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Global warming may lead to carbon transfers from soils to the atmosphere, yet this positive feedback to the climate system remains highly uncertain, especially in subsoils (Ilyina and Friedlingstein, 2016; Shi et al., 2018). Using natural geothermal soil warming gradients of up to +6.4 ∘C in subarctic grasslands (Sigurdsson et al., 2016), we show that soil organic carbon (SOC) stocks decline strongly and linearly with warming (−2.8 t ha−1 ∘C−1). Comparison of SOC stock changes following medium-term (5 and 10 years) and long-term (>50 years) warming revealed that all SOC stock reduction occurred within the first 5 years of warming, after which continued warming no longer reduced SOC stocks. This rapid equilibration of SOC observed in Andosol suggests a critical role for ecosystem adaptations to warming and could imply short-lived soil carbon–climate feedbacks. Our data further revealed that the soil C loss occurred in all aggregate size fractions and that SOC stock reduction was only visible in topsoil (0–10 cm). SOC stocks in subsoil (10–30 cm), where plant roots were absent, showed apparent conservation after >50 years of warming. The observed depth-dependent warming responses indicate that explicit vertical resolution is a prerequisite for global models to accurately project future SOC stocks for this soil type and should be investigated for soils with other mineralogies.

Diterpenes (C20H32) are biogenically emitted volatile compounds that only recently have been observed in ambient air. They are expected to be highly reactive, and their oxidation is likely to form condensable vapors. However, until now, no studies have investigated gas-phase diterpene oxidation. In this paper, we explored the ozonolysis of a diterpene, ent-kaurene, in a simulation chamber. Using state-of-the-art mass spectrometry, we characterized diterpene oxidation products for the first time, and we identified several products with varying oxidation levels, including highly oxygenated organic molecules (HOM), monomers, and dimers. The most abundant monomers measured using a nitrate chemical ionization mass spectrometer were C19H28O8 and C20H30O5, and the most abundant dimers were C38H60O6 and C39H62O6. The exact molar yield of HOM from kaurene ozonolysis was hard to quantify due to uncertainties in both the kaurene and HOM concentrations, but our best estimate was a few percent, which is similar to values reported earlier for many monoterpenes. We also monitored the decrease in the gas-phase oxidation products in response to an increased condensation sink in the chamber to deduce their affinity to condense. The oxygen content was a critical parameter affecting the volatility of products, with four to five O atoms needed for the main monomeric species to condense onto 80 nm particles. Finally, we report on the observed fragmentation and clustering patterns of kaurene in a Vocus proton-transfer-reaction time-of-flight mass spectrometer. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation, but more studies on different diterpenes are needed for a broader view of their role in atmospheric chemistry.

Terrestrial biosphere models typically use the biochemical model of Farquhar, von Caemmerer, and Berry (1980) to simulate photosynthesis, which requires accurate values of photosynthetic capacity of different biomes. However, data on tropical forests are sparse and highly variable due to the high species diversity, and it is still highly uncertain how these tropical forests respond to nutrient limitation in terms of C uptake. Tropical forests often grow on soils low in phosphorus (P) and are, in general, assumed to be P rather than nitrogen (N) limited. However, the relevance of P as a control of photosynthetic capacity is still debated. Here, we provide a comprehensive dataset of vertical profiles of photosynthetic capacity and important leaf traits, including leaf N and P concentrations, from two 3-year, large-scale nutrient addition experiments conducted in two tropical rainforests in French Guiana. These data present a unique source of information to further improve model representations of the roles of N, P, and other leaf nutrients in photosynthesis in tropical forests. To further facilitate the use of our data in syntheses and model studies, we provide an elaborate list of ancillary data, including important soil properties and nutrients, along with the leaf data. As environmental drivers are key to improve our understanding of carbon (C) and nutrient cycle interactions, this comprehensive dataset will aid to further enhance our understanding of how nutrient availability interacts with C uptake in tropical forests. The data are available at https://doi.org/10.5281/zenodo.5638236 (Verryckt, 2021).

Abstract Mycorrhizas are known to have a positive impact on plant growth and ability to resist major biotic and abiotic stresses. However, the metabolic alterations underlying mycorrhizal symbiosis are still understudied. By using metabolomics and transcriptomics approaches, cork oak roots colonized by the ectomycorrhizal fungus Pisolithus tinctorius were compared with non-colonized roots. Results show that compounds putatively corresponding to carbohydrates, organic acids, tannins, long-chain fatty acids and monoacylglycerols, were depleted in ectomycorrhizal cork oak colonized roots. Conversely, non-proteogenic amino acids, such as gamma-aminobutyric acid (GABA), and several putative defense-related compounds, including oxylipin-family compounds, terpenoids and B6 vitamers were induced in mycorrhizal roots. Transcriptomic analysis suggests the involvement of GABA in ectomycorrhizal symbiosis through increased synthesis and inhibition of degradation in mycorrhizal roots. Results from this global metabolomics analysis suggest decreases in root metabolites which are common components of exudates, and in compounds related to root external protective layers which could facilitate plant-fungal contact and enhance symbiosis. Root metabolic pathways involved in defense against stress were induced in ectomycorrhizal roots that could be involved in a plant mechanism to avoid uncontrolled growth of the fungal symbiont in the root apoplast. Several of the identified symbiosis-specific metabolites, such as GABA, may help to understand how ectomycorrhizal fungi such as P. tinctorius benefit their host plants.

