Modelling study of the impact of isoprene and terpene biogenic emissions on European ozone levels

The impact of biogenic volatile organic compound (BVOC) emissions on European ozone distributions has not yet been evaluated in a comprehensive way. Using the CHIMERE chemistry-transport model the variability of surface ozone levels from April to September for 4 years (1997, 2000, 2001, 2003) resulting from biogenic emissions is investigated. It is shown that BVOC emissions increased on average summer daily ozone maxima over Europe by 2.5 ppbv (5%). The impact is most significant in Portugal (up to 15 ppbv) and in the Mediterranean region (about 5 ppbv), being smaller in the northern part of Europe (1.3 ppbv north of 47.5°N). The average impact is rather similar for the three summers (1997, 2000, 2001), but is much larger during the extraordinarily hot summer of 2003. Here, the biogenic contribution to surface ozone doubles compared to other years at some locations. Interaction with anthropogenic NO_x emissions is found to be a key process for ozone production of biogenic precursors. Comparing the impact of the state-of-the-art BVOC emission inventory compiled within the NatAir project and an earlier, widely used BVOC inventory derived from Simpson et al. [1999. Inventorying emissions from nature in Europe. Journal of Geophysical Research 104(D7), 8113–8152] on surface ozone shows that ozone produced from biogenic precursors is less in central and northern Europe but in certain southern areas much higher e.g. Iberian Peninsula and the Mediterranean Sea. The uncertainty in the regionally averaged impact of BVOC on ozone build-up in Europe is estimated to be ±50%.     

A land use database and examples of biogenic isoprene emission estimates for the state of Texas, USA

Using data from a variety of sources, land use and vegetation in Texas were mapped with a spatial resolution of approximately 1 km. Over 600 classifications were used to characterize the land use and land cover throughout the state and field surveys were performed to assign leaf biomass densities, by species, to the land cover classifications. The total leaf biomass densities associated with these land use classifications ranged from 0 to 556 g/m², with the highest assigned total and oak leaf biomass densities located in central and eastern Texas. The land cover data were used as input to a biogenic emissions model, GLOBEIS2. Estimates of biogenic emissions of isoprene based on GLOBEIS2 and the new land cover data showed significant differences when compared to biogenic isoprene emissions estimated using previous land cover data and emission estimation procedures. For example, for one typical domain in eastern Texas, total daily isoprene emissions increased by 38% with the new modeling tools. These results may ultimately affect the way in which ozone and other photochemical pollutants are modeled and evaluated in the state of Texas.     

Measurements of biogenic VOC emissions: sampling,analysis and calibration

We describe an experimental system and techniques for sampling and analyzing biogenic emissions of volatile organic compounds (VOC). The system uses a Teflon chamber to enclose a single branch of a tree. Temperature, photosynthetic active radiation (PAR), relative humidity and carbon dioxide concentration are continuously monitored with a time resolution of five minutes. VOCs are sampled on tubes containing solid adsorbents (Tenax TA and Carbotrap) with a time resolution of 1 h. Composition and concentration of VOC emissions are measured with a gas chromatographic system equipped with a flame ionization detector (FID) for quantitative and a mass spectrometer (MS) for qualitative analysis. To calibrate the system, a diffusion source was built to produce standard mixtures of up to 36 different compounds with mixing ratios at low concentrations and high accuracy. The diffusion rates were monitored over 17 months and showed variations between 0.2 and 7.6% for monoterpenes (expect for α-phellandrene, α-terpinene and γ-terpinene) and between 10.6 and 22.6% for sesquiterpenes. FID response factors calculated from calibration measurements were corrected using correction factors based on the effective carbon number concept. The individual response factors of 23 compounds were combined to a mean response factor (RF_m) with a value of 23,100 μV s ng⁻¹ and a standard deviation of 9%. The system described here was used to measure VOC emission rates of Scots pine (Pinus sylvestris) in 1998 and 1999.     

