Biogenic Isoprene Emissions Research Articles

Influence of Oil and Gas End-Use on Summertime Particulate Matter and Ozone Pollution in the Eastern US.

The influence of oil and gas end-use activities on ambient air quality is complex and understudied, particularly in regions where intensive end-use activities and large biogenic emissions of isoprene coincide. In these regions, vehicular emissions of nitrogen oxides (NOx≡NO + NO2) modulate the oxidative fate of isoprene, a biogenic precursor of the harmful air pollutants ozone, formaldehyde, and particulate matter (PM2.5). Here, we investigate the direct and indirect influence of the end-use emissions on ambient air quality. To do so, we use the GEOS-Chem model with focus on the eastern United States (US) in summer. Regional mean end-use NOx of 1.4 ppb suppresses isoprene secondary organic aerosol (OA) formation by just 0.02 μg m-3 and enhances abundance of the carcinogen formaldehyde by 0.3 ppb. Formation of other reactive oxygenated volatile organic compounds is also enhanced, contributing to end-use maximum daily mean 8-h ozone (MDA8 O3) of 8 ppb. End-use PM2.5 is mostly (67%) anthropogenic OA, followed by 20% secondary inorganic sulfate, nitrate and ammonium and 11% black carbon. These adverse effects on eastern US summertime air quality suggest potential for severe air quality degradation in regions like the tropics with year-round biogenic emissions, growing oil and gas end-use and limited environmental regulation.

High-Resolution Modeling of Summertime Biogenic Isoprene Emissions in New York City.

As cities strive for ambitious increases in tree canopy cover and reductions in anthropogenic volatile organic compound (AVOC) emissions, accurate assessments of the impacts of biogenic VOCs (BVOCs) on air quality become more important. In this study, we aim to quantify the impact of future urban greening on ozone production. BVOC emissions in dense urban areas are often coarsely represented in regional models. We set up a high-resolution (30 m) MEGAN (The Model of Emissions of Gases and Aerosols from Nature version 3.2) to estimate summertime biogenic isoprene emissions in the New York City metro area (NYC-MEGAN). Coupling an observation-constrained box model with NYC-MEGAN isoprene emissions successfully reproduced the observed isoprene concentrations in the city core. We then estimated future isoprene emissions from likely urban greening scenarios and evaluated the potential impact on future ozone production. NYC-MEGAN predicts up to twice as much isoprene emissions in NYC as the coarse-resolution (1.33 km) Biogenic Emission Inventory System version 3.61 (BEIS) on hot summer days. We find that BVOCs drive ozone production on hot summer days, even in the city core, despite large AVOC emissions. If high isoprene emitting species (e.g., oak trees) are planted, future isoprene emissions could increase by 1.4-2.2 times in the city core, which would result in 8-19 ppbv increases in peak ozone on ozone exceedance days with current NOx concentrations. We recommend planting non- or low-isoprene emitting trees in cities with high NOx concentrations to avoid an increase in the frequency and severity of future ozone exceedance events.

Ozone Pollution in China Affected by Climate Change in a Carbon Neutral Future as Predicted by a Process‐Based Interpretable Machine Learning Method

AbstractOzone (O3) pollution is a severe air quality issue in China, posing a threat to human health and ecosystems. The climate change will affect O3 levels by directly changing physical and chemical processes of O3 and indirectly changing natural emissions of O3 precursors. In this study, near‐surface O3 concentrations in China in 2030 and 2060 are predicted using the process‐based interpretable Extreme Gradient Boosting (XGBoost) model integrated with multi‐source data. The results show that the climate‐driven O3 levels over eastern China are projected to decrease by more than 0.4 ppb in 2060 under the carbon neutral scenario (SSP1‐1.9) compared with the high emission scenario (SSP5‐8.5). Among this reduction, 80% is attributed to the changes in physical and chemical processes of O3 related to a cooler climate, while the remaining 20% is attributed to the reduced biogenic isoprene emissions.

