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Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O ₃ and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget. Significance Extremely low volatility organic compounds (ELVOC) are suggested to promote aerosol particle formation and cloud condensation nuclei (CCN) production in the atmosphere. We show that the capability of biogenic VOC (BVOC) to produce ELVOC depends strongly on their chemical structure and relative oxidant levels. BVOC with an endocyclic double bond, representative emissions from, e.g., boreal forests, efficiently produce ELVOC from ozonolysis. Compounds with exocyclic double bonds or acyclic compounds including isoprene, emission representative of the tropics, produce minor quantities of ELVOC, and the role of OH radical oxidation is relatively larger. Implementing these findings into a global modeling framework shows that detailed assessment of ELVOC production pathways is crucial for understanding biogenic secondary organic aerosol and atmospheric CCN formation.

The effect of an increase in atmospheric aerosol concentrations on the distribution and radiative properties of Earth’s clouds is the most uncertain component of the overall global radiative forcing from preindustrial time. General circulation models (GCMs) are the tool for predicting future climate, but the treatment of aerosols, clouds, and aerosol–cloud radiative effects carries large uncertainties that directly affect GCM predictions, such as climate sensitivity. Predictions are hampered by the large range of scales of interaction between various components that need to be captured. Observation systems (remote sensing, in situ) are increasingly being used to constrain predictions, but significant challenges exist, to some extent because of the large range of scales and the fact that the various measuring systems tend to address different scales. Fine-scale models represent clouds, aerosols, and aerosol–cloud interactions with high fidelity but do not include interactions with the larger scale and are therefore limited from a climatic point of view. We suggest strategies for improving estimates of aerosol–cloud relationships in climate models, for new remote sensing and in situ measurements, and for quantifying and reducing model uncertainty.

The Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) together with the Modern-Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields were used to create a global emission data set of biogenic volatile organic compounds (BVOC) available on a monthly basis for the time period of 1980–2010. This data set, developed under the Monitoring Atmospheric Composition and Climate project (MACC), is called MEGAN–MACC. The model estimated mean annual total BVOC emission of 760 Tg (C) yr−1 consisting of isoprene (70%), monoterpenes (11%), methanol (6%), acetone (3%), sesquiterpenes (2.5%) and other BVOC species each contributing less than 2%. Several sensitivity model runs were performed to study the impact of different model input and model settings on isoprene estimates and resulted in differences of up to ±17% of the reference isoprene total. A greater impact was observed for a sensitivity run applying parameterization of soil moisture deficit that led to a 50% reduction of isoprene emissions on a global scale, most significantly in specific regions of Africa, South America and Australia. MEGAN–MACC estimates are comparable to results of previous studies. More detailed comparison with other isoprene inventories indicated significant spatial and temporal differences between the data sets especially for Australia, Southeast Asia and South America. MEGAN–MACC estimates of isoprene, α-pinene and group of monoterpenes showed a reasonable agreement with surface flux measurements at sites located in tropical forests in the Amazon and Malaysia. The model was able to capture the seasonal variation of isoprene emissions in the Amazon forest.