Effects of temperature and land use on predictions of biogenic emissions in Eastern Texas,USA

Accurate estimates of biogenic volatile organic compound emissions are critical for air quality planning in areas such as Eastern Texas where biogenic emissions comprise a significant fraction of the total volatile organic compound inventory. Uncertainties in biogenic volatile organic chemical emission estimates associated with different land use databases, surface temperature databases, and temperature interpolation methods were quantified and compared. The sensitivity of isoprene emissions to land use classification was investigated by comparing predictions based on land use data recently compiled for Eastern Texas to those based on the Biogenic Emissions Landcover Database version 3.1 (BELD3). Previous studies have only made these comparisons with the previous BELD version 2 database. Isoprene emission increased throughout much of Eastern Texas because areas classified as agricultural or savannah in BELD3 were more accurately classified as Post Oak, Live Oak, mesquite, and juniper in the new database. These results indicate the need for land use studies in areas poorly characterized in the BELD3. The sensitivity of isoprene emission estimates to uncertainties in surface temperatures were investigated by comparing predictions based on two different temperature databases and three different interpolation techniques. Spatial interpolations of surface temperatures collected at available Automated Surface Observing System (ASOS) stations in Houston, Austin, and Dallas were similar to the spatial interpolations of surface temperatures obtained from the ETA Data Assimilation System (EDAS). As a result, substantial variations in isoprene emissions were not observed over the majority of the modeling domain; however, differences of 4 F over localized regions produced a 35% difference in isoprene emissions. Comparisons between the isoprene emissions of the three interpolation methods sometimes revealed large variations, with maximum temperature differences of 4 F resulting in 60% differences in isoprene emissions in areas with the highest isoprene emissions. It was noted that the ASOS stations were clustered in urban areas and not in areas with the highest biogenic emissions. More ambient temperature monitors need to be located in rural locations to provide robust estimates of biogenic emissions and facilitate validation of interpolated temperature fields.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

The oxidation of isoprene in the troposphere: Mechanism and model calculations

A chemical mechanism describing the oxidation of isoprene by OH and O³ in the troposphere has been developed and incorporated into a one-dimensional steady-state photochemical model. Calculations have been performed for continental conditions at two latitudes, 15°N and 45°N. At 45°N latitude, the effects of anthropogenic hydrocarbon emissions on the vertical profiles of NO_x (NO + NO₂) and HNO₃ overshadow the effects of isoprene emissions; at 15°N, the reduced anthropogenic emissions and the increased isoprene emissions produce increases of 26 and 4% in the column contents of NO_x and HNO₃, respectively. The integrated columns of CO at 45°N and 15°N latitude increased by 10 and 31 %, respectively, when isoprene chemistry was included, but these increases are much smaller than those that would have been obtained if all the carbon in isoprene had been photochemically transformed into CO. It appears that the fate of a significant quantity of isoprene is in the formation of longer carbon-chain (R > CH₃) oxygenated organic species. The longer carbon-chain alkylhydroperoxides and alkylperoxyacids appear to be important free radical sinks in the tropics given the lower NO_x concentrations generally found in the tropics.     

Temporal,spatial characteristics and uncertainty of biogenic VOC emissions in the Pearl River Delta region,China