Machine Learning to Characterize Biogenic Isoprene Emissions and Atmospheric Formaldehyde with Their Environmental Drivers in the Marine Boundary Layer

Oceanic biogenic emissions exert a significant impact on the atmospheric environment within the marine boundary layer (MBL). This study employs the extreme gradient boosting (XGBoost) machine learning method and clustering method combined with satellite observations and model simulations to discuss the effects of marine biogenic emissions on MBL formaldehyde (HCHO). The study reveals that HCHO columnar concentrations peaked in summer with 8.25 × 1015 molec/cm2, but the sea–air exchange processes controlled under the wind and sea surface temperature (SST) made marine biogenic emissions represented by isoprene reach their highest levels in winter with 95.93 nmol/m2/day. Analysis was conducted separately for factors influencing marine biogenic emissions and affecting MBL HCHO. It was found that phytoplankton functional types (PFTs) and biological degradation had a significant impact on marine biogenic emissions, with ratio range of 0.07~15.87 and 1.02~5.42 respectively. Machine learning methods were employed to simulate the conversion process of marine biogenic emissions to HCHO in MBL. Based on the SHAP values of the learning model, the importance results indicate that the factors influencing MBL HCHO mainly included NO2, as well as temperature (T) and relative humidity (RH). Specifically, the influence of NO2 on atmospheric HCHO was 1.3 times that of T and 1.6 times that of RH. Wind speed affected HCHO by influencing both marine biogenic emission and the atmospheric physical conditions. Increased marine biogenic emissions in air masses heavily influenced by human activities can reduce HCHO levels to some extent. However, in areas less affected by human activities, marine biogenic emissions can lead to higher levels of HCHO pollution. This research explores the impact of marine biogenic emissions on the HCHO status of the MBL under different atmospheric chemical conditions, offering significant insights into understanding chemical processes in marine atmospheres.

Application of advanced causal analyses to identify processes governing secondary organic aerosols

Understanding how different physical and chemical atmospheric processes affect the formation of fine particles has been a persistent challenge. Inferring causal relations between the various measured features affecting the formation of secondary organic aerosol (SOA) particles is complicated since correlations between variables do not necessarily imply causality. Here, we apply a state-of-the-art information transfer measure coupled with the Koopman operator framework to infer causal relations between isoprene epoxydiol SOA (IEPOX-SOA) and different chemistry and meteorological variables derived from detailed regional model predictions over the Amazon rainforest. IEPOX-SOA represents one of the most complex SOA formation pathways and is formed by the interactions between natural biogenic isoprene emissions and anthropogenic emissions affecting sulfate, acidity and particle water. Since the regional model captures the known relations of IEPOX-SOA with different chemistry and meteorological features, their simulated time series implicitly include their causal relations. We show that our causal model successfully infers the known major causal relations between total particle phase 2-methyl tetrols (the dominant component of IEPOX-SOA over the Amazon) and input features. We provide the first proof of concept that the application of our causal model better identifies causal relations compared to correlation and random forest analyses performed over the same dataset. Our work has tremendous implications, as our methodology of causal discovery could be used to identify unknown processes and features affecting fine particles and atmospheric chemistry in the Earth’s atmosphere.

Impacts of global biogenic isoprene emissions on surface ozone during 2000–2019

Biogenic isoprene is an important precursor of tropospheric ozone (O3). Here, a coupled chemistry–vegetation model was used to quantify the contributions of isoprene emissions to surface O3 pollution on the global scale during 2000–2019. The biogenic isoprene emissions showed high values in mid–low latitudes and seasonal peaks in the summer hemispheres. They promote global surface O3 concentrations by 1.75 ppbv annually with regional hotspots of 4.39 ppbv (8.8%) in China and 5.36 ppbv (11.1%) in the U.S. in boreal summer. In the past two decades, isoprene emissions increased by 1.32 TgC yr−1 (0.67% yr−1) in the Northern Hemisphere but decreased by 0.71 TgC yr−1 (0.44% yr−1) in the Southern Hemisphere. Such changes of isoprene made opposite contributions to the surface O3 trend, with 0.26 ppbv yr−1 in eastern China but −0.32 ppbv yr−1 in the southeastern U.S. due to the changes in the background regime of chemical reactions. The impact of anthropogenic changes on the O3 trend is consistent with that of biogenic isoprene, but two to four times stronger in magnitude. This study revealed that the effective control of anthropogenic NOx emissions could mitigate regional O3 pollution even with the increased isoprene emissions under global warming.

Identifying and correcting interferences to PTR-ToF-MS measurements of isoprene and other urban volatile organic compounds

Abstract. Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra.