It is unclear whether plant trait relationships found at the global scale extend to climatic extremes. Here the authors analyse six major aboveground traits to show that known plant trait relationships extend to the tundra biomes and exhibit the same two dimensions of variation detected at the global scale.

Continuous atmospheric CO2 monitoring data indicate an increase in the amplitude of seasonal CO2-cycle exchange (SCANBP) in northern high latitudes. The major drivers of enhanced SCANBP remain unclear and intensely debated, with land-use change, CO2 fertilization and warming being identified as likely contributors. We integrated CO2-flux data from two atmospheric inversions (consistent with atmospheric records) and from 11 state-of-the-art land-surface models (LSMs) to evaluate the relative importance of individual contributors to trends and drivers of the SCANBP of CO2 fluxes for 1980–2015. The LSMs generally reproduce the latitudinal increase in SCANBP trends within the inversions range. Inversions and LSMs attribute SCANBP increase to boreal Asia and Europe due to enhanced vegetation productivity (in LSMs) and point to contrasting effects of CO2 fertilization (positive) and warming (negative) on SCANBP. Our results do not support land-use change as a key contributor to the increase in SCANBP. The sensitivity of simulated microbial respiration to temperature in LSMs explained biases in SCANBP trends, which suggests that SCANBP could help to constrain model turnover times.

Measuring in situ soil fluxes of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) continuously at high frequency requires appropriate technology. We tested the combination of a commercial automated soil CO2 flux chamber system (LI-8100A) with a CH4 and N2O analyzer (Picarro G2308) in a tropical rainforest for 4 months. A chamber closure time of 2 min was sufficient for a reliable estimation of CO2 and CH4 fluxes (100 % and 98.5 % of fluxes were above minimum detectable flux – MDF, respectively). This closure time was generally not suitable for a reliable estimation of the low N2O fluxes in this ecosystem but was sufficient for detecting rare major peak events. A closure time of 25 min was more appropriate for reliable estimation of most N2O fluxes (85.6 % of measured fluxes are above MDF ± 0.002 nmol m−2 s−1). Our study highlights the importance of adjusted closure time for each gas.

Canopy nitrogen (N) concentration and content are linked to several vegetation processes. Therefore, canopy N concentration is a state variable in global vegetation models with coupled carbon (C) and N cycles. While there are ample C data available to constrain the models, widespread N data are lacking. Remotely sensed vegetation indices have been used to detect canopy N concentration and canopy N content at the local scale in grasslands and forests. Vegetation indices could be a valuable tool to detect canopy N concentration and canopy N content at larger scale. In this paper, we conducted a regional case-study analysis to investigate the relationship between the Medium Resolution Imaging Spectrometer (MERIS) Terrestrial Chlorophyll Index (MTCI) time series from European Space Agency (ESA) Envisat satellite at 1 km spatial resolution and both canopy N concentration (%N) and canopy N content (N g m−2, of ground area) from a Mediterranean forest inventory in the region of Catalonia, in the northeast of Spain. The relationships between the datasets were studied after resampling both datasets to lower spatial resolutions (20, 15, 10 and 5 km) and at the original spatial resolution of 1 km. The results at higher spatial resolution (1 km) yielded significant log–linear relationships between MTCI and both canopy N concentration and content: r2 = 0.32 and r2 = 0.17, respectively. We also investigated these relationships per plant functional type. While the relationship between MTCI and canopy N concentration was strongest for deciduous broadleaf and mixed plots (r2 = 0.24 and r2 = 0.44, respectively), the relationship between MTCI and canopy N content was strongest for evergreen needleleaf trees (r2 = 0.19). At the species level, canopy N concentration was strongly related to MTCI for European beech plots (r2 = 0.69). These results present a new perspective on the application of MTCI time series for canopy N detection.

Current land surface models (LSMs) typically represent soils in a very simplistic way, assuming soil organic carbon (SOC) as a bulk, and thus impeding a correct representation of deep soil carbon dynamics. Moreover, LSMs generally neglect the production and export of dissolved organic carbon (DOC) from soils to rivers, leading to overestimations of the potential carbon sequestration on land. This common oversimplified processing of SOC in LSMs is partly responsible for the large uncertainty in the predictions of the soil carbon response to climate change. In this study, we present a new soil carbon module called ORCHIDEE-SOM, embedded within the land surface model ORCHIDEE, which is able to reproduce the DOC and SOC dynamics in a vertically discretized soil to 2 m. The model includes processes of biological production and consumption of SOC and DOC, DOC adsorption on and desorption from soil minerals, diffusion of SOC and DOC, and DOC transport with water through and out of the soils to rivers. We evaluated ORCHIDEE-SOM against observations of DOC concentrations and SOC stocks from four European sites with different vegetation covers: a coniferous forest, a deciduous forest, a grassland, and a cropland. The model was able to reproduce the SOC stocks along their vertical profiles at the four sites and the DOC concentrations within the range of measurements, with the exception of the DOC concentrations in the upper soil horizon at the coniferous forest. However, the model was not able to fully capture the temporal dynamics of DOC concentrations. Further model improvements should focus on a plant- and depth-dependent parameterization of the new input model parameters, such as the turnover times of DOC and the microbial carbon use efficiency. We suggest that this new soil module, when parameterized for global simulations, will improve the representation of the global carbon cycle in LSMs, thus helping to constrain the predictions of the future SOC response to global warming.

The application of phosphorus (P) fertilizer to agricultural soils increased by 3.2 % annually from 2002 to 2010. We quantified in detail the P inputs and outputs of cropland and pasture and the P fluxes through human and livestock consumers of agricultural products on global, regional, and national scales from 2002 to 2010. Globally, half of the total P inputs into agricultural systems accumulated in agricultural soils during this period, with the rest lost to bodies of water through complex flows. Global P accumulation in agricultural soil increased from 2002 to 2010 despite decreases in 2008 and 2009, and the P accumulation occurred primarily in cropland. Despite the global increase in soil P, 32 % of the world's cropland and 43 % of the pasture had soil P deficits. Increasing soil P deficits were found for African cropland vs. increasing P accumulation in eastern Asia. European and North American pasture had a soil P deficit because the continuous removal of biomass P by grazing exceeded P inputs. International trade played a significant role in P redistribution among countries through the flows of P in fertilizer and food among countries. Based on country-scale budgets and trends we propose policy options to potentially mitigate regional P imbalances in agricultural soils, particularly by optimizing the use of phosphate fertilizer and the recycling of waste P. The trend of the increasing consumption of livestock products will require more P inputs to the agricultural system, implying a low P-use efficiency and aggravating P-stock scarcity in the future. The global and regional phosphorus budgets and their PUEs in agricultural systems are publicly available at https://doi.pangaea.de/10.1594/PANGAEA.875296.

Abstract Soil phosphatase levels strongly control the biotic pathways of phosphorus (P), an essential element for life, which is often limiting in terrestrial ecosystems. We investigated the influence of climatic and soil traits on phosphatase activity in terrestrial systems using metadata analysis from published studies. This is the first analysis of global measurements of phosphatase in natural soils. Our results suggest that organic P (Porg), rather than available P, is the most important P fraction in predicting phosphatase activity. Structural equation modeling using soil total nitrogen (TN), mean annual precipitation, mean annual temperature, thermal amplitude and total soil carbon as most available predictor variables explained up to 50% of the spatial variance in phosphatase activity. In this analysis, Porg could not be tested and among the rest of available variables, TN was the most important factor explaining the observed spatial gradients in phosphatase activity. On the other hand, phosphatase activity was also found to be associated with climatic conditions and soil type across different biomes worldwide. The close association among different predictors like Porg, TN and precipitation suggest that P recycling is driven by a broad scale pattern of ecosystem productivity capacity.

Site-level quantification of Net Ecosystem Production (NEP) and associated components rely on eddy covariance and biometric methods. Here these techniques are compared for global forest carbon fluxes, revealing differences in NEP, but similar estimates of ecosystem respiration and gross primary production.

Land surface phenology from time series of satellite data are expected to contribute to improve the representation of vegetation phenology in earth system models. We characterized the baseline phenology of the vegetation at the global scale from GEOCLIM-LAI, a global climatology of leaf area index (LAI) derived from 1-km SPOT VEGETATION time series for 1999-2010. The calibration with ground measurements showed that the start and end of season were best identified using respectively 30% and 40% threshold of LAI amplitude values. The satellite-derived phenology was spatially consistent with the global distributions of climatic drivers and biome land cover. The accuracy of the derived phenological metrics, evaluated using available ground observations for birch forests in Europe, cherry in Asia and lilac shrubs in North America showed an overall root mean square error lower than 19 days for the start, end and length of season, and good agreement between the latitudinal gradients of VEGETATION LAI phenology and ground data.

Dissolved organic carbon (DOC) in surface waters is connected to DOC in soil solution through hydrological pathways. Therefore, it is expected that long-term dynamics of DOC in surface waters reflect DOC trends in soil solution. However, a multitude of site studies have failed so far to establish consistent trends in soil solution DOC, whereas increasing concentrations in European surface waters over the past decades appear to be the norm, possibly as a result of recovery from acidification. The objectives of this study were therefore to understand the long-term trends of soil solution DOC from a large number of European forests (ICP Forests Level II plots) and determine their main physico-chemical and biological controls. We applied trend analysis at two levels: (1) to the entire European dataset and (2) to the individual time series and related trends with plot characteristics, i.e., soil and vegetation properties, soil solution chemistry and atmospheric deposition loads. Analyses of the entire dataset showed an overall increasing trend in DOC concentrations in the organic layers, but, at individual plots and depths, there was no clear overall trend in soil solution DOC. The rate change in soil solution DOC ranged between −16.8 and +23 % yr−1 (median = +0.4 % yr−1) across Europe. The non-significant trends (40 %) outnumbered the increasing (35 %) and decreasing trends (25 %) across the 97 ICP Forests Level II sites. By means of multivariate statistics, we found increasing trends in DOC concentrations with increasing mean nitrate (NO3−) deposition and increasing trends in DOC concentrations with decreasing mean sulfate (SO42−) deposition, with the magnitude of these relationships depending on plot deposition history. While the attribution of increasing trends in DOC to the reduction of SO42− deposition could be confirmed in low to medium N deposition areas, in agreement with observations in surface waters, this was not the case in high N deposition areas. In conclusion, long-term trends of soil solution DOC reflected the interactions between controls acting at local (soil and vegetation properties) and regional (atmospheric deposition of SO42− and inorganic N) scales.

Dynamic global vegetation models are used to predict the response of vegetation to climate change. They are essential for planning ecosystem management, understanding carbon cycle–climate feedbacks, and evaluating the potential impacts of climate change on global ecosystems. JULES (the Joint UK Land Environment Simulator) represents terrestrial processes in the UK Hadley Centre family of models and in the first generation UK Earth System Model. Previously, JULES represented five plant functional types (PFTs): broadleaf trees, needle-leaf trees, C3 and C4 grasses, and shrubs. This study addresses three developments in JULES. First, trees and shrubs were split into deciduous and evergreen PFTs to better represent the range of leaf life spans and metabolic capacities that exists in nature. Second, we distinguished between temperate and tropical broadleaf evergreen trees. These first two changes result in a new set of nine PFTs: tropical and temperate broadleaf evergreen trees, broadleaf deciduous trees, needle-leaf evergreen and deciduous trees, C3 and C4 grasses, and evergreen and deciduous shrubs. Third, using data from the TRY database, we updated the relationship between leaf nitrogen and the maximum rate of carboxylation of Rubisco (Vcmax), and updated the leaf turnover and growth rates to include a trade-off between leaf life span and leaf mass per unit area.Overall, the simulation of gross and net primary productivity (GPP and NPP, respectively) is improved with the nine PFTs when compared to FLUXNET sites, a global GPP data set based on FLUXNET, and MODIS NPP. Compared to the standard five PFTs, the new nine PFTs simulate a higher GPP and NPP, with the exception of C3 grasses in cold environments and C4 grasses that were previously over-productive. On a biome scale, GPP is improved for all eight biomes evaluated and NPP is improved for most biomes – the exceptions being the tropical forests, savannahs, and extratropical mixed forests where simulated NPP is too high. With the new PFTs, the global present-day GPP and NPP are 128 and 62 Pg C year−1, respectively. We conclude that the inclusion of trait-based data and the evergreen/deciduous distinction has substantially improved productivity fluxes in JULES, in particular the representation of GPP. These developments increase the realism of JULES, enabling higher confidence in simulations of vegetation dynamics and carbon storage.

Atmospheric deposition of iron (Fe) plays an important role in controlling oceanic primary productivity. However, the sources of Fe in the atmosphere are not well understood. In particular, the combustion sources of Fe and the subsequent deposition to the oceans have been accounted for in only few ocean biogeochemical models of the carbon cycle. Here we used a mass-balance method to estimate the emissions of Fe from the combustion of fossil fuels and biomass by accounting for the Fe contents in fuel and the partitioning of Fe during combustion. The emissions of Fe attached to aerosols from combustion sources were estimated by particle size, and their uncertainties were quantified by a Monte Carlo simulation. The emissions of Fe from mineral sources were estimated using the latest soil mineralogical database to date. As a result, the total Fe emissions from combustion averaged for 1960–2007 were estimated to be 5.3 Tg yr−1 (90% confidence of 2.3 to 12.1). Of these emissions, 1, 27 and 72% were emitted in particles < 1 μm (PM1), 1–10 μm (PM1-10), and > 10 μm (PM> 10), respectively, compared to a total Fe emission from mineral dust of 41.0 Tg yr−1 in a log-normal distribution with a mass median diameter of 2.5 μm and a geometric standard deviation of 2. For combustion sources, different temporal trends were found in fine and medium-to-coarse particles, with a notable increase in Fe emissions in PM1 since 2000 due to an increase in Fe emission from motor vehicles (from 0.008 to 0.0103 Tg yr−1 in 2000 and 2007, respectively). These emissions have been introduced in a global 3-D transport model run at a spatial resolution of 0.94° latitude by 1.28° longitude to evaluate our estimation of Fe emissions. The modelled Fe concentrations as monthly means were compared with the monthly (57 sites) or daily (768 sites) measured concentrations at a total of 825 sampling stations. The deviation between modelled and observed Fe concentrations attached to aerosols at the surface was within a factor of 2 at most sampling stations, and the deviation was within a factor of 1.5 at sampling stations dominated by combustion sources. We analysed the relative contribution of combustion sources to total Fe concentrations over different regions of the world. The new mineralogical database led to a modest improvement in the simulation relative to station data even in dust-dominated regions, but could provide useful information on the chemical forms of Fe in dust for coupling with ocean biota models. We estimated a total Fe deposition sink of 8.4 Tg yr−1 over global oceans, 7% of which originated from the combustion sources. Our central estimates of Fe emissions from fossil fuel combustion (mainly from coal) are generally higher than those in previous studies, although they are within the uncertainty range of our estimates. In particular, the higher than previously estimated Fe emission from coal combustion implies a larger atmospheric anthropogenic input of soluble Fe to the northern Atlantic and northern Pacific Oceans, which is expected to enhance the biological carbon pump in those regions.

Evergreen trees in the Mediterranean region must cope with a wide range of environmental stresses from summer drought to winter cold. The mildness of Mediterranean winters can periodically lead to favourable environmental conditions above the threshold for a positive carbon balance, benefitting evergreen woody species more than deciduous ones. The comparatively lower solar energy input in winter decreases the foliar light saturation point. This leads to a higher susceptibility to photoinhibitory stress especially when chilly (< 12 °C) or freezing temperatures (< 0 °C) coincide with clear skies and relatively high solar irradiances. Nonetheless, the advantage of evergreen species that are able to photosynthesize all year round where a significant fraction can be attributed to winter months, compensates for the lower carbon uptake during spring and summer in comparison to deciduous species. We investigated the ecophysiological behaviour of three co-occurring mature evergreen tree species (Quercus ilex L., Pinus halepensis Mill., and Arbutus unedo L.). Therefore, we collected twigs from the field during a period of mild winter conditions and after a sudden cold period. After both periods, the state of the photosynthetic machinery was tested in the laboratory by estimating the foliar photosynthetic potential with CO2 response curves in parallel with chlorophyll fluorescence measurements. The studied evergreen tree species benefited strongly from mild winter conditions by exhibiting extraordinarily high photosynthetic potentials. A sudden period of frost, however, negatively affected the photosynthetic apparatus, leading to significant decreases in key physiological parameters such as the maximum carboxylation velocity (Vc, max), the maximum photosynthetic electron transport rate (Jmax), and the optimal fluorometric quantum yield of photosystem II (Fv/Fm). The responses of Vc, max and Jmax were highly species specific, with Q. ilex exhibiting the highest and P. halepensis the lowest reductions. In contrast, the optimal fluorometric quantum yield of photosystem II (Fv/Fm) was significantly lower in A. unedo after the cold period. The leaf position played an important role in Q. ilex showing a stronger winter effect on sunlit leaves in comparison to shaded leaves. Our results generally agreed with the previous classifications of photoinhibition-tolerant (P. halepensis) and photoinhibition-avoiding (Q. ilex) species on the basis of their susceptibility to dynamic photoinhibition, whereas A. unedo was the least tolerant to photoinhibition, which was chronic in this species. Q. ilex and P. halepensis seem to follow contrasting photoprotective strategies. However, they seemed equally successful under the prevailing conditions exhibiting an adaptive advantage over A. unedo. These results show that our understanding of the dynamics of interspecific competition in Mediterranean ecosystems requires consideration of the physiological behaviour during winter which may have important implications for long-term carbon budgets and growth trends.

Landscape-scale fluxes of biogenic gases were surveyed by deploying a 100 m Teflon tube attached to a tethered balloon as a sampling inlet for a fast-response proton-transfer-reaction mass spectrometer (PTRMS). Along with meteorological instruments deployed on the tethered balloon and a 3 m tripod and outputs from a regional weather model, these observations were used to estimate landscape-scale biogenic volatile organic compound fluxes with two micrometeorological techniques: mixed layer variance and surface layer gradients. This highly mobile sampling system was deployed at four field sites near Barcelona to estimate landscape-scale biogenic volatile organic compound (BVOC) emission factors in a relatively short period (3 weeks). The two micrometeorological techniques were compared with emissions predicted with a biogenic emission model using site-specific emission factors and land-cover characteristics for all four sites. The methods agreed within the uncertainty of the techniques in most cases, even though the locations had considerable heterogeneity in species distribution and complex terrain. Considering the wide range in reported BVOC emission factors for individual vegetation species (more than an order of magnitude), this temporally short and inexpensive flux estimation technique may be useful for constraining BVOC emission factors used as model inputs.

As a key component of the carbon cycle, soil CO2 efflux (SCE) is being increasingly studied to improve our mechanistic understanding of this important carbon flux. Predicting ecosystem responses to climate change often depends on extrapolation of current relationships between ecosystem processes and their climatic drivers to conditions not yet experienced by the ecosystem. This raises the question of to what extent these relationships remain unaltered beyond the current climatic window for which observations are available to constrain the relationships. Here, we evaluate whether current responses of SCE to fluctuations in soil temperature and soil water content can be used to predict SCE under altered rainfall patterns. Of the 58 experiments for which we gathered SCE data, 20 were discarded because either too few data were available or inconsistencies precluded their incorporation in the analyses. The 38 remaining experiments were used to test the hypothesis that a model parameterized with data from the control plots (using soil temperature and water content as predictor variables) could adequately predict SCE measured in the manipulated treatment. Only for 7 of these 38 experiments was this hypothesis rejected. Importantly, these were the experiments with the most reliable data sets, i.e., those providing high-frequency measurements of SCE. Regression tree analysis demonstrated that our hypothesis could be rejected only for experiments with measurement intervals of less than 11 days, and was not rejected for any of the 24 experiments with larger measurement intervals. This highlights the importance of high-frequency measurements when studying effects of altered precipitation on SCE, probably because infrequent measurement schemes have insufficient capacity to detect shifts in the climate dependencies of SCE. Hence, the most justified answer to the question of whether current moisture responses of SCE can be extrapolated to predict SCE under altered precipitation regimes is "no" – as based on the most reliable data sets available. We strongly recommend that future experiments focus more strongly on establishing response functions across a broader range of precipitation regimes and soil moisture conditions. Such experiments should make accurate measurements of water availability, should conduct high-frequency SCE measurements, and should consider both instantaneous responses and the potential legacy effects of climate extremes. This is important, because with the novel approach presented here, we demonstrated that, at least for some ecosystems, current moisture responses could not be extrapolated to predict SCE under altered rainfall conditions.

Atmospheric volatile organic compounds (VOCs) have key environmental and biological roles, but little is known about the daily VOC mixing ratios in Mediterranean urban and natural environments. We measured VOC mixing ratios concurrently at an urban and a rural site during the winter DAURE campaign in the northeastern Iberian Peninsula, by means of PTR-MS at both locations: a PTR-Quad-MS at the urban site and a PTR-ToF-MS at the rural site. All VOC mixing ratios measured were higher at the urban site (e.g. acetaldehyde, isoprene, benzene, and toluene with averages up to 1.68, 0.31, 0.58 and 2.71 ppbv, respectively), with the exception of some short-chain oxygenated VOCs such as acetone (with similar averages of 0.7–1.6 ppbv at both sites). The average diurnal pattern also differed between the sites. Most of the VOCs at the urban location showed their highest mixing ratios in the morning and evening. These peaks coincided with traffic during rush hour, the main origin of most of the VOCs analyzed. Between these two peaks, the sea breeze transported the urban air inland, thus helping to lower the VOC loading at the urban site. At the rural site, most of the measured VOCs were advected by the midday sea breeze, yielding the highest daily VOC mixing ratios (e.g. acetaldehyde, isoprene, benzene, and toluene with averages up to 0.65, 0.07, 0.19, and 0.41 ppbv, respectively). Only biogenic monoterpenes showed a clear local origin at this site. In addition, the concentrations of fine particulate matter observed at both sites, together with the synoptic meteorological conditions and radio-sounding data, allowed the identification of different atmospheric scenarios that had a clear influence on the measured VOC mixing ratios. These results highlight the differences and relationships in VOC mixing ratios between nearby urban and rural areas in Mediterranean regions. Further research in other urban-rural areas is warranted to better understand the urban-rural influence on atmospheric VOC mixing ratios under different atmospheric conditions.

In this study, we compare annual fluxes of methane (CH4), nitrous oxide (N2O) and soil respiratory carbon dioxide (CO2) measured at nine European peatlands (n = 4) and shrublands (n = 5). The sites range from northern Sweden to Spain, covering a span in mean annual air temperature from 0 to 16 °C, and in annual precipitation from 300 to 1300 mm yr−1. The effects of climate change, including temperature increase and prolonged drought, were tested at five shrubland sites. At one peatland site, the long-term (> 30 yr) effect of drainage was assessed, while increased nitrogen deposition was investigated at three peatland sites. The shrublands were generally sinks for atmospheric CH4, whereas the peatlands were CH4 sources, with fluxes ranging from −519 to +6890 mg CH4-C m−2 yr−1 across the studied ecosystems. At the peatland sites, annual CH4 emission increased with mean annual air temperature, while a negative relationship was found between net CH4 uptake and the soil carbon stock at the shrubland sites. Annual N2O fluxes were generally small ranging from −14 to 42 mg N2O-N m−2 yr−1. Highest N2O emission occurred at the sites that had highest nitrate (NO3−) concentration in the soil water. Furthermore, experimentally increased NO3− deposition led to increased N2O efflux, whereas prolonged drought and long-term drainage reduced the N2O efflux. Soil CO2 emissions in control plots ranged from 310 to 732 g CO2-C m−2 yr−1. Drought and long-term drainage generally reduced the soil CO2 efflux, except at a hydric shrubland where drought tended to increase soil respiration. In terms of fractional importance of each greenhouse gas to the total numerical global warming response, the change in CO2 efflux dominated the response in all treatments (ranging 71–96%), except for NO3− addition where 89% was due to change in CH4 emissions. Thus, in European peatlands and shrublands the effect on global warming induced by the investigated anthropogenic disturbances will be dominated by variations in soil CO2 fluxes.

The DO3SE (Deposition of O3 for Stomatal Exchange) model is an established tool for estimating ozone (O3) deposition, stomatal flux and impacts to a variety of vegetation types across Europe. It has been embedded within the EMEP (European Monitoring and Evaluation Programme) photochemical model to provide a policy tool capable of relating the flux-based risk of vegetation damage to O3 precursor emission scenarios for use in policy formulation. A key limitation of regional flux-based risk assessments has been the assumption that soil water deficits are not limiting O3 flux due to the unavailability of evaluated methods for modelling soil water deficits and their influence on stomatal conductance (gsto), and subsequent O3 flux. This paper describes the development and evaluation of a method to estimate soil moisture status and its influence on gsto for a variety of forest tree species. This DO3SE soil moisture module uses the Penman-Monteith energy balance method to drive water cycling through the soil-plant-atmosphere system and empirical data describing gsto relationships with pre-dawn leaf water status to estimate the biological control of transpiration. We trial four different methods to estimate this biological control of the transpiration stream, which vary from simple methods that relate soil water content or potential directly to gsto, to more complex methods that incorporate hydraulic resistance and plant capacitance that control water flow through the plant system. These methods are evaluated against field data describing a variety of soil water variables, gsto and transpiration data for Norway spruce (Picea abies), Scots pine (Pinus sylvestris), birch (Betula pendula), aspen (Populus tremuloides), beech (Fagus sylvatica) and holm oak (Quercus ilex) collected from ten sites across Europe and North America. Modelled estimates of these variables show consistency with observed data when applying the simple empirical methods, with the timing and magnitude of soil drying events being captured well across all sites and reductions in transpiration with the onset of drought being predicted with reasonable accuracy. The more complex methods, which incorporate hydraulic resistance and plant capacitance, perform less well, with predicted drying cycles consistently underestimating the rate and magnitude of water loss from the soil. A sensitivity analysis showed that model performance was strongly dependent upon the local parameterisation of key model drivers such as the maximum gsto, soil texture, root depth and leaf area index. The results suggest that the simple modelling methods that relate gsto directly to soil water content and potential provide adequate estimates of soil moisture and influence on gsto such that they are suitable to be used to assess the potential risk posed by O3 to forest trees across Europe.

PM1 (particulate matter with an aerodynamic diameter This paper presents a method for estimating cooking organic aerosol in ambient datasets based on the fractions of organic mass fragments at m/z 55 and 57: their data points fall into a V-shape in a scatter plot, with strongly influenced HOA data aligned to the right arm and strongly influenced COA data points aligned to the left arm. HR data show that this differentiation is mainly driven by the oxygen-containing ions C3H3O+ and C3H5O+, even though their contributions to m/z 55 and 57 are low compared to the reduced ions C4H7+ and C4H9+. A simple estimation method based on the markers m/z 55, 57, and 44 is developed here and allows for a first-order-estimation of COA in urban air. This study emphasizes the importance of cooking activities for ambient air quality and confirms the importance of chemical composition measurements with a high mass and time resolution.

We present results from the international field campaign DAURE (Determination of the sources of atmospheric Aerosols in Urban and Rural Environments in the Western Mediterranean), with the objective of apportioning the sources of fine carbonaceous aerosols. Submicron fine particulate matter (PM1) samples were collected during February–March 2009 and July 2009 at an urban background site in Barcelona (BCN) and at a forested regional background site in Montseny (MSY). We present radiocarbon (14C) analysis for elemental and organic carbon (EC and OC) and source apportionment for these data. We combine the results with those from component analysis of aerosol mass spectrometer (AMS) measurements, and compare to levoglucosan-based estimates of biomass burning OC, source apportionment of filter data with inorganic composition + EC + OC, submicron bulk potassium (K) concentrations, and gaseous acetonitrile concentrations. At BCN, 87 % and 91 % of the EC on average, in winter and summer, respectively, had a fossil origin, whereas at MSY these fractions were 66 % and 79 %. The contribution of fossil sources to organic carbon (OC) at BCN was 40 % and 48 %, in winter and summer, respectively, and 31 % and 25 % at MSY. The combination of results obtained using the 14C technique, AMS data, and the correlations between fossil OC and fossil EC imply that the fossil OC at Barcelona is ∼47 % primary whereas at MSY the fossil OC is mainly secondary (∼85 %). Day-to-day variation in total carbonaceous aerosol loading and the relative contributions of different sources predominantly depended on the meteorological transport conditions. The estimated biogenic secondary OC at MSY only increased by ∼40 % compared to the order-of-magnitude increase observed for biogenic volatile organic compounds (VOCs) between winter and summer, which highlights the uncertainties in the estimation of that component. Biomass burning contributions estimated using the 14C technique ranged from similar to slightly higher than when estimated using other techniques, and the different estimations were highly or moderately correlated. Differences can be explained by the contribution of secondary organic matter (not included in the primary biomass burning source estimates), and/or by an overestimation of the biomass burning OC contribution by the 14C technique if the estimated biomass burning EC/OC ratio used for the calculations is too high for this region. Acetonitrile concentrations correlate well with the biomass burning EC determined by 14C. K is a noisy tracer for biomass burning.

Atmospheric volatile organic compounds (VOCs) are involved in ozone and aerosol generation, thus having implications for air quality and climate. VOCs and their emissions by vegetation also have important ecological roles as they can protect plants from stresses and act as communication cues between plants and between plants and animals. In spite of these key environmental and biological roles, the reports on seasonal and daily VOC mixing ratios in the literature for Mediterranean natural environments are scarce. We conducted seasonal (winter and summer) measurements of VOC mixing ratios in an elevated (720 m a.s.l.) holm oak Mediterranean forest site near the metropolitan area of Barcelona (NE Iberian Peninsula). Methanol was the most abundant compound among all the VOCs measured in both seasons. While aromatic VOCs showed almost no seasonal variability, short-chain oxygenated VOCs presented higher mixing ratios in summer, presumably due to greater emission by vegetation and increased photochemistry, both enhanced by the high temperatures and solar radiation in summer. Isoprenoid VOCs showed the biggest seasonal change in mixing ratios: they increased by one order of magnitude in summer, as a result of the vegetation's greater physiological activity and emission rates. The maximum diurnal concentrations of ozone increased in summer too, most likely due to more intense photochemical activity and the higher levels of VOCs in the air. The daily variation of VOC mixing ratios was mainly governed by the wind regime of the mountain, as the majority of the VOC species analyzed followed a very similar diel cycle. Mountain and sea breezes that develop after sunrise advect polluted air masses to the mountain. These polluted air masses had previously passed over the urban and industrial areas surrounding the Barcelona metropolitan area, where they were enriched in NOx and in VOCs of biotic and abiotic origin. Moreover, these polluted air masses receive additional biogenic VOCs emitted in the local valley by the vegetation, thus enhancing O3 formation in this forested site. The only VOC species that showed a somewhat different daily pattern were monoterpenes because of their local biogenic emission. Isoprene also followed in part the daily pattern of monoterpenes, but only in summer when its biotic sources were stronger. The increase by one order of magnitude in the concentrations of these volatile isoprenoids highlights the importance of local biogenic summer emissions in these Mediterranean forested areas which also receive polluted air masses from nearby or distant anthropic sources.

The capacity for volatile isoprenoid production under standardized environmental conditions at a certain time (ES, the emission factor) is a key characteristic in constructing isoprenoid emission inventories. However, there is large variation in published ES estimates for any given species partly driven by dynamic modifications in ES due to acclimation and stress responses. Here we review additional sources of variation in ES estimates that are due to measurement and analytical techniques and calculation and averaging procedures, and demonstrate that estimations of ES critically depend on applied experimental protocols and on data processing and reporting. A great variety of experimental setups has been used in the past, contributing to study-to-study variations in ES estimates. We suggest that past experimental data should be distributed into broad quality classes depending on whether the data can or cannot be considered quantitative based on rigorous experimental standards. Apart from analytical issues, the accuracy of ES values is strongly driven by extrapolation and integration errors introduced during data processing. Additional sources of error, especially in meta-database construction, can further arise from inconsistent use of units and expression bases of ES. We propose a standardized experimental protocol for BVOC estimations and highlight basic meta-information that we strongly recommend to report with any ES measurement. We conclude that standardization of experimental and calculation protocols and critical examination of past reports is essential for development of accurate emission factor databases.

The rate of constitutive isoprenoid emissions from plants is driven by plant emission capacity under specified environmental conditions (ES, the emission factor) and by responsiveness of the emissions to instantaneous variations in environment. In models of isoprenoid emission, ES has been often considered as intrinsic species-specific constant invariable in time and space. Here we analyze the variations in species-specific values of ES under field conditions focusing on abiotic stresses, past environmental conditions and developmental processes. The reviewed studies highlight strong stress-driven, adaptive (previous temperature and light environment and growth CO2 concentration) and developmental (leaf age) variations in ES values operating at medium to long time scales. These biological factors can alter species-specific ES values by more than an order of magnitude. While the majority of models based on early concepts still ignore these important sources of variation, recent models are including some of the medium- to long-term controls. However, conceptually different strategies are being used for incorporation of these longer-term controls with important practical implications for parameterization and application of these models. This analysis emphasizes the need to include more biological realism in the isoprenoid emission models and also highlights the gaps in knowledge that require further experimental work to reduce the model uncertainties associated with biological sources of variation.

In models of plant volatile isoprenoid emissions, the instantaneous compound emission rate typically scales with the plant's emission potential under specified environmental conditions, also called as the emission factor, ES. In the most widely employed plant isoprenoid emission models, the algorithms developed by Guenther and colleagues (1991, 1993), instantaneous variation of the steady-state emission rate is described as the product of ES and light and temperature response functions. When these models are employed in the atmospheric chemistry modeling community, species-specific ES values and parameter values defining the instantaneous response curves are often taken as initially defined. In the current review, we argue that ES as a characteristic used in the models importantly depends on our understanding of which environmental factors affect isoprenoid emissions, and consequently need standardization during experimental ES determinations. In particular, there is now increasing consensus that in addition to variations in light and temperature, alterations in atmospheric and/or within-leaf CO2 concentrations may need to be included in the emission models. Furthermore, we demonstrate that for less volatile isoprenoids, mono- and sesquiterpenes, the emissions are often jointly controlled by the compound synthesis and volatility. Because of these combined biochemical and physico-chemical drivers, specification of ES as a constant value is incapable of describing instantaneous emissions within the sole assumptions of fluctuating light and temperature as used in the standard algorithms. The definition of ES also varies depending on the degree of aggregation of ES values in different parameterization schemes (leaf- vs. canopy- or region-scale, species vs. plant functional type levels) and various aggregated ES schemes are not compatible for different integration models. The summarized information collectively emphasizes the need to update model algorithms by including missing environmental and physico-chemical controls, and always to define ES within the proper context of model structure and spatial and temporal resolution.

Large uncertainties exist in our knowledge of regional emissions of non-methane biogenic volatile organic compounds (BVOC). We address these uncertainties through a two-pronged approach by compiling a state of the art database of the emissions potentials for 80 European forest species, and by a model assessment and inter-comparison, both at the local and regional scale, under present and projected future climatic conditions. We coupled three contrasting isoprenoid models with the ecophysiological forest model GOTILWA+ to evaluate leaf and ecosystem isoprenoid emissions, build an emissions inventory for European forests, and to consider model behaviour in present climate and under projected future climate change conditions. Hourly, daily and annual isoprene emissions as simulated by the models were evaluated against flux measurements. The validation highlighted a general model capacity to capture gross fluxes but inefficiencies in capturing short term variability. A regional inventory of isoprenoid emissions for European forests was created using each of the three modelling approaches. The models agreed on an average European emissions budget of 1.03 TgC a−1 for isoprene and 0.97 TgC a−1 for monoterpenes for the period 1960–1990, which was dominated by a few species with largest aerial coverage. Species contribution to total emissions depended both on species emission potential and geographical distribution. For projected future climate conditions, however, emissions budgets proved highly model dependent, illustrating the current uncertainty associated with isoprenoid emissions responses to potential future conditions. These results suggest that current model estimates of isoprenoid emissions concur well, but future estimates are highly uncertain. We conclude that development of reliable models is highly urgent, but for the time being, future BVOC emission scenario estimates should consider results from an ensemble of available emission models.

Muchos de los modelos actuales para estimar la productividad primaria bruta (PPB) de los ecosistemas terrestres dependen de la eficiencia del uso de la radiación (EUR), el cociente entre el CO2 absorbido y la radiación absorbida. Una metodología para estimar la EUR a partir de satelitales independizaría a las estimaciones de productividad primaria de los datos climáticos hasta ahora usados para estimar la EUR. En este trabajo mostramos que los bosques mediterráneos presentan muy leves cambios estacionales de los índices de vegetación, indicadores de biomasa verde y, por el contrario, grandes cambios estacionales en la absorción de CO2 . El Índice de Reflectancia Fotoquímica (PRI), calculado a partir de la reflectancia obtenida con el sensor MODIS, presentó una alta correlación con la variabilidad estacional de la EUR estimada a escala de ecosistema con técnicas de covarianza turbulenta en dos bosques mediterráneos, a lo largo de cinco años. Estos resultados nos muestran que es posible estimar la variabilidad temporal de la EUR utilizando el PRI y mejorar las estimaciones de la absorción de carbono. Este avance conceptual y tecnológico evita así la necesidad de realizar supuestos sobre las variaciones de la EUR y la relación con sus controles climáticos.

No abstract available.