Reading tea leaves worldwide: Decoupled drivers of initial litter decomposition mass-loss rate and stabilization.

The breakdown of plant material fuels soil functioning and biodiversity. Currently, process understanding of global decomposition patterns and the drivers of such patterns are hampered by the lack of coherent large-scale datasets. We buried 36,000 individual litterbags (tea bags) worldwide and found an overall negative correlation between initial mass-loss rates and stabilization factors of plant-derived carbon, using the Tea Bag Index (TBI). The stabilization factor quantifies the degree to which easy-to-degrade components accumulate during early-stage decomposition (e.g. by environmental limitations). However, agriculture and an interaction between moisture and temperature led to a decoupling between initial mass-loss rates and stabilization, notably in colder locations. Using TBI improved mass-loss estimates of natural litter compared to models that ignored stabilization. Ignoring the transformation of dead plant material to more recalcitrant substances during early-stage decomposition, and the environmental control of this transformation, could overestimate carbon losses during early decomposition in carbon cycle models.

Cell wall ester modifications and volatile emission signatures of plant response to abiotic stress.

Growth suppression and defence signalling are simultaneous strategies that plants invoke to respond to abiotic stress. Here, we show that the drought stress response of poplar trees (Populus trichocarpa) is initiated by a suppression in cell wall derived methanol (MeOH) emissions and activation of acetic acid (AA) fermentation defences. Temperature sensitive emissions dominated by MeOH (AA/MeOH <30%) were observed from physiologically active leaves, branches, detached stems, leaf cell wall isolations and whole ecosystems. In contrast, drought treatment resulted in a suppression of MeOH emissions and strong enhancement in AA emissions together with volatiles acetaldehyde, ethanol, and acetone. These drought-induced changes coincided with a reduction in stomatal conductance, photosynthesis, transpiration, and leaf water potential. The strong enhancement in AA/MeOH emission ratios during drought (400%-3500%) was associated with an increase in acetate content of whole leaf cell walls, which became significantly 13 C2 -labelled following the delivery of 13 C2 -acetate via the transpiration stream. The results are consistent with both enzymatic and nonenzymatic MeOH and AA production at high temperature in hydrated tissues associated with accelerated primary cell wall growth processes, which are downregulated during drought. While the metabolic source(s) require further investigation, the observations are consistent with drought-induced activation of aerobic fermentation driving high rates of foliar AA emissions and enhancements in leaf cell wall O-acetylation. We suggest that atmospheric AA/MeOH emission ratios could be useful as a highly sensitive signal in studies investigating environmental and biological factors influencing growth-defence trade-offs in plants and ecosystems.

Dry Deposition of Ozone over Land: Processes, Measurement, and Modeling.

Dry deposition of ozone is an important sink of ozone in near surface air. When dry deposition occurs through plant stomata, ozone can injure the plant, altering water and carbon cycling and reducing crop yields. Quantifying both stomatal and nonstomatal uptake accurately is relevant for understanding ozone's impact on human health as an air pollutant and on climate as a potent short-lived greenhouse gas and primary control on the removal of several reactive greenhouse gases and air pollutants. Robust ozone dry deposition estimates require knowledge of the relative importance of individual deposition pathways, but spatiotemporal variability in nonstomatal deposition is poorly understood. Here we integrate understanding of ozone deposition processes by synthesizing research from fields such as atmospheric chemistry, ecology, and meteorology. We critically review methods for measurements and modeling, highlighting the empiricism that underpins modeling and thus the interpretation of observations. Our unprecedented synthesis of knowledge on deposition pathways, particularly soil and leaf cuticles, reveals process understanding not yet included in widely-used models. If coordinated with short-term field intensives, laboratory studies, and mechanistic modeling, measurements from a few long-term sites would bridge the molecular to ecosystem scales necessary to establish the relative importance of individual deposition pathways and the extent to which they vary in space and time. Our recommended approaches seek to close knowledge gaps that currently limit quantifying the impact of ozone dry deposition on air quality, ecosystems, and climate.

Water use strategy affects avoidance of ozone stress by stomatal closure in Mediterranean trees-A modelling analysis.