On the formation of biogenic secondary organic aerosol in chemical transport models: an evaluation of the WRF-CHIMERE (v2020r2) model with a focus over the Finnish boreal forest

Abstract. We present an evaluation of the regional chemical transport model (CTM) WRF-CHIMERE (v2020r2) for the formation of biogenic secondary organic aerosol (BSOA) with a focus over the Finnish boreal forest. Formation processes of biogenic aerosols are still affected by different sources of uncertainties, and model predictions vary greatly depending on the levels of details of the adopted chemical and emissions schemes. In this study, air quality simulations were conducted for the summer of 2019 using different organic aerosol (OA) schemes (as currently available in the literature) to treat the formation of BSOA. First, we performed a set of simulations in the framework of the volatility basis set (VBS) scheme carrying different assumptions for the treatment of the aging processes of BSOA. The results of the model were compared against high-resolution (i.e., 1 h) organic aerosol mass and size distribution measurements performed at the Station for Measuring Ecosystem–Atmosphere Relations (SMEAR-II) site located in Hyytiälä, in addition to other gas-phase species such as ozone (O3), nitrogen oxides (NOx), and biogenic volatile organic compound (BVOC) measurements of isoprene (C5H10) and monoterpenes. We show that WRF-CHIMERE could reproduce well the diurnal variation of the measured OA concentrations for all the investigated scenarios (along with the standard meteorological parameters) as well as the increase in concentrations during specific heat wave episodes. However, the modeled OA concentrations varied greatly between the schemes used to describe the aging processes of BSOA, as also confirmed by an additional evaluation using organic carbon (OC) measurement data retrieved from the EBAS European databases. Comparisons with isoprene and monoterpene air concentrations revealed that the model captured the observed monoterpene concentrations, but isoprene was largely overestimated, a feature that was mainly attributed to the overstated biogenic emissions of isoprene. We investigated the potential consequences of such an overestimation by inhibiting isoprene emissions from the modeling system. Results indicated that the modeled BSOA concentrations increased in the northern regions of the domain (e.g., Finland) compared to southern European countries, possibly due to a shift in the reactions of monoterpene compounds against available radicals, as further suggested by the reduction in α-pinene modeled air concentrations. Finally, we briefly analyze the differences in the modeled cloud liquid water content (clwc) among the simulations carrying different chemical schemes for the treatment of the aging processes of BSOA. The results of the model indicated an increase in clwc values at the SMEAR-II site, for simulations with higher biogenic organic aerosol loads, most likely as a result of the increased number of biogenic aerosol particles capable of activating cloud droplets.

Biogenic isoprene emissions, dry deposition velocity, and surface ozone concentration during summer droughts, heatwaves, and normal conditions in southwestern Europe

Abstract. At high concentrations, tropospheric ozone (O3) deteriorates air quality, inducing adverse effects on human and ecosystem health. Meteorological conditions are key to understanding the variability in O3 concentration, especially during extreme weather events. In addition to modifying photochemistry and atmospheric transport, droughts and heatwaves affect the state of vegetation and thus the biosphere–troposphere interactions that control atmospheric chemistry, namely biogenic emissions of precursors and gas dry deposition. A major source of uncertainty and inaccuracy in the simulation of surface O3 during droughts and heatwaves is the poor representation of such interactions. This publication aims at quantifying the isolated and combined impacts of both extremes on biogenic isoprene (C5H8) emissions, O3 dry deposition, and surface O3 in southwestern Europe. First, the sensitivity of biogenic C5H8 emissions, O3 dry deposition, and surface O3 to two specific effects of droughts, the decrease in soil moisture and in biomass, is analysed for the extremely dry summer 2012 using the biogenic emission model MEGANv2.1 and the chemistry transport model CHIMEREv2020r1. Despite a significant decrease in biogenic C5H8 emissions and O3 dry deposition velocity, characterized by a large spatial variability, the combined effect on surface O3 concentration remains limited (between +0.5 % and +3 % over the continent). The variations in simulated biogenic C5H8 emissions, O3 dry deposition, and surface O3 during the heatwaves and agricultural droughts are then analysed for summer 2012 (warm and dry), 2013 (warm), and 2014 (relatively wet and cool). We compare the results with large observational data sets, namely O3 concentrations from Air Quality (AQ) e-Reporting (2000–2016) and total columns of formaldehyde (HCHO, which is used as a proxy for biogenic emissions of volatile organic compounds) from the Ozone Monitoring Instrument (OMI) of the Aura satellite (2005–2016). Based on a cluster approach using the percentile limit anomalies indicator, we find that C5H8 emissions increase by +33 % during heatwaves compared to normal conditions, do not vary significantly during all droughts (either accompanied or not by a heatwave), and decrease by −16 % during isolated droughts. OMI data confirm an average increase in HCHO during heatwaves (between +15 % and +31 % depending on the product used) and decrease in HCHO (between −2 % and −6 %) during isolated droughts over the 2005–2016 summers. Simulated O3 dry deposition velocity decreases by −25 % during heatwaves and −35 % during all droughts. Simulated O3 concentrations increase by +7 % during heatwaves and by +3 % during all droughts. Compared to observations, CHIMERE tends to underestimate the daily maximum O3. However, similar sensitivity to droughts and heatwaves are obtained. The analysis of the AQ e-Reporting data set shows an average increase of +14 % during heatwaves and +7 % during all droughts over the 2000–2016 summers (for an average daily concentration value of 69 µg m−3 under normal conditions). This suggests that identifying the presence of combined heatwaves is fundamental to the study of droughts on surface–atmosphere interactions and O3 concentration.

