (i.e., NEEACI and NBP) was summarized as regional means from the ACIs and TRENDY ensemble outputs, and air temperature was summarized as regional means from CRU temperature. The slope of the regression line was interpreted as the spring temperature sensitivity of the CO2 cycle. Simple linear regression was used here mainly due to the strong influence of spring temperature on the seasonal and annual CO2 cycle in NHL ecosystems30. Temperature sensitivity (γ: g C m−2 day−1 K−1) is the change in net CO2 flux (g C m−2 day−1) in response to a 1-degree temperature change. The sensitivity of net CO2 uptake to warm spring anomalies was calculated for different seasons (EGS, LGS, and annual) and regions (i.e., permafrost and non-permafrost), and the T-test was used to test for the difference in γ among different regions, seasons, and datasets. Similarly, direct effects of temperature on net CO2 uptake were calculated using the same season data (Fig. S14).Observationally-constrained estimates (EC and ACIs) showed that the sensitivity of net CO2 uptake in the EGS to spring temperature is positive (γ  > 0) and not statistically different (p  > 0.05) between permafrost and non-permafrost regions (({gamma }_{{ACI}}^{{np}})=0.125 ± 0.020 gC m−2 d−1 K−1; ({gamma }_{{EC}}^{{np}}) = 0.052 ± 0.013 gC m−2 d−1 K−1). In contrast, the sensitivity of net CO2 uptake in LGS to spring temperature is negative (γ  More

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    Nocturnal plant respiration is under strong non-temperature control

    Literature values of R
    To and Q10 of leaf respirationData of RTo were read from texts, tables, and figures in all available literature (18 species; Supplementary Tables 1, 2) when measured more than once within a period of darkness in lab- and field studies where measurement temperature, To, was kept constant. The RTo-initial was defined as the initial measurement of RTo for each study/species, and further values of RTo at later points within the same night of the same study were read as well.Apparent- and inherent temperature sensitivities (Q10, Equation 1; Fig. 2b) were obtained from all available literature (ten species; Supplementary Table 2) where in the same study/species, both nocturnal values of Q10,app and of Q10,inh were obtained in response to long-term natural T-changes in the environment during the night (hours) and nocturnal values were obtained in response to short-term artificial T-changes (max 30 min), respectively.Measurements of R
    To and Q10 of leaf respirationIn the field (United Kingdom, Denmark, Panama, Colombia and Brazil), RTo (µmol CO2 m−2 s−1) in 16 species (Supplementary Tables 1, 3) was measured through nocturnal periods at constant To (controlled either by block-T or leaf-T) with infra-red gas analysers (Li-Cor-6400(XT) or Li-Cor-6800, Lincoln, Nebraska, USA). Mature, attached leaves positioned in the sunlight throughout the day were chosen. Target [CO2] in the leaf cuvette was set to ambient, ranging from 390 to 410 ppm, depending on when measurements were made, and target RH = 65 ± 10%, with a flow rate of 300 µmol s–1. The RTo-initial was defined as RTo at first measurement after darkness 30 min after sunset (to conservatively avoid light-enhanced dark respiration, LEDR50,51. Leak tests were conducted prior to measurements52. The temporal resolution of measurements varied between every three minutes to once per hour for the different species. Data were subsequently binned in hourly bins.Measurements to derive Q10,inh and Q10,app were conducted in two species in a T-controlled growth cabinet and in six species in the field (Supplementary Table 2), where Q10,inh was measured in response to 10–30 min of artificial changes in T and Q10,app was calculated from measurements of RT in response to T of the environment (growth cabinet or field) at the beginning of the night and again at the end of the night (hours apart).Tree level measurements in whole-tree chambersThe night-time respiratory efflux of the entire above-ground portion (crown and bole) in large growing trees of Eucalyptus tereticornis was measured in whole-tree chambers (WTCs) in Richmond, New South Wales (Australia, (33°36ʹ40ʺS, 150°44ʹ26.5ʺE). The WTCs are large cylindrical structures topped with a cone that enclose a single tree rooted in soil (3.25 m in diameter, 9 m in