Among the biogenic volatile organic compounds (BVOCs) emitted by plant foliage, isoprene is by far the most important in terms of both global emission and atmospheric impact. It is highly reactive in the air, and its degradation favours the generation of ozone (in the presence of NOx) and secondary organic aerosols. A critical aspect of BVOC emission modelling is the representation of land use and land cover (LULC). The current emission inventories are usually based on land cover maps that are either modelled and dynamic or satellite-based and static. In this study, we use the state-of-the-art Model of Emissions of Gases and Aerosols from Nature (MEGAN) model coupled with the canopy model MOHYCAN (Model for Hydrocarbon emissions by the CANopy) to generate and evaluate emission inventories relying on satellite-based LULC maps at annual time steps. To this purpose, we first intercompare the distribution and evolution (2001–2016) of tree coverage from three global satellite-based datasets, MODerate resolution Imaging Spectroradiometer (MODIS), ESA Climate Change Initiative Land Cover (ESA CCI-LC), and the Global Forest Watch (GFW), and from national inventories. Substantial differences are found between the datasets; e.g. the global areal coverage of trees ranges from 30 to 50×106 km2, with trends spanning from −0.26 to +0.03 % yr−1 between 2001 and 2016. At the national level, the increasing trends in forest cover reported by some national inventories (in particular for the US) are contradicted by all remotely sensed datasets. To a great extent, these discrepancies stem from the plurality of definitions of forest used. According to some local censuses, clear cut areas and seedling or young trees are classified as forest, while satellite-based mappings of trees rely on a minimum height. Three inventories of isoprene emissions are generated, differing only in their LULC datasets used as input: (i) the static distribution of the stand-alone version of MEGAN, (ii) the time-dependent MODIS land cover dataset, and (iii) the MODIS dataset modified to match the tree cover distribution from the GFW database. The mean annual isoprene emissions (350–520 Tg yr−1) span a wide range due to differences in tree distributions, especially in isoprene-rich regions. The impact of LULC changes is a mitigating effect ranging from 0.04 to 0.33 % yr−1 on the positive trends (0.94 % yr−1) mainly driven by temperature and solar radiation. This study highlights the uncertainty in spatial distributions of and temporal variability in isoprene associated with remotely sensed LULC datasets. The interannual variability in the emissions is evaluated against spaceborne observations of formaldehyde (HCHO), a major isoprene oxidation product, through simulations using the global chemistry transport model (CTM) IMAGESv2. A high correlation (R > 0.8) is found between the observed and simulated interannual variability in HCHO columns in most forested regions. The implementation of LULC change has little impact on this correlation due to the dominance of meteorology as a driver of short-term interannual variability. Nevertheless, the simulation accounting for the large tree cover declines of the GFW database over several regions, notably Indonesia and Mato Grosso in Brazil, provides the best agreement with the HCHO column trends observed by the Ozone Monitoring Instrument (OMI). Overall, our study indicates that the continuous tree cover fields at fine resolution provided by the GFW database are our preferred choice for constraining LULC (in combination with discrete LULC maps such as those of MODIS) in biogenic isoprene emission models.

Wetlands cover only 3 % of the global land surface area, but boreal wetlands are experiencing an unprecedented warming of four times the global average. These wetlands emit isoprene and terpenes (including monoterpenes (MT), sesquiterpenes (SQT), and diterpenes (DT)), which are climate-relevant highly reactive biogenic volatile organic compounds (BVOCs) with an exponential dependence on temperature. In this study, we present ecosystem-scale eddy covariance (EC) fluxes of isoprene, MT, SQT, and DT (hereafter referred to together as terpenes) at Siikaneva, a boreal fen in southern Finland, from the start to the peak of the growing season of 2021 (19 May 2021 to 28 June 2021). These are the first EC fluxes reported using the novel state-of-the-art Vocus proton transfer reaction mass spectrometer (Vocus-PTR) and the first-ever fluxes reported for DTs from a wetland. Isoprene was the dominant compound emitted by the wetland, followed by MTs, SQTs, and DTs, and they all exhibited a strong exponential temperature dependence. The Q10 values, the factor by which terpene emissions increases for every 10 ∘C rise in temperature, were up to five times higher than those used in most BVOC models. During the campaign, the air temperature peaked above 31 ∘C on 21–22 June 2021, which is abnormally high for boreal environments, and the maximum flux for all terpenes coincided with this period. We observed that terpene emissions were elevated after this abnormally “high-temperature stress period”, indicating that past temperatures alter emissions significantly. The standardized emission factor (EF) of the fen for isoprene (EFiso) was 11.1 ±  0.3 nmol m−2 s−1, which is at least two times higher than in previous studies and as high as the emission factors typical for broadleaf and other forests in the lower latitudes. We observed EFMT of 2.4 ±  0.1 nmol m−2 s−1, EFSQT of 1.3 ± 0.03 nmol m−2 s−1, higher than typical for needle leaf and broadleaf tree functional types, and EFDT of 0.011 ± 0.001 nmol m−2 s−1. We also compared the landscape average emissions to the model of emissions of gases and aerosols from nature (MEGAN) v2.1 and found that the emissions were underestimated by over 9 times for isoprene, over 300 times for MTs, and 800 times for SQTs. Our results show that due to very high EFs and high sensitivity to increasing temperatures, these high-latitude ecosystems can be a large source of terpenes to the atmosphere, and anthropogenic global warming could induce much higher BVOC emissions from wetlands in the future.