Modeling the biogenic isoprene emission and its impact on ozone pollution in Zhejiang province, China

Isoprene is the most abundantly emitted biogenic volatile organic compound (BVOC), which plays an essential role in producing tropospheric ozone (O3). However, the simulations of isoprene emissions have not been sufficiently verified over Yangtze River Delta (YRD), and few studies have specifically addressed its impact on O3 formation. In this study, we simulated the isoprene emissions in Zhejiang Province (ZJ), a region with the largest BVOC emission in YRD, in August 2020 using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the latest Moderate Resolution Imaging Spectroradiometer (MODIS) products, and investigated its contributions to O3 using the Weather Research and Forecasting (WRF)-Community Multiscale Air Quality (CMAQ) model. The model has a good performance on isoprene simulations over urban and suburban areas, with mean biases of −0.16–0.12 ppb, but underestimated the concentrations at forest sites (mainly due to bamboo). Regionally, the simulated formaldehyde concentrations over forests agree well with the satellite observations. In August 2020, the total isoprene emission in ZJ was 125.1 GgC, with higher emissions in western ZJ and relatively lower emissions in eastern coastal regions. The spatial pattern of isoprene concentrations is similar to its emissions, and the maximum daytime average concentrations are above 3.5 ppb. The spatial pattern of its contribution to daily maximum 8 h average O3 concentrations is significantly different from the emissions and concentrations, which shows a higher impact in northern ZJ (>6 ppb) and relatively lower impact in southern ZJ (1–3 ppb). The mean contribution over ZJ is 8.9 %, with daily variation in the range of 3.1 % to 13.4 %. For different cities, the monthly mean contribution is in the range of 4.6 % to 14.3 %, and the maximum daily contribution reaches about 25 %. These findings help understand the summertime O3 pollution in ZJ and the YRD region of China.

Satellite-derived constraints on the effect of drought stress on biogenic isoprene emissions in the southeastern US