Both ozone (O3 ) and drought can limit carbon fixation by forest trees. To cope with drought stress, plants have isohydric or anisohydric water use strategies. Ozone enters plant tissues through stomata. Therefore, stomatal closure can be interpreted as avoidance to O3 stress. Here, we applied an optimization model of stomata involving water, CO2 , and O3 flux to test whether isohydric and anisohydric strategies may affect avoidance of O3 stress by stomatal closure in four Mediterranean tree species during drought. The data suggest that stomatal closure represents a response to avoid damage to the photosynthetic mechanisms under elevated O3 depending on plant water use strategy. Under high-O3 and well-watered conditions, isohydric species limited O3 fluxes by stomatal closure, whereas anisohydric species activated a tolerance response and did not actively close stomata. Under both O3 and drought stress, however, anisohydric species enhanced the capacity of avoidance by closing stomata to cope with the severe oxidative stress. In the late growing season, regardless of the water use strategy, the efficiency of O3 stress avoidance decreased with leaf ageing. As a result, carbon assimilation rate was decreased by O3 while stomata did not close enough to limit transpirational water losses.

Current and future impacts of drought and ozone stress on Northern Hemisphere forests.

Rising ozone (O3 ) concentrations, coupled with an increase in drought frequency due to climate change, pose a threat to plant growth and productivity which could negatively affect carbon sequestration capacity of Northern Hemisphere (NH) forests. Using long-term observations of O3 mixing ratios and soil water content (SWC), we implemented empirical drought and O3 stress parameterizations in a coupled stomatal conductance-photosynthesis model to assess their impacts on plant gas exchange at three FLUXNET sites: Castelporziano, Blodgett and Hyytiälä. Model performance was evaluated by comparing model estimates of gross primary productivity (GPP) and latent heat fluxes (LE) against present-day observations. CMIP5 GCM model output data were then used to investigate the potential impact of the two stressors on forests by the middle (2041-2050) and end (2091-2100) of the 21st century. We found drought stress was the more significant as it reduced model overestimation of GPP and LE by ~11%-25% compared to 1%-11% from O3 stress. However, the best model fit to observations at all the study sites was obtained with O3 and drought stress combined, such that the two stressors counteract the impact of each other. With the inclusion of drought and O3 stress, GPP at CPZ, BLO and HYY is projected to increase by 7%, 5% and 8%, respectively, by mid-century and by 14%, 11% and 14% by 2091-2100 as atmospheric CO2 increases. Estimates were up to 21% and 4% higher when drought and O3 stress were neglected respectively. Drought stress will have a substantial impact on plant gas exchange and productivity, off-setting and possibly negating CO2 fertilization gains in future, suggesting projected increases in the frequency and severity of droughts in the NH will play a significant role in forest productivity and carbon budgets in future.

Testing Removal of Carbon Dioxide, Ozone, and Atmospheric Particles by Urban Parks in Italy.

Cities are responsible for more than 80% of global greenhouse gas emissions. Sequestration of air pollutants is one of the main ecosystem services that urban forests provide to the citizens. The atmospheric concentration of several pollutants such as carbon dioxide (CO2), tropospheric ozone (O3), and particulate matter (PM) can be reduced by urban trees through processes of adsorption and deposition. We predict the quantity of CO2, O3, and PM removed by urban tree species with the multilayer canopy model AIRTREE in two representative urban parks in Italy: Park of Castel di Guido, a 3673 ha reforested area located northwest of Rome, and Park of Valentino, a 42 ha urban park in downtown Turin. We estimated a total annual removal of 1005 and 500 kg of carbon per hectare, 8.1 and 1.42 kg of ozone per hectare, and 8.4 and 8 kg of PM10 per hectare. We highlighted differences in pollutant sequestration between urban areas and between species, shedding light on the importance to perform extensive in situ measurements and modeling analysis of tree characteristics to provide realistic estimates of urban parks to deliver ecosystem services.

Isoprene is more affected by climate drivers than monoterpenes: A meta-analytic review on plant isoprenoid emissions.