height, volume of ~53 m3) and under natural sunlight, air temperature and humidity conditions. An automated system measured the net exchange of CO2 between the canopy and the atmosphere within each chamber at 15-min resolution. During the night, we used the direct measurements of CO2 evolution (measured with an infra-red gas analyser; Licor 7000, Li-Cor, Inc., Lincoln, NE)53,54 as a measure of respiration.Due to the high noise-to-signal ratio in the CO2-exchange measurements from this system when analysing the high-resolution temporal variation through each night, we chose to only analyse temporal variation in tree-RT for the nights when tree-RT-initial were amongst the top 10% of CO2-exchange signals for the entire data set. The resulting data spanned 62 nights and included hourly average measurements from three replicate chambers.Data analysis of R
    To
    Measurements of nocturnal leaf respiration under constant temperature conditions (RTo) were divided by the initial rate of respiration (RTo-initial) at the onset of each night. Hourly means of RTo/RTo-initial were calculated for each leaf replicate to remove measurement noise and reduce bias due to the measurement of some species at more frequent intervals throughout the night. For species with multiple leaf replicates, these hourly means of RTo/RTo-initial were then combined to create hourly averages of RTo/RTo-initial at the species level. For each species, these values were plotted as a function of time to demonstrate how RTo/RTo-initial decreases with time since the onset of darkness, from sunset until sunrise (Supplementary Fig. 1). For each species, hourly means of RTo/RTo-initial plotted as a function of time were linearised by log-transforming data and the slope of the relationship determined. To test whether the slopes of the lines differed significantly within plant functional groups (woody, non-woody), species originating from the same biome (temperate, tropical) or species measured under the same conditions (lab, field), the slopes of the lines for all species from a given functional group, biome or measurement condition were tested pairwise against each other using the slope, standard error and sample size (number of points on the x-axis) for each line and applying a 0.05 cut-off for p values after Bonferroni correction for multiple testing. 11 out of 701 comparisons came out as being significantly different, which is why within-group slope differences were considered to be overall non-significant for this analysis. t-tests were used to test whether the slopes differed between plant functional groups (tree, non-woody), species originating from different biomes (temperate, tropical) and species measured under different environmental conditions (lab, field). In these tests, the degrees of freedom varied according to the different sample sizes. Since RTo/RTo-initial plotted as a function of time always starts at 1, the intercepts do not differ between species. t-tests were performed on linearised power functions by log-transforming data in order to test potential differences between lab and field, origin of species, between woody and non-woody species and between temperate and tropical biomes. Since these functions were statistically indistinguishable in each pairing, all measurements of nocturnal leaf respiration under constant temperature conditions (n = 967 nights, 31 species) were collated into a single plot. The data were binned hourly since some studies had very few measurements on half-hourly steps. A power function was fitted with a weighting of each hourly binned value using 1/(standard error of the mean). The power function was chosen as it, better than the exponential- or linear function, can capture both sudden steep- as well as slower decrease in RTo/RTo-initial in different species. The 95% confidence interval of the power function, following the new model equation, overlaps with all the 95% confidence intervals of the hourly binned values (Fig. 1a). All data analysis, including statistical analysis and figures were performed using Python version 3.9.4.Evaluation of new equationWe performed four sets of simulations (S1-S4) using different representations of leaf and plant respiration as outlined in Supplementary Table 4. Evaluation of Equation 4 (S2; Equation 3 from Fig. 1a merged with Equation 1) in