Abstract. While substantial progress has been made to improve our understanding of biogenic isoprene emissions under unstressed conditions, large uncertainties remain with respect to isoprene emissions under stressed conditions. Here, we use the US Drought Monitor (USDM) as a weekly drought severity index and tropospheric columns of formaldehyde (HCHO), the key product of isoprene oxidation, retrieved from the Ozone Monitoring Instrument (OMI) to derive top-down constraints on the response of summertime isoprene emissions to drought stress in the southeastern United States (SE US), a region of high isoprene emissions that is also prone to drought. OMI HCHO column density is found to be 6.7 % (mild drought) to 23.3 % (severe drought) higher than that under non-drought conditions. A global chemical transport model, GEOS-Chem, with version 2.1 of the Model of Emissions of Gases and Aerosols from Nature (MEGAN2.1) emission algorithm can simulate this direction of change, but the simulated increases at the corresponding drought levels are 1.1–1.5 times that of OMI HCHO, suggesting the need for a drought-stress algorithm in the model. By minimizing the model–OMI differences in HCHO to temperature sensitivity under different drought levels, we derived a top-down drought stress factor (γd_OMI) in GEOS-Chem that parameterizes using water stress and temperature. The algorithm led to an 8.6 % (mild drought) to 20.7 % (severe drought) reduction in isoprene emissions in the SE US relative to the simulation without it. With γd_OMI the model predicts a nonlinear increasing trend in isoprene emissions with drought severity that is consistent with OMI HCHO and a single site's isoprene flux measurements. Compared with a previous drought stress algorithm derived from the latter, the satellite-based drought stress factor performs better with respect to capturing the regional-scale drought–isoprene responses, as indicated by the near-zero mean bias between OMI and simulated HCHO columns under different drought conditions. The drought stress algorithm also reduces the model's high bias in organic aerosol (OA) simulations by 6.60 % (mild drought) to 11.71 % (severe drought) over the SE US compared to the no-stress simulation. The simulated ozone response to the drought stress factor displays a spatial disparity due to the isoprene-suppressing effect on oxidants, with an <1 ppb increase in O3 in high-isoprene regions and a 1–3 ppbv decrease in O3 in low-isoprene regions. This study demonstrates the unique value of exploiting long-term satellite observations to develop empirical stress algorithms on biogenic emissions where in situ flux measurements are limited.

Changes in the Relative Importance of Biogenic Isoprene and Soil NOx Emissions on Ozone Concentrations in Nonattainment Areas of the United States

AbstractReductions in anthropogenic emissions have drawn increasing attention to the role of the biosphere in O3 production chemistry in U.S. cities. We report the results of chemical transport model sensitivity simulations exploring the relative impacts of biogenic isoprene and soil nitrogen oxides (NOx) emissions on O3 and its temporal variability. We compare scenarios with high and low anthropogenic NOx emissions representing the reductions that have occurred in recent decades. As expected, summertime O3 concentrations become less sensitive to perturbations in biogenic isoprene emissions as anthropogenic NOx emissions decline. However, we demonstrate for the first time that across policy relevant O3 nonattainment areas of the United States, O3 becomes more sensitive to perturbations in soil NOx emissions than to identical perturbations in isoprene emissions. We show that interannual variability in soil NOx emissions may now have larger impacts on interannual O3 variability than isoprene emissions in many areas where the latter would have dominated in the recent past.

An Inversion Framework for Optimizing Non‐Methane VOC Emissions Using Remote Sensing and Airborne Observations in Northeast Asia During the KORUS‐AQ Field Campaign

We aim to reduce uncertainties in CH2O and other volatile organic carbon (VOC) emissions through assimilation of remote sensing data. We first update a three‐dimensional (3D) chemical transport model, GEOS‐Chem with the KORUSv5 anthropogenic emission inventory and inclusion of chemistry for aromatics and C2H4, leading to modest improvements in simulation of CH2O (normalized mean bias (NMB): −0.57 to −0.51) and O3 (NMB: −0.25 to −0.19) compared against DC‐8 aircraft measurements during KORUS‐AQ; the mixing ratio of most VOC species are still underestimated. We next constrain VOC emissions using CH2O observations from two satellites (OMI and OMPS) and the DC‐8 aircraft during KORUS‐AQ. To utilize data from multiple platforms in a consistent manner, we develop a two‐step Hybrid Iterative Finite Difference Mass Balance and four‐dimensional variational inversion system (Hybrid IFDMB‐4DVar). The total VOC emissions throughout the domain increase by 47%. The a posteriori simulation reduces the low biases of simulated CH2O (NMB: −0.51 to −0.15), O3 (NMB: −0.19 to −0.06), and VOCs. Alterations to the VOC speciation from the 4D‐Var inversion include increases of biogenic isoprene emissions in Korea and anthropogenic emissions in Eastern China. We find that the IFDMB method alone is adequate for reducing the low biases of VOCs in general; however, 4D‐Var provides additional refinement of high‐resolution emissions and their speciation. Defining reasonable emission errors and choosing optimal regularization parameters are crucial parts of the inversion system. Our new hybrid inversion framework can be applied for future air quality campaigns, maximizing the value of integrating measurements from current and upcoming geostationary satellite instruments.