Isoprene and monoterpenes (MTs) are among the most abundant and reactive volatile organic compounds produced by plants (biogenic volatile organic compounds). We conducted a meta-analysis to quantify the mean effect of environmental factors associated to climate change (warming, drought, elevated CO2 , and O3 ) on the emission of isoprene and MTs. Results indicated that all single factors except warming inhibited isoprene emission. When subsets of data collected in experiments run under similar change of a given environmental factor were compared, isoprene and photosynthesis responded negatively to elevated O3 (-8% and -10%, respectively) and drought (-15% and -42%), and in opposite ways to elevated CO2 (-23% and +55%) and warming (+53% and -23%, respectively). Effects on MTs emission were usually not significant, with the exceptions of a significant stimulation caused by warming (+39%) and by elevated O3 (limited to O3 -insensitive plants, and evergreen species with storage organs). Our results clearly highlight individual effects of environmental factors on isoprene and MT emissions, and an overall uncoupling between these secondary metabolites produced by the same methylerythritol 4-phosphate pathway. Future results from manipulative experiments and long-term observations may help untangling the interactive effects of these factors and filling gaps featured in the current meta-analysis.

Interaction of drought and ozone exposure on isoprene emission from extensively cultivated poplar.

The combined effects of ozone (O3 ) and drought on isoprene emission were studied for the first time. Young hybrid poplars (clone 546, Populus deltoides cv. 55/56 x P. deltoides cv. Imperial) were exposed to O3 (charcoal-filtered air, CF, and non-filtered air +40 ppb, E-O3 ) and soil water stress (well-watered, WW, and mild drought, MD, one-third irrigation) for 96 days. Consistent with light-saturated photosynthesis (Asat ), intercellular CO2 concentration (Ci ) and chlorophyll content, isoprene emission depended on drought, O3 , leaf position and sampling time. Drought stimulated emission (+38.4%), and O3 decreased it (-40.4%). Ozone increased the carbon cost per unit of isoprene emission. Ozone and drought effects were stronger in middle leaves (13th-15th from the apex) than in upper leaves (6th-8th). Only Asat showed a significant interaction between O3 and drought. When the responses were up-scaled to the entire-plant level, however, drought effects on total leaf area translated into around twice higher emission from WW plants in clean air than in E-O3 . Our results suggest that direct effects on plant emission rates and changes in total leaf area may affect isoprene emission from intensively cultivated hybrid poplar under combined MD and O3 exposure, with important feedbacks for air quality.

Rapid leaf development drives the seasonal pattern of volatile organic compound (VOC) fluxes in a 'coppiced' bioenergy poplar plantation.

Leaves of fast-growing, woody bioenergy crops often emit volatile organic compounds (VOC). Some reactive VOC (especially isoprene) play a key role in climate forcing and may negatively affect local air quality. We monitored the seasonal exchange of VOC using the eddy covariance technique in a 'coppiced' poplar plantation. The complex interactions of VOC fluxes with climatic and physiological variables were also explored by using an artificial neural network (Self Organizing Map). Isoprene and methanol were the most abundant VOC emitted by the plantation. Rapid development of the canopy (and thus of the leaf area index, LAI) was associated with high methanol emissions and high rates of gross primary production (GPP) since the beginning of the growing season, while the onset of isoprene emission was delayed. The highest emissions of isoprene, and of isoprene photo-oxidation products (Methyl Vinyl Ketone and Methacrolein, iox ), occurred on the hottest and sunniest days, when GPP and evapotranspiration were highest, and formaldehyde was significantly deposited. Canopy senescence enhanced the exchange of oxygenated VOC. The accuracy of methanol and isoprene emission simulations with the Model of Emissions of Gases and Aerosols from Nature increased by applying a function to modify their basal emission factors, accounting for seasonality of GPP or LAI.

Removal of Ozone by Urban and Peri-Urban Forests: Evidence from Laboratory, Field, and Modeling Approaches.

A crucial issue in urban environments is the interaction between urban trees and atmospheric pollution, particularly ozone (O). Ozone represents one of the most harmful pollutants in urban and peri-urban environments, especially in warm climates. Besides the large interest in reducing anthropogenic and biogenic precursors of O emissions, there is growing scientific activity aimed at understanding O removal by vegetation, particularly trees. The intent of this paper is to provide the state of the art and suggestions to improve future studies of O fluxes and to discuss implications of O flux studies to maximize environmental services through the planning and management of urban forests. To evaluate and quantify the potential of O removal in urban and peri-urban forests, we describe experimental approaches to measure O fluxes, distinguishing laboratory experiments, field measurements, and model estimates, including recent case studies. We discuss the strengths and weaknesses of the different approaches and conclude that the combination of the three levels of investigation is essential for estimating O removal by urban trees. We also comment on the implications of these findings for planning and management of urban forests, suggesting some key issues that should be considered to maximize O removal by urban and peri-urban forests.