Emissions of biogenic volatile organic compounds (BVOCs) are a crucial component of biosphere–atmosphere interactions. In northern latitudes, climate change is amplified by feedback processes in which BVOCs have a recognized, yet poorly quantified role, mainly due to a lack of measurements and concomitant modeling gaps. Hence, current Earth system models mostly rely on temperature responses measured on vegetation from lower latitudes, rendering their predictions highly uncertain. Here, we show how tundra isoprene emissions respond vigorously to temperature increases, compared to model results. Our unique dataset of direct eddy covariance ecosystem-level isoprene measurements in two contrasting ecosystems exhibited Q 10 (the factor by which the emission rate increases with a 10 °C rise in temperature) temperature coefficients of up to 20.8, that is, 3.5 times the Q 10 of 5.9 derived from the equivalent model calculations. Crude estimates using the observed temperature responses indicate that tundra vegetation could enhance their isoprene emissions by up to 41% (87%)—that is, 46% (55%) more than estimated by models—with a 2 °C (4°C) warming. Our results demonstrate that tundra vegetation possesses the potential to substantially boost its isoprene emissions in response to future rising temperatures, at rates that exceed the current Earth system model predictions.

Satellite observations reveal that China has been leading the global greening trend in the past 2 decades. We assessed the impact of land cover change as well as climate variability on total biogenic volatile organic compound (BVOC) emission in China from 2001–2016. We found the greening trend in China is leading a national-scale increase in BVOC emission. The BVOC emission level in 2016 could be 11.7 % higher than that in 2001 because of higher tree cover fraction and vegetation biomass. On the regional scale, the BVOC emission level from 2013–2016 could be 8.6 %–19.3 % higher than that from 2001–2004 in hotspots including (1) northeastern China, (2) Beijing and its surrounding areas, (3) the Qin Mountains, (4) Yunnan Province, (5) Guangxi–Guangdong provinces, and (6) Hainan island because of the land cover change without considering the impact of climate variability. The comparison among different scenarios showed that vegetation changes resulting from land cover management are the main driver of BVOC emission change in China. Climate variability contributed significantly to interannual variations but not much to the changing trend during the study period. In the standard scenario, which considers both land cover change and climate variability, a statistically significant increasing trend can still be found in regions including Beijing and its surroundings, Yunnan Province, and Hainan island, and BVOC emission total amount in these regions from 2013–2016 is 11.0 %–17.2 % higher that from 2001–2004. We compared the long-term HCHO vertical columns (VC) from the satellite-based Ozone Monitoring Instrument (OMI) with the estimation of isoprene emission in summer. The results showed statistically significant positive correlation coefficients over the regions with high vegetation cover fractions. In addition, the isoprene emission and HCHO VC both showed statistically significant increasing trends in the south of China where these two variables have high positive correlation coefficients. This result may support our estimation of the variability and trends of BVOC emission in this region; however, the comparison still has large uncertainties since the chemical and physical processes, including transportation, diffusion and chemical reactions, were not considered. Our results suggest that the continued increase in BVOC will enhance the importance of considering BVOC when making policies for controlling ozone pollution in China along with ongoing efforts to increase the forest cover fraction.

It has been widely reported that isoprene emissions from the Arctic ecosystem have a strong temperature response. Here we identify sedges ( Carex spp. and Eriophorum spp.) as key contributors to this high sensitivity using plant chamber experiments. We observe that sedges exhibit a markedly stronger temperature response compared to that of other isoprene emitters and predictions by the widely accepted isoprene emission model, the Model of Emissions of Gases and Aerosols from Nature (MEGAN). MEGAN is able to reproduce eddy-covariance flux observations at three high-latitude sites by integrating our findings. Furthermore, the omission of the strong temperature responses of Arctic isoprene emitters causes a 20% underestimation of isoprene emissions for the high-latitude regions of the Northern Hemisphere during 2000-2009 in the Community Land Model with the MEGAN scheme. We also find that the existing model had underestimated the long-term trend of isoprene emissions from 1960 to 2009 by 55% for the high-latitude regions. The authors identify that sedges in the Arctic have a different isoprene temperature response than other temperate plants, and this finding explains the high temperature sensitivity of isoprene emissions from Arctic terrestrial ecosystems.