Simulation of Isoprene Emission with Satellite Microwave Emissivity Difference Vegetation Index as Water Stress Factor in Southeastern China during 2008

Isoprene is one of the most important biogenic volatile organic compounds (BVOCs) emitted by vegetation. The biogenic isoprene emissions are widely estimated by the Model of Emission of Gases and Aerosols from Nature (MEGAN) considering different environmental stresses. The response of isoprene emission to the water stress is usually parameterized using soil moisture in previous studies. In this study, we designed a new parameterization scheme of water stress in MEGAN as a function of a novel, satellite, passive microwave-based vegetation index, Emissivity Difference Vegetation Index (EDVI), which indicates the vegetation inner water content. The isoprene emission rates in southeastern China were simulated with different water stress indicators including soil moisture, EDVI, Normalized Difference Vegetation Index (NDVI) and Enhanced Vegetation Index (EVI). Then the simulated isoprene emission rates were compared to associated satellite top-down estimations. The results showed that in southeastern China, the spatiotemporal correlations between those simulations and top-down retrieval are all high with different biases. The simulated isoprene emission rates with EDVI-based water stress factor are most consistent with top-down estimation with higher temporal correlation, lower bias and lower RMSE, while soil moisture alters the emission rates little, and optical vegetation indices (NDVI and EVI) slightly increase the correlation with top-down. The temporal correlation coefficients are increased after applied with EDVI water stress factor in most areas; especially in the Yunnan-Guizhou Plateau and Yangtze River Delta (>0.12). Overall, higher consistency of simulation and top-down estimation is shown when EDVI is applied, which indicates the possibility of estimating the effect of vegetation water stress on biogenic isoprene emission using microwave observations.

Season-wise analyses of VOCs, hydroxyl radicals and ozone formation chemistry over north-west India reveal isoprene and acetaldehyde as the most potent ozone precursors throughout the year

The north-west Indo-Gangetic Plain is the agricultural cereal-basket of India owing to its prolific wheat and rice production. Surface ozone pollution is of growing concern over it, yet no detailed year-round in-situ measurements of its most reactive precursors, particularly the volatile organic compounds (VOCs) are available from this region. Here, using the first year-long continuous measurements of 23 major VOCs, ozone, NOx, CO and their atmospheric oxidation products from a regionally representative site in north-west India, we evaluated speciated OH reactivities (OHR), ozone formation potential (OFP) and ozone production regimes (OPR) across all seasons. The average seasonal OHR ranged from 14 s−1 (winter) to 21.5 s−1 (summer). We provide the first estimate of OH radical mixing ratios varying between 0.06 and 0.37 ppt in different seasons for the peak daytime hours in this region. Recycling via HO2+NO was the most important pathway contributing to >85% of the OH production throughout the year. Contrary to satellite derived proxies and chemical transport models which predict NOx sensitive OPR, we show it to be strongly sensitive to both VOCs and NOx (>90% days in a year). Remarkably for densely populated regions, isoprene and acetaldehyde collectively accounted for ~30–50% of the total OFP in all seasons. Biogenic emissions of isoprene (reaching 12.9 mg/m2/h) and high acetaldehyde from anthropogenic and photochemical sources were observed for all seasons. Monitoring and control of isoprene and acetaldehyde are therefore urgently required for efforts focused on mitigating surface ozone pollution in this demographically important region of the world.

Global and regional impacts of land cover changes on isoprene emissions derived from spaceborne data and the MEGAN model

Abstract. 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.

Characteristics of PM2.5-bound secondary organic aerosol tracers in a coastal city in Southeastern China: Seasonal patterns and pollution identification

Abstract Secondary organic aerosol (SOA) plays an important role in global climate change and air quality, and SOA tracers most directly characterize the sources and formation mechanisms of SOA. Four seasons of observation of SOA tracers was carried out in a coastal city of southeastern China. Fourteen PM2.5-bound SOA tracers, including isoprene (SOAI), α/β-pinene (SOAM), β-caryophyllene (SOAC), and toluene (SOAA), were measured using the GC–MS method. The concentrations of SOA tracers in Fuzhou were 25.9 ± 19.9 ng m−3 (SOAM), 7.45 ± 8.53 ng m−3 (SOAI), 3.15 ± 1.99 ng m−3 (SOAC), and 2.63 ± 1.54 ng m−3 (SOAA). The elevated SOAI concentration in summer was mainly controlled by high biogenic isoprene emission and strong oxidation, and biomass burning contributed strongly to DHOPA (SOAA) in fall. SO42− and H+insitu had an increased impact on later-generation SOAI products and low-NOx SOAM products. Based on the ratio of MGA/MTLs and MBTCA/(PA + PNA), atmospheric oxidation capacity (Ox, =NO2+O3) had a significant impact on the aerosol aging of SOA tracers. The increased proportions of low-NOx SOAI products were 3.23–7.21 times higher than those of high-NOx products from non-haze to haze periods, suggesting the influence of high SO42− concentration and RH on the reaction channel for SOAI formation. The percentages of later-generation SOAM products during RT were 2.46 times higher than those of first-generation products, suggesting the influence of aerosol aging during the regional transport. Both continental Asian outflow and biomass-burning plumes promoted precursor emissions and the formation process of SOA during the haze pollution events. These related findings help to understand the occurrence, sources and formation of SOA in coastal areas.

