Explore the vast range of titles available.

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.

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.

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

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.

Biogenic volatile organic compounds (BVOCs) are important components of the atmosphere due to their contribution to atmospheric chemistry and biogeochemical cycles. Tropical forests are the largest source of the dominant BVOC emissions (e.g. isoprene and monoterpenes). In this study, we report isoprene and total monoterpene flux measurements with a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) using the eddy covariance (EC) method at the Tapajós National Forest (2.857∘ S, 54.959∘ W), a primary rainforest in eastern Amazonia. Measurements were carried out from 1 to 16 June 2014, during the wet-to-dry transition season. During the measurement period, the measured daytime (06:00–18:00 LT) average isoprene mixing ratios and fluxes were 1.15±0.60 ppb and 0.55±0.71 mg C m−2 h−1, respectively, whereas the measured daytime average total monoterpene mixing ratios and fluxes were 0.14±0.10 ppb and 0.20±0.25 mg C m−2 h−1, respectively. Midday (10:00–14:00 LT) average isoprene and total monoterpene mixing ratios were 1.70±0.49 and 0.24±0.05 ppb, respectively, whereas midday average isoprene and monoterpene fluxes were 1.24±0.68 and 0.46±0.22 mg C m−2 h−1, respectively. Isoprene and total monoterpene emissions in Tapajós were correlated with ambient temperature and solar radiation. Significant correlation with sensible heat flux, SHF (r2=0.77), was also observed. Measured isoprene and monoterpene fluxes were strongly correlated with each other (r2=0.93). The MEGAN2.1 (Model of Emissions of Gases and Aerosols from Nature version 2.1) model could simulate most of the observed diurnal variations (r2=0.7 to 0.8) but declined a little later in the evening for both isoprene and total monoterpene fluxes. The results also demonstrate the importance of site-specific vegetation emission factors (EFs) for accurately simulating BVOC fluxes in regional and global BVOC emission models.

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m−3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O:C up to O:C∼1.0, and then decreased as O:C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C=C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the nearcanopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330%from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.