Using the Global Biosphere Emissions and Interactions System model (GloBEIS), 3 × 3 km gridded and hourly biogenic volatile organic compound (BVOC) emissions in the Pearl River Delta (PRD) were estimated for the year 2006. The study used newly available land cover database, observed meteorological data, and recent measurements of emission rates for tree species in China. The results show that the total BVOC emission in the PRD region in 2006 was 296 kt (2.2 × 10¹¹ gC), of which isoprene contributes about 25% (73 kt, 6.4 × 10¹⁰ gC), monoterpenes about 34% (102 kt, 8.9 × 10¹⁰ gC), and other VOCs (OVOC) about 41% (121 kt, 6.8 × 10¹⁰ gC). BVOC emissions in the PRD region exhibit a marked seasonal pattern with the peak emission in July and the lowest emission in January, and are mainly distributed over the outlying areas of the PRD region, where the economy and land use are less developed. The uncertainties in BVOC emission estimates were quantified using Monte Carlo simulation; the results indicate high uncertainties in isoprene emission estimates, with a relative error of ?82 to +177%, ranging from 12.4 to 186.4 kt; ?41 to +58% uncertainty for monoterpenes emissions, ranging from 67.7 to 181.9 kt; and ?26 to +30% uncertainty in OVOC emissions, ranging from 88.8 to 156.2 kt on the 95% confidence intervals. The key uncertainty sources include emission factors and the model empirical coefficients α, C_T1, C_L, and E_opt for estimating isoprene emission, and emission factors and foliar density for estimating monoterpenes and OVOC emissions. This implies that determining these empirical coefficient values properly and conducting more field measurements of emission rates of tree species are key approaches for reducing uncertainties in BVOC emission estimates. Improving future BVOC emission inventory work in the PRD region requires giving priority to research on shrub land, coniferous forests, and irrigated cropland and pasture.     

Assimilation of conventional and satellite wind observations in a mesoscale atmospheric model for studying atmospheric dispersion

A mesoscale atmospheric model PSU/NCAR MM5 is used to provide operational weather forecasts for a nuclear emergency response decision support system on the southeast coast of India. In this study the performance of the MM5 model with assimilation of conventional surface and upper-air observations along with satellite derived 2-d surface wind data from QuickSCAT sources is examined. Two numerical experiments with MM5 are conducted: one with static initialization using NCEP FNL data and second with dynamic initialization by assimilation of observations using four dimensional data assimilation (FDDA) analysis nudging for a pre-forecast period of 12 h. Dispersion simulations are conducted for a hypothetical source at Kalpakkam location with the HYSPLIT Lagrangian particle model using simulated wind field from the above experiments. The present paper brings out the differences in the atmospheric model predictions and the differences in dispersion model results from control and assimilation runs. An improvement is noted in the atmospheric fields from the assimilation experiment which has led to significant alteration in the trajectory positions, plume orientation and its distribution pattern. Sensitivity tests using different PBL and surface parameterizations indicated the simple first order closure schemes (Blackadar, MRF) coupled with the simple soil model have given better results for various atmospheric fields. The study illustrates the impact of the assimilation of the scatterometer wind and automated weather stations (AWS) observations on the meteorological model predictions and the dispersion results.     

Interactions of climate,socio-economics,and global mercury pollution in the North Water

Despite the remoteness of the North Water, Northwest Greenland, the local Inughuit population is affected by global anthropogenic pollution and climate change. Using a cross-disciplinary approach combining Mercury (Hg) analysis, catch information, and historical and anthropological perspectives, this article elucidates how the traditional diet is compromised by Hg pollution originating from lower latitudes. In a new approach we here show how the Inughuits in Avanersuaq are subject to high Hg exposure from the hunted traditional food, consisting of mainly marine seabirds and mammals. Violation of the provisional tolerably yearly intake of Hg, on average by a factor of 11 (range 7–15) over the last 20 years as well as the provisional tolerably monthly intake by a factor of 6 (range 2–16), raises health concerns. The surplus of Selenium (Se) in wildlife tissues including narwhals showed Se:Hg molar ratios of 1.5, 2.3, and 16.7 in muscle, liver, and mattak, respectively, likely to provide some protection against the high Hg exposure.     

A review of the global climate change impacts,adaptation, and sustainable mitigation measures

Environmental Science and Pollution Research - Climate change is a long-lasting change in the weather arrays across tropics to polls. It is a global threat that has embarked on to put stress on...     