Terpenoids influence atmospheric chemistry through rapid oxidation reactions which form secondary products including ozone and secondary organic aerosols (SOA). Source apportionment of terpenoids is complicated in urban environments because there are biogenic and anthropogenic sources. This study utilizes measured fluxes of isoprene, monoterpenes, and sesquiterpenes with MEGAN, a biogenic emissions model, and FIVE-VCP, an anthropogenic emissions inventory, to characterize urban terpenoid emissions. Volatile organic compound (VOC) mixing ratios were measured using a Vocus proton-transfer reaction mass spectrometer (PTR-MS) during the URBAN-EC (Urban Research on Biogenic and ANthropogenic Emissions of Carbon) study in Berkeley, California from May to November 2022. Fluxes were calculated using the eddy covariance technique. Median fluxes of isoprene, monoterpenes, and sesquiterpenes were 0.269, 0.182, and 0.013 nmol m−2 s−1 respectively. Terpenoids were 2 % of the measured molar flux, 26 % of OH reactivity flux, and 21 % of SOA formation potential. The MEGAN isoprene emission factor was 4.56 nmol (m2 leaf area)−1 s−1. MEGAN isoprene fluxes matched URBAN-EC distributions seasonally and diurnally, while MEGAN monoterpene and sesquiterpene fluxes had more pronounced seasonal trends and lower morning emissions relative to URBAN-EC. Weekday/weekend differences were used to determine if terpenoids had anthropogenic sources. Monoterpene and sesquiterpene fluxes were significantly higher on weekdays (p<0.05); these differences were not represented in MEGAN or FIVE-VCP. Monoterpenes and sesquiterpenes had lower-bound anthropogenic fractions of 23 % and 24 %. Personal care products were not an important contributor to monoterpene emissions. This study presents a detailed analysis of urban terpenoid fluxes and contributes to better understanding their sources.

Warming climate in the Arctic is leading to an increase in isoprene emission from ecosystems. We assessed the influence of temperature on isoprene emission from Arctic willows with laboratory and field measurements. Our findings indicate that the hourly temperature response curve of Salix spp., the dominant isoprene emitting shrub in the Arctic, aligns with that of temperate plants. In contrast, the isoprene capacity of willows exhibited a more substantial than expected response to the mean ambient temperature of the previous day, which is much stronger than the daily temperature response predicted by the current version of the Model of Emissions of Gases and Aerosols from Nature (MEGAN). With a modified algorithm from this study, MEGAN predicts 66% higher isoprene emissions for Arctic willows during an Arctic heatwave. However, despite these findings, we are still unable to fully explain the high temperature sensitivity of isoprene emissions from high latitude ecosystems. Plain Language Summary Isoprene plays an important role in atmospheric chemistry and climate. As the climate warms, ecosystems release more isoprene into the air due to higher temperatures and changes in plant species composition. The Arctic is a hotspot for climate change. In this study, we investigated how temperature affects isoprene emissions from Arctic willow shrubs by conducting experiments in both the lab and the field. Our results show that the response of Salix spp. (willows) in the Arctic react to short‐term temperature changes is similar to plants in temperate regions. Interestingly, the amount of isoprene that willows release responds strongly to the average temperature of the previous day. This response is much stronger than predicted by models. Considering the insights from our study, isoprene emissions from Arctic willows are much higher during Arctic heatwaves than previously thought. This study can help us understand how isoprene from Arctic willows will affect atmospheric composition and climate and contribute to corresponding feedbacks on the local climate. Key Points The hourly temperature response curve of Arctic Salix spp. is similar to temperate plants and is well represented by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) model The isoprene capacity of willows exhibited a pronounced response to the mean temperature of the previous day MEGAN predicts a 66% higher isoprene emission for Arctic willows during an Arctic heatwave after incorporating the findings of this study