comparison with Equation 1 (S1) and Equation 5 (S4) in comparison with Equation 2 (S3), respectively, for predictions of nocturnal variation in response to natural variation in temperature, was conducted by use of independent sets of leaf level data and tree scale data. The effect of including variable nocturnal RTo is estimated as the difference between S1 and S2 and between S3 and S4, respectively.The first data set used for the evaluation consists of nine broad-leaf species for which spot measurements of leaf respiration under ambient conditions were taken at sunset and before sunrise in the field (Fig. 1b and Supplementary Fig. 2a). Of these nine species, three species (Fig. 1c) were further measured throughout the night at ambient conditions. Further, whole-tree measurements measured throughout the night at ambient conditions (Supplementary Fig. 3a–d) were also used for evaluation. Finally, comparisons of Q10,inh with Q10,app in another ten species were used to test if RTo appeared constant as assumed in Equation 1 (Supplementary Tables 2, 3 and Fig. 2b).To validate the suitability of Equation 4 and Equation 5 over equations with full temporal control, modelled respiration values were compared against observed measurements for three species at the leaf level (Supplementary Fig. 2b–d) and for Eucalyptus tereticornis at the whole-tree level using three chamber replicates and during 62 nights using hourly measurements (Supplementary Fig. 3a–d). Linear fits were applied, using ordinary least squares regressions, to plots of normalised respiration (({R}_{T}/{R}_{{T}_{0}})) predicted by the four models against the observed values. The first measurements of the night were excluded from the fits, as these were necessarily equal to unity. The standardised residuals (S) in Supplementary Figs. 2c, 3b are calculated using the equation ({S}_{i}=({R}_{{{{{{{rm{modelled}}}}}}}_{i}}/{R}_{{{{{{{rm{Modelled}}}}}}}_{0}}-{R}_{{T}_{i}}/{R}_{{T}_{0}})/sqrt{(mathop{sum }nolimits_{i}^{N}{({R}_{{{{{{{rm{modelled}}}}}}}_{i}}/{R}_{{{{{{{rm{Modelled}}}}}}}_{0}}-{R}_{{T}_{i}}/{R}_{{T}_{0}})}^{2})/{df}}), for the residual of the ith measurement, where the sum is over all measurements, df is the number of degrees of freedom, and Rmodelled are the respiration values modelled by the four equations in Supplementary Table 4.Evaluation is done by comparing observed and simulated RT/RT, initial. We evaluate the nocturnal evolution of RT/RT, initial and use (i) one-to-one line figures that include fitted regression line, R2, p value and RMSE, (ii) Taylor diagrams and (iii) use plots of standardised residuals against temperature and hours since darkness for a qualitative assessment of the simulations, to identify whether there are any model biases at specific times or temperatures. Model evaluation, statistical analysis and figures were done using python version 3.9.4.Global scale modelling of plant R and NPP
    We applied the novel formulation derived in this study (Equation 4 and Equation 5) to quantify the impact of incorporating variable RTo on simulated plant R and NPP globally using the JULES land surface model32,33 following simulations outlined in Supplementary Table 4.Plant respiration in JULES and simulations for this study: The original leaf respiration representation in JULES follows either eqn 1 ({{R}_{T}={R}_{{T}_{0}}{Q}}_{10}^{(T-{T}_{0})/10}) with Q10 = 2 and To = 25 oC or Equation 1 with an additional denominator ({{R}_{T}={R}_{{T}_{0}}{Q}}_{10}^{(T-{T}_{0})/10}/leftlfloor left(1+{e}^{0.3(T-{T}_{{upp}})}right)times left(1+{e}^{0.3({T}_{{low}}-T)}right)rightrfloor) (Equation 6). For the purpose of this application, we have used Equation 1 to represent leaf respiration in standard JULES simulations. The remaining components of maintenance respiration in JULES, i.e. fine root and wood are represented as a function of leaf to root and leaf to wood nitrogen ratios and leaf respiration rates following RT (β + (Nr + Ns)/Nl) (Equation 6) with RT as leaf respiration, Nr, Ns and Nl as root, stem and leaf Nitrogen content respectively and β as a soil water factor (Equation 42 in ref. 32). This implies that any variation in leaf respiration is passed to root and wood respiration as well30,31,35. Growth respiration is estimated as a fraction (25%) of the difference between GPP and maintenance respiration (Rm) expressed as Rg = 0.25 (GPP-Rm).JULES version 5.2 was modified to simulate leaf and plant respiration using the various descriptions (Equations 1–5) outlined in the modelling protocol in Supplementary Table 4. JULES uses standard astronomical equations to calculate the times of sunrise and sunset on a given day at each grid point. We used the model leaf temperature and RT at the timestep at or immediately preceding sunset to represent Tsunset, and RT,sunset and at every timestep through the night, the time since sunset (h) was updated. We performed global simulations for the period 2000–2018 with JULES, using the global physical configuration GL8, which is an update from GL755. We used WFDEI meteorological forcing data56 available at 0.5-degree spatial resolution and 3-h temporal resolution, and disaggregated and run in JULES with a 15 min timestep. Simulations were performed using nine plant functional types (PFTs)33. To isolate the effects of the new formulation on simulated Rp and NPP from possible impacts on leaf area index (LAI) or vegetation dynamics, we prescribed vegetation phenology via seasonal LAI fields and vegetation fractional cover based on the European Space Agency’s Land Cover Climate Change Initiative (ESA LC_CCI) global vegetation distribution57, processed to the JULES nine PFTs and re-gridded to the WFDEI grid. Annual variable fields of CO2 concentrations are based on annual mean observations from Mauna Loa58. JULES was spun up using the three cycles of the 2000–2018 meteorological forcing data to equilibrate the soil moisture stores. The mean annual output of Rp and NPP over the study period (2000–2018) is computed for all simulations and the effect of the new formulation is presented as the difference between the temporal mean of simulations with and without nocturnal variation in whole plant RTo for NPP and vice versa for Rp and as percentage respect to simulations without nocturnal variation in RTo. Results are presented for grid cells where grid level NPP is >50 g m−2 yr −1 in the standard simulations to avoid excessively large % effects at very low NPP. Output from JULES was analysed and plotted using python version 2.7.16.PermitsNo permit was required in Denmark as measurements were taken in private land (of author) and public land and measurements were non-destructive. Data were collected under the Panama Department of the Environment (current name MiAmbiente) research permit under the name of Dr Kaoru Kitajima. Permit number: SE/P-16-12. Data in Brazil were collected under the minister of Environment (Ministério do Meio Ambiente—MMA), Instituto Chico Mendes de Conservação da Biodiversidade—ICMBio, Sistema de Autorização e Informação em Biodiversidade—SISBIO permit number 47080-3. No permit was required in Colombia as measurements were taken on private land, no plant samples were collected, and trees were part of an existing experiment for which one of the co-authors is the lead. No access permits were required in the UK as they were conducted on the campus of own university plus in their own private garden.Reporting summaryFurther information on research design is available in the Nature Research Reporting Summary linked to this article. More

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    Tracking 21st century anthropogenic and natural carbon fluxes through model-data integration

    External datasetsWoody biomass carbon dataThe dataset by ref. 16 maps annual global woody biomass carbon densities for 2000–2019 at a spatial resolution of ~10 km. The annual estimates represent averages for the tropical regions and growing-season (April–October) averages for the extra-tropical regions. Ref. 16 analyse global trends of gains and losses in woody biomass carbon for 2000–2019. Overall, they find that grid cells with (significant) net gains of vegetation carbon are by a factor of 1.4 more abundant than grid cells with net losses of vegetation carbon, indicating that there is a global greening trend when only considering the areal extent of biomass gains and not the magnitude of carbon gains. Their regionally distinct analysis of trends shows that almost all regions, except for the tropical moist forests in South America and parts of Southeast Asia, experienced net gains in biomass carbon. On the country scale, the largest net increase in biomass