Carbon bed fires and the use of carbon canisters for air emissions control on fixed-roof tanks

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

Modeling sorbent injection for mercury control in baghouse filters: II--pilot-scale studies and model evaluation

Activated carbon injection for Hg control in a 500-lb/hr pilot-scale coal-fired furnace equipped with a fabric filter for particulate control was evaluated at different operating conditions. The pilot-scale tests showed that Hg removal was improved at lower temperatures and higher C/Hg ratios. The two-stage mathematical model developed to describe Hg removal using powdered activated carbon injection upstream of a baghouse filter was used to obtain Langmuir isotherm parameters as a function of temperature by fitting the model to a subset of experimental data. The predictive capability of the model was then tested by comparing model calculations with additional experimental data from this system obtained using different operating temperatures and sorbent to Hg ratios. Model predictions were in good agreement with experimentally measured Hg removal efficiency. Based on the model predictions, Hg removal in the duct appears to be limited and higher C/Hg ratio, lower operating temperature, and longer cleaning cycle of the baghouse filter should be utilized to achieve higher Hg removal in this system.     

Density of foliage mass and area in the boreal forest cover in Finland,with applications to the estimation of monoterpene and isoprene emissions

The distribution of the density of foliage mass and area in forest canopies throughout Finland (60–70°N) were determined on the basis of the permanent sample plots used in the Finnish National Forest Inventory. These parameters were linked to the long-term monthly mean air temperatures for 1961–1990, which had been converted to hourly temperature and radiation values with the help of a weather simulator in order to calculate the spatial distribution of mean yearly emissions of monoterpene and isoprene over Finland. The mean total density of foliage mass in southern Finland (60°⩽latitude<65°N) was around 500 g m⁻², equivalent to 4–5 m² of total foliage area per m² of land area. In northern Finland (65°⩽latitude<70°N), the maximum values remained below 200–300 g m⁻², or 2–3 m² m⁻². The highest values were achieved in forests dominated by mature Norway spruces. The higher temperatures and longer growing season in southern Finland led to greater emissions than in the rest of the country. Total annual emissions of monoterpene were 1070 kg km⁻² yr⁻¹ in southern Finland and 460 kg km⁻² yr⁻¹ in the north, and those of isoprene from Norway spruce canopies 150 and 40 kg km⁻² yr⁻¹, respectively.     

Toward verifying fossil fuel CO2 emissions with the CMAQ model: Motivation,model description and initial simulation

Motivated by the question of whether and how a state-of-the-art regional chemical transport model (CTM) can facilitate characterization of CO₂ spatiotemporal variability and verify CO₂ fossil-fuel emissions, we for the first time applied the Community Multiscale Air Quality (CMAQ) model to simulate CO₂. This paper presents methods, input data, and initial results for CO₂ simulation using CMAQ over the contiguous United States in October 2007. Modeling experiments have been performed to understand the roles of fossil-fuel emissions, biosphere–atmosphere exchange, and meteorology in regulating the spatial distribution of CO₂ near the surface over the contiguous United States. Three sets of net ecosystem exchange (NEE) fluxes were used as input to assess the impact of uncertainty of NEE on CO₂ concentrations simulated by CMAQ. Observational data from six tall tower sites across the country were used to evaluate model performance. In particular, at the Boulder Atmospheric Observatory (BAO), a tall tower site that receives urban emissions from Denver, CO, the CMAQ model using hourly varying, high-resolution CO₂ fossil-fuel emissions from the Vulcan inventory and CarbonTracker optimized NEE reproduced the observed diurnal profile of CO₂ reasonably well but with a low bias in the early morning. The spatial distribution of CO₂ was found to correlate with NOx, SO₂, and CO, because of their similar fossil-fuel emission sources and common transport processes. These initial results from CMAQ demonstrate the potential of using a regional CTM to help interpret CO₂ observations and understand CO₂ variability in space and time. The ability to simulate a full suite of air pollutants in CMAQ will also facilitate investigations of their use as tracers for CO₂ source attribution. This work serves as a proof of concept and the foundation for more comprehensive examinations of CO₂ spatiotemporal variability and various uncertainties in