Biogenic Isoprene Emissions and Temporal and Spatial Distribution Characteristics in Tianjin

Based on the localized improved GLOBEIS model, the total amount of biogenic isoprene emissions in Tianjin in 2018 was estimated and the temporal and spatial distribution characteristics were analysed by using the land-use type data interpreted from remote sensing images and the observed hourly meteorological data. The results show that the total amount of biogenic isoprene emission in Tianjin reached 694 t (calculated by C, the same below) in 2018, and the emission intensity was 0.06 t/km2/a. The diurnal, monthly and seasonal variations of biogenic isoprene emissions are obvious: High at noon and low at night; Highest in August and lowest in January; Emissions in summer are the largest while the smallest in winter. The spatial characteristics are closely related to land-use types, and the emissions of biogenic isoprene are mainly concentrated in the forest areas, and the emissions are small in the Urban districts of the city and Binhai New District. Finally, the uncertainty sources of biogenic isoprene emission estimation were analysed.

Observed dependence of surface ozone on increasing temperature in Shanghai, China

Eight-year measurements at urban (Xujiahui, XJH) and remote (Dongtan, DT) sites during time period 2010–2017 are employed to examine the surface ozone (O3)-temperature relationship in Shanghai, China. O3 pollution was getting worse in Shanghai, with daily maximum O3 concentrations increasing at a rate of 2.47 ppb yr−1 in urban site. The climate penalty (mO3-T), defined as the slope of O3 change with increasing temperature, exhibited largest values in summer. Summertime O3 increased faster as temperature increased, with mean rates of 6.65 and 13.68 ppb °C−1, respectively in XJH and DT above 30 °C. Sensitivity experiments indicate that the temperature dependence of biogenic volatile organic compounds (VOCs) emissions could be the main chemical driver of the high-temperature O3 response in summer, since the simulated mO3-T are most sensitive to changes of biogenic isoprene emissions. NOx emission reductions strengthened the high-temperature O3 response, with summer mean mO3-T values increasing from 1.52 ppb°C−1 during 2010–2012 to 2.97 ppb °C−1 during 2013–2017. As NOx emissions continue to decrease, the O3 production in urban Shanghai tend to become transitional and the dependence of mO3-T on the biogenic VOC emissions might be weakened. Model results suggest that anthropogenic VOC emission reductions would effectively relieve O3 pollution and reduce the sensitivity of O3 to increasing temperatures in urban Shanghai. Tailored emission reductions as well as scientific city planning strategies should be formulated to balance VOC/NOx ratios, so as to wrestle with the challenges for future O3 pollution under a warming climate.

Dependence of Summertime Surface Ozone on NOx and VOC Emissions Over the United States: Peak Time and Value

AbstractWe apply the Regional chEmistry and trAnsport Model to analyze summertime O3 observations over the contiguous United States. We show that the evaluation of simulated timing of surface ozone maximum with observations provides another independent constraint on the model in addition to O3 concentrations. Over regions with massive biogenic isoprene emissions,O3 peak values are sensitive to the emissions of NOx but not VOCs; however, O3 peak time is sensitive to isoprene emissions and increasing isoprene emissions leads to earlier peak time. By such relationships and model evaluation with the observations, we find that the underestimation of soil NOx emissions leads to a low bias of simulated O3 peak value in the south, while the overestimation of biogenic isoprene emissions results in earlier than observed O3 peak time in the central, south, and southeast regions. The latter is corroborated by the evaluation using Ozone Monitoring Instrument observations of HCHO tropospheric columns.