carbon is shown in China, which is mainly attributed to the large-scale afforestation programs in the southern part of the country and increased carbon uptake of established forests. On the other hand, the largest vegetation carbon losses are shown for Brazil and Indonesia, which is partly attributed to deforestation, degradation, and drought events. All of the mentioned trends have been found to be significant16. The decreasing carbon sink in Brazil is in line with ref. 44, who, considering both natural and anthropogenic fluxes, show that the southeastern Amazon has even turned from a carbon sink to a carbon source, mainly owing to fire emissions from forest clearing. Isolating carbon fluxes in intact, old-growth Amazonian rainforests (i.e., SLAND,B), ref. 45 also find evidence for a significantly decreasing carbon sink due to the negative effects of increasing temperatures and droughts on carbon uptake since the 1990s.The dataset was remapped to the BLUE resolution of 0.25∘ through conservative remapping (i.e., area-weighted averaging).ERA-5 dataThe ERA-5 variables were downloaded from the Copernicus Climate Data Store (https://cds.climate.copernicus.eu/cdsapp#!/home). Monthly air temperature (Ta) at 2 m height was averaged over each year, and annual precipitation was calculated by taking the sum of the monthly total precipitation (P). Both variables were regridded from the original resolution of ~0.1° to 0.25° resp. to the TRENDY resolution of 0.5° through conservative remapping.TRENDY dataWe used the TRENDY model ensemble version 8 (conducted for the 2019 GCB; ref. 8). We used net biome production (NBP) and annual vegetation carbon stocks (cVeg) for 2000–2018 from four different model setups (S2, S3, S5, and S6) and eight resp. 13 DGVMs (depending on the data available). The selection of DGVMs is done as in ref. 19 (Supplementary Tab. 3), but we included one additional model (ISAM) for the S2 simulations. The terrestrial biomass carbon sink (SLAND,B) was calculated for 13 DGVMs following the GCB 2020 approach, i.e., from the S2 simulation, which is the simulation without LULCC (i.e., fixed pre-industrial land cover) under transient environmental conditions (climate, nitrogen deposition, CO2 evolution). SLAND,B is the annual difference of cVeg and makes no statements about the further fate of biomass if cVeg decreases. SLAND,B, therefore, should not be interpreted as equivalent to the flux to/from the atmosphere, since parts of cVeg may be transferred to litter, dead wood, or soil. The same applies to our BLUE estimates of SLAND,B, ensuring comparability between our BLUE estimates and the TRENDY estimates. Increases (decreases) of cVeg between two years are a net uptake (release) of carbon from the terrestrial biosphere. The global sums of biomass carbon stocks under transient climate and CO2 were calculated from the S3 setup (LULCC under historical environmental conditions), whereas the S5 setup provides biomass carbon under constant present-day environmental forcing (closest to the classical bookkeeping approach). In line with the GCB, ELUC was calculated under historical environmental conditions as the difference in NBP between the S2 and S3 simulations (ELUC = NBP_S2 – NBP_S3). ELUC under constant present-day environmental forcing was calculated as the difference in NBP between the S6 (fixed pre-industrial land cover under present-day environmental forcing) and S5 simulations (ELUC = NBP_S6 – NBP_S5)19. All datasets were remapped to a common resolution of 0.5∘ through conservative remapping (area-weighted average) for the data analysis.Assimilation of observed woody biomass carbon in BLUEThe observed woody biomass carbon densities by ref. 16 are assimilated in BLUE in several steps.Carbon transfer in the default setup of BLUEThe BLUE simulation is started in AD 850. Biomass and soil vegetation carbon densities are based on ref. 17, which are converted to exponential time constants. A detailed explanation of the exponential model can be found in ref. 5.While in the default setup, changes are only due to LULCC, our assimilation approach now introduces environmental effects on woody vegetation carbon by assimilating the observed woody biomass carbon densities in BLUE from 2000 onward according to the methodological considerations explained below.Calculation of woody biomass