Bidirectional Flux of Methyl Vinyl Ketone and Methacrolein in Trees with Different Isoprenoid Emission under Realistic Ambient Concentrations.

Methyl vinyl ketone (MVK) and methacrolein (MAC) are key oxidation products (iox) of isoprene, the most abundant volatile organic compound (VOC) emitted by vascular plants in the atmosphere. Increasing attention has been dedicated to iox, as they are involved in the photochemical cycles ultimately leading to ozone (O3) and particle formation. However, the capacity of plants to exchange iox under low and realistic ambient concentrations of iox needs to be assessed. We hypothesized that a foliar uptake of iox exists even under realistic concentrations of iox. We tested the capacity of iox exchange in trees constitutively emitting isoprene (Populus nigra) or monoterpenes (Quercus ilex), or that do not emit isoprenoids (Paulownia imperialis). Laboratory experiments were carried out at the leaf level using enclosures under controlled environmental factors and manipulating isoprene and reactive oxygen species (ROS) production by using the isoprene specific inhibitor fosmidomycin, acute O3 exposure (300 ppbv for 4 h), and dark conditions. We also tested whether stress conditions inducing accumulation of ROS significantly enhance iox formation in the leaf, and their emission. Our results show a negligible level of constitutive iox emission in unstressed plants, and in plants treated with high O3. The uptake of iox increased linearly with exposure to increasing concentrations of ambient iox (from 0 to 6 ppbv of a 1:1 = MVK/MAC mixture) in all the investigated species, indicating iox fast removal and low compensation point in unstressed and stressed conditions. Plant capacity to take up iox should be included in global models that integrate estimates of iox formation, emission, and photochemical reactions in the atmosphere.

Bidirectional exchange of biogenic volatiles with vegetation: emission sources, reactions, breakdown and deposition.

Biogenic volatile organic compound (BVOC) emissions are widely modelled as inputs to atmospheric chemistry simulations. However, BVOC may interact with cellular structures and neighbouring leaves in a complex manner during volatile diffusion from the sites of release to leaf boundary layer and during turbulent transport to the atmospheric boundary layer. Furthermore, recent observations demonstrate that the BVOC emissions are bidirectional, and uptake and deposition of BVOC and their oxidation products are the rule rather than the exception. This review summarizes current knowledge of within-leaf reactions of synthesized volatiles with reactive oxygen species (ROS), uptake, deposition and storage of volatiles, and their oxidation products as driven by adsorption on leaf surface and solubilization and enzymatic detoxification inside leaves. The available evidence indicates that because of the reactions with ROS and enzymatic metabolism, the BVOC gross production rates are much larger than previously thought. The degree to which volatiles react within leaves and can be potentially taken up by vegetation depends upon compound reactivity, physicochemical characteristics, as well as upon their participation in leaf metabolism. We argue that future models should be based upon the concept of bidirectional BVOC exchange and consider modification of BVOC sink/source strengths by within-leaf metabolism and storage.

Observations of diurnal to weekly variations of monoterpene-dominated fluxes of volatile organic compounds from mediterranean forests: implications for regional modeling.

The Estate of Castelporziano (Rome, Italy) hosts many ecosystems representative of Mediterranean vegetation, especially holm oak and pine forests and dune vegetation. In this work, basal emission factors (BEFs) of biogenic volatile organic compounds (BVOCs) obtained by Eddy Covariance in a field campaign using a proton transfer reaction-time-of-flight-mass spectrometer (PTR-TOF-MS) were compared to BEFs reported in previous studies that could not measure fluxes in real-time. Globally, broadleaf forests are dominated by isoprene emissions, but these Mediterranean ecosystems are dominated by strong monoterpene emitters, as shown by the new BEFs. The original and new BEFs were used to parametrize the model of emissions of gases and aerosols from nature (MEGAN v2.1), and model outputs were compared with measured fluxes. Results showed good agreement between modeled and measured fluxes when a model was used to predict radiative transfer and energy balance across the canopy. We then evaluated whether changes in BVOC emissions can affect the chemistry of the atmosphere and climate at a regional level. MEGAN was run together with the land surface model (community land model, CLM v4.0) of the community earth system model (CESM v1.0). Results highlighted that tropospheric ozone concentration and air temperature predicted from the model are sensitive to the magnitude of BVOC emissions, thus demonstrating the importance of adopting the proper BEF values for model parametrization.

Temperature dependence of emission of volatile organic compounds (VOC) from litters collected in two Mediterranean ecosystems determined before the flaming phase of biomass burning.

Fire represents a major threat to Mediterranean terrestrial ecosystems because of the high temperatures reached during summer. While massive loads of organic, inorganic compounds and particulate matter are known to be emitted into the atmosphere from forest wildfires, less is known about the emission from vegetation surrounding fires where air temperatures higher than 100 °C can be reached. Little information exists on the emission from dead vegetation accumulated as litter over forest soils, from which fires often starts. In this study, the response of litter to heatwaves generated by nearby fires was investigated under controlled conditions. Litter samples collected in a Mediterranean maquis and a Holm oak stand during summer were placed in an enclosure flushed with a continuous flow of air, the temperature of the enclosure was progressively risen to 125 °C, until some smog developed but no flaming occurred. The gas from the enclosure was analysed for the content of CO2, H2O, and volatile organic compounds (VOC) to assess the dependence of emission from the air temperature. VOC emission was continuously determined by Proton-Transfer-Reaction mass spectrometry with time of flight (PTR-TOF-MS). Data obtained were complemented with those obtained by collecting VOC on traps that were later analysed by Gas chromatography-mass spectrometry (GC-MS). Results provided useful information to understand the emission mechanism of VOC and other gases from dead vegetation present in the litter of two Mediterranean ecosystems, both dominated by evergreen vegetation species. The study demonstrated that low molecular weight VOC and aromatic hydrocarbons (arenes) produced mostly by thermal oxidation of the wood biopolymers are emitted in addition to isoprenoids typically associated to storage organs and photosynthetic pathway. Moreover, our results support parameterization of litter VOC emission processes in air quality models.

Detection and attribution of an anomaly in terrestrial photosynthesis in Europe during the COVID-19 lockdown.

Carbon dioxide (CO2) uptake by plant photosynthesis, referred to as gross primary production (GPP) at the ecosystem level, is sensitive to environmental factors, including pollutant exposure, pollutant uptake, and changes in the scattering of solar shortwave irradiance (SWin) - the energy source for photosynthesis. The 2020 spring lockdown due to COVID-19 resulted in improved air quality and atmospheric transparency, providing a unique opportunity to assess the impact of air pollutants on terrestrial ecosystem functioning. However, detecting these effects can be challenging as GPP is influenced by other meteorological drivers and management practices. Based on data collected from 44 European ecosystem-scale CO2 flux monitoring stations, we observed significant changes in spring GPP at 34 sites during 2020 compared to 2015-2019. Among these, 14 sites showed an increase in GPP associated with higher SWin, 10 sites had lower GPP linked to atmospheric and soil dryness, and seven sites were subjected to management practices. The remaining three sites exhibited varying dynamics, with one experiencing colder and rainier weather resulting in lower GPP, and two showing higher GPP associated with earlier spring melts. Analysis using the regional atmospheric chemical transport model (LOTOS-EUROS) indicated that the ozone (O3) concentration remained relatively unchanged at the research sites, making it unlikely that O3 exposure was the dominant factor driving the primary production anomaly. In contrast, SWin increased by 9.4 % at 36 sites, suggesting enhanced GPP possibly due to reduced aerosol optical depth and cloudiness. Our findings indicate that air pollution and cloudiness may weaken the terrestrial carbon sink by up to 16 %. Accurate and continuous ground-based observations are crucial for detecting and attributing subtle changes in terrestrial ecosystem functioning in response to environmental and anthropogenic drivers.

Leaf-level coordination principles propagate to the ecosystem scale.

Fundamental axes of variation in plant traits result from trade-offs between costs and benefits of resource-use strategies at the leaf scale. However, it is unclear whether similar trade-offs propagate to the ecosystem level. Here, we test whether trait correlation patterns predicted by three well-known leaf- and plant-level coordination theories - the leaf economics spectrum, the global spectrum of plant form and function, and the least-cost hypothesis - are also observed between community mean traits and ecosystem processes. We combined ecosystem functional properties from FLUXNET sites, vegetation properties, and community mean plant traits into three corresponding principal component analyses. We find that the leaf economics spectrum (90 sites), the global spectrum of plant form and function (89 sites), and the least-cost hypothesis (82 sites) all propagate at the ecosystem level. However, we also find evidence of additional scale-emergent properties. Evaluating the coordination of ecosystem functional properties may aid the development of more realistic global dynamic vegetation models with critical empirical data, reducing the uncertainty of climate change projections.

Warming homogenizes apparent temperature sensitivity of ecosystem respiration.

Warming-induced carbon loss through terrestrial ecosystem respiration (Re) is likely getting stronger in high latitudes and cold regions because of the more rapid warming and higher temperature sensitivity of Re (Q 10). However, it is not known whether the spatial relationship between Q 10 and temperature also holds temporally under a future warmer climate. Here, we analyzed apparent Q 10 values derived from multiyear observations at 74 FLUXNET sites spanning diverse climates and biomes. We found warming-induced decline in Q 10 is stronger at colder regions than other locations, which is consistent with a meta-analysis of 54 field warming experiments across the globe. We predict future warming will shrink the global variability of Q 10 values to an average of 1.44 across the globe under a high emission trajectory (RCP 8.5) by the end of the century. Therefore, warming-induced carbon loss may be less than previously assumed because of Q 10 homogenization in a warming world.

Volatile emissions and phenolic compound concentrations along a vertical profile of Populus nigra leaves exposed to realistic ozone concentrations.

Plants are exposed to increasing levels of tropospheric ozone concentrations. This pollutant penetrates in leaves through stomata and quickly reacts inside leaves, thus making plants valuable ozone sinks, but at the same time triggers oxidation processes which lead to leaf injuries. To counteract these negative effects, plants produce an array of antioxidants which react with ozone and reactive molecules which ozone generates in the leaf tissues. In this study, we measured the effect of an ozone concentration which is likely to be attained in many areas of the world in the near future (80 ppb) on leaves of the vertical profile of the widespread agroforestry species Populus nigra. Changes in (1) physiological parameters (photosynthesis and stomatal conductance), (2) ozone uptake, (3) emission of volatile organic compounds (VOCs, i.e. isoprene, methanol and other oxygenated compounds), (4) concentration of antioxidant surface compounds, and (5) concentration of phenolic compounds were assessed. The aim was to assess whether the defensive pathways leading to isoprenoids and phenolics formation were induced when a moderate and chronic increment of ozone is not able to damage photosynthesis. No visual injuries and minor changes in physiology and ozone uptake were observed. The emission of isoprene and oxygenated six-carbon (C6) volatiles were inhibited by ozone, whereas methanol emission was increased, especially in developing leaves. We interpret these results as suggesting an ontogenetic shift in ozone-treated leaves, leading to a slower development and a faster senescence. Most surface and phenolic compounds showed a declining trend in concentration from the youngest to the fully expanded leaves. Ozone reduced the concentrations of chlorogenic acid derivatives at the leaf surface, whereas in total leaf extracts a metabolic shift towards few phenolics with higher antioxidant capacity was observed.

Determinants of ozone fluxes and metrics for ozone risk assessment in plants.

Tropospheric ozone concentration is increasing and represents a threat to single plants and whole ecosystems. The deleterious ozone effects mainly occur when (i) ozone concentration in the air builds up; (ii) the pollutant enters the leaf through stomatal uptake, and (iii) ozone-produced reactive oxygen species are not efficiently scavenged by leaf antioxidants and then oxidize leaf tissues. The sensitivity of plants to ozone is species-specific, and a correct risk assessment should be based on a metric that correctly takes into account the ambient concentration of ozone, the physiological control on stomatal apertures, and the efficiency of leaf antioxidant system. Current methodologies have been analysed to evaluate ozone risk assessment, and, by phasing-in and phasing out sources and sinks of ozone, elements of improvements for the current metrics have been suggested.