carbon densities for different land cover types and PFTsWithin each 0.25° cell of the global grid, the (remapped) woody biomass carbon density from ref. 16 must be the sum of woody biomass carbon stored in all woody PFTs of all woody land cover types. The distribution of the woody biomass carbon across PFTs and land cover types is achieved by distributing the observed (i.e., actual) woody biomass carbon densities (ρBa) from ref. 16 across the two land cover types (j) and the eight PFTs (l) that can be woody vegetation (primary land, called virgin, “v” in BLUE and secondary, “s”, land) according to the fraction of total woody biomass carbon (fB) contained in each land cover type and each PFT (fB,j,l) as estimated by BLUE. fB,j,l varies for different PFTs and land cover types, depending on their history of LULCC and their potential for carbon uptake (i.e., the potential carbon densities).fB,j,l is extracted from the default simulations for the first year of the time series (i.e., 2000) and calculated for subsequent years from the BLUE simulations using the assimilated woody vegetation carbon densities for that year:$${f}_{B,j,l}(t)=frac{{C}_{B,j,l}(t)}{{C}_{B}(t)}$$
    (1)
    where CB is the woody biomass carbon stock.Consequently, the assimilated woody biomass carbon stock per cover type and PFT (CB_as,j,l) at each time step can be calculated as:$${C}_{B_as,j,l}(t)={rho }_{Ba}(t);*;A;*;{f}_{B,j,l}(t)$$
    (2)
    with j{v, s}; l{1. . 8}; t{2000. . 2019}. A is the area per grid cell.Thresholds for excluding inconsistent woody biomass carbon densitiesWe eliminate unrealistically large values for woody biomass carbon densities that our assimilation framework produces. Woody biomass carbon densities in BLUE that exceed the highest value (~374 t ha−1) of the original dataset indicate inconsistencies between the observed woody biomass carbon estimates and the fractional grid cell areas per PFT and land cover types that BLUE simulates. To account for uncertainties related to the criteria for exclusion of grid cells, multiple threshold approaches are applied and the results are compared. To maintain a temporally and spatially consistent time series of woody biomass carbon, grid cells that are excluded according to the chosen threshold approach are interpolated through linear barycentric interpolation. A first approach relies on a uniform upper threshold of More

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    Waste slag benefits for correction of soil acidity

    Structural characterization of slag samplesThe FTIR spectra of granulated blast furnace slag (Sample 1), waste slag dumped in landfill (Sample 2) and combination of both 50% granulated blast furnace slag + 50% waste slag dumped in landfill (Sample 3) are presented in Fig. 1.Figure 1FTIR spectra of slag samples.Full size imageBy analysing the spectrum (detailed figure) in the range of 700–1100 cm−1, it can be found that there are obvious absorption peaks in the spectrum of all the slag samples. The granulated blast furnace slag shows the characteristic absorption bands at 3640, 1418, 980, 944, 861, 753 and 710 cm−1. The band at 3640 cm−1 is assigned to the stretching vibration of the hydroxyl group originated from the weakly absorbed water molecules on the slag surface24. The characteristic absorption bands at 1418, 861 and 710 cm−1 are ascribed to the asymmetric stretching mode and bending mode of carbonate group, respectively and the band at 980 cm−1 are attributable to the stretching vibrations of Si–O25. The band at 944 and 752 cm−1 represent the internal vibration of [SiO4]4− and [AlO4]5− tetrahedral and comes from Si (Al)–O-antisymmetric stretching vibration26.The different vibration modes for the sample of waste slag can be observed in the FTIR spectrum. The absorption bands shown are at 1418, 873, 712, 667 and 419 cm−1. The peak at 1418 cm−1 is assigned to the asymmetric stretching mode and bending mode of carbonate group. Calcite phase is confirmed by characteristic peaks at 712 cm−1 (ʋ2 out of plane bending vibration of the CO3−2 ion) and 873 cm−1 peak (ʋ2 split in-plane bending vibrations of the CO3−2 ion27. Calcium aluminate phase is identified by characteristic peak at 419 cm−128. Peak around 667 cm−1 is described as absorption band for different M–O (metal oxide) such as Al–O, Fe–O, Mg–O etc.29.In the case of combination of both 50% granulated blast furnace slag and 50% waste slag dumped in landfill the intensity of absorption peaks is smaller in comparison with Sample 1 and Sample 2 of slag. The characteristic absorption peaks (978 and 753 cm−1) which correspond with characteristic peaks of Sample 1 are shifted compared to the Sample 1, assigned to the stretching vibrations of Si–O and to the Si (Al)–O-antisymmetric stretching vibration, respectively, can provide important evidence of chemical interaction between Sample 1 and Sample 2. The decrease of the intensity of the bands appearing at 875 and 709 cm−1 cans be attributed to overlapping the vibrations of the CO3−2 ion from calcite phase.Figure 2 presents the SEM micrographs of the slag samples (Sample 1–3). One can see the characteristic morphology- the sizes and the forms of the slag samples.Figure 2SEM images of slag samples.Full size imageAt larger magnifications it can be observed that the surface is rough and uneven, and one can notice rounded grain-like rugged formations. The slag samples display aggregated particles with average diameter of a few microns. Also, in these rounded formations it can be seen different morphologies like spheres, rods, boards specific each compound/phase from metallurgical slags.Figure 3 illustrates the EDX elemental analysis of granulated blast furnace slag (Sample 1), waste slag dumped in landfill (Sample 2) and combination of both 50% granulated blast furnace slag + 50% waste slag dumped in landfill (Sample 3).Figure 3EDX elemental map of slag samples.Full size imageOne can observe that the predominant elements in the examined area are constated in carbon, oxygen, calcium, and iron, confirming the FTIR spectra.Figure 4 shows EDX spectra of slag samples recorded on different selected punctual area, to obtain more information about the elemental composition of specific areas. For all the tested slag samples have similar elements content.Figure 4EDX spectra analysis of slag samples.Full size imageThe selected punctual areas are highlighted thus: the spheric structure are with yellow line and the structure like boards are with green line for all the analysed slag samples. In the case of Sample 1 for both structures the values of chemical elements present are similar and the silicon has a higher value at spheric structure which can be correlated with the presence of silica (SiO2). The higher content of calcium reveals that the Sample 1 is blast furnace slag dominated by calcium and silicon compositions. In the case of slag dumped in landfill (Sample 2) the content of carbon increase for both structures and some chemical elements like titanium, barium, manganese doesn`t appear in EDX spectra and the explanation for this phenomenon is that the slag was dumped in landfill for more than 30 years. One can observe for combination of both 50% granulated blast furnace slag + 50% waste slag dumped in landfill (Sample 3) that the values of all the chemical elements for both spheric and board-like structure are between the first two samples, confirming the FTIR spectra regarding chemical interaction between Sample 1.XRD patterns of the slag samples with the phases identified are shown in Fig. 5. Sample 1 show minor peaks of free CaO and MgO, which may be deleterious and cause reduction in strength. The phases and amorphous contents of the Sample 1 granulated blast furnace slag are broadly consistent with literature30. Sample 3 of slag consists of crystalline phase – Ca2Mg2SiO7, Ca2Fe2AlO5, CaCO3 and CaO as observed by the XRD analysis. In terms of the relations of phase thermal equilibrium, the compounds identified form an isomorphic series of melilites that is specific to basic metallurgical slags.Figure 5X-ray diffraction patterns of slag samples.Full size imageIn Table 1 are presented the values expressed as ppm of chemical element detected in slag samples (Sample 1, 2 and 3).Table 1 XRF analysis of the slag samples.Full size tableThe results show a large quantity of calcium in all three samples of slag. Also, the elements detected such as Fe, Al, Mg and Si are in accordance with XRD spectra.Physical–chemical characterization of soil-slag mixturesThe chemical composition of the major elements that compound the soil, soil- slag and slag samples was determined by XRF. The values expressed as ppm of chemical elements are presented in Table 2. In the case of soil sample the content of the main constituents is iron, titanium, manganese, and potentially toxic elements (PTE) such as arsenic, zinc, copper, and cobalt. For soil-slag 1 with weight ratio soil: slag (1:1) it can be observed the disappearance of the potentially toxic elements (PTE) founded in soil sample and the decrease of concentration value of zinc. When the weight ratio of slag increases at 3 (soil-slag 2 sample) the values of main component increased in accordance with values of slag sample, but in the case of soil-slag 3 sample where the weight ratio of soil is bigger (3) it can be observed the cobalt presence. Based on these XRF results we can say that take place an elimination of potentially toxic elements in contaminated soil by applying slag in a bigger proportion.Table 2 XRF analysis of the soil-slag samples.Full size tableWith the aid of a pH meter, CONSORT C 533 the important parameters of soil and slag solutions were measured as: the pH, conductivity, and the salinity, as shown in Table 3. The data presented in Table 3 suggest that the soil sampled has the pH = 5.2 corresponding to a medium acid soil, which does not sustain a high fertility and is not able to offer proper conditions for crops. Also, the pH of soil has important influence on soil fertility, decreases the availability of essential elements and the activity of soil microorganisms which can determine calcium and magnesium deficiency in plants and decreases phosphorous availability. The pH value of slag solution (12.5) corresponds as strongly basic character which is beneficial in amelioration process of acidic soils and the presence of this type of slag sustain the improving of soil characteristics, too. For the soil-slag samples the pH value increase with the increasing of the weight ratio of slag and the mixtures soil-slag obtained can be framed into the category of weakly alkaline soils.Table 3 The physical–chemical characteristics of soil and slag solutions.Full size tableThe data given in Table 4 show that the humidity of soil is bigger and decreases in soil-slag samples with adding of slag content. The values of total soil-slag porosity are between 40 and 50% and depends on the density and apparent density of the soil being influenced by the mineralogical composition, the content of organic matter and the degree of compaction and loosening of the soil, the crystalline structure of soil minerals.Table 4 The physical–chemical characteristics of soil-slag samples.Full size tableConsidering the structural and morphological characterization of the investigated slag samples we propose a recipe of blast furnace slag and of waste slag dumped in landfill in accordance with the waste directive 2008/98/EC regarding the strategic goal of EU to a complete elimination of the disposal of wastes. The slag dump of Steel Plant of Galati has an enormous quantity of unused waste slag which may be mixed with granulated blast furnace slag, to save the natural resources used as raw materials in the metallurgical technological process.The presence of Ca2+ in the composition of the slag can maintain high alkalinity in the soil for a long time in the natural environment. The alkaline pH of the soil may contribute to a decrease the available concentration of heavy metals by reducing metal mobility and bonding metals into more stable fractions. One of the objectives of this research is improving the quality of the environment by using the mixture between two different slags on agricultural lands and reintroducing them in the agricultural centre, especially in acid soils. Acidic soils are characterized by an acidic pH that has spread in recent years due to excessive fertilizers or far too aggressive work31. The production is significantly influenced, and the treatment of acid soils is usually done using a series of natural materials (lime, dolomite), the consumption being approx. 20 t/hectare depending on the acidity of the soil and the nature of the plants grown on the respective surfaces.Our research consists in improving the characteristics and qualities of the acidic soils and helping to reintroduce it into the agricultural circuit by transforming a waste into a new material friendly-environmental, the mixture of blast furnace slag and waste slag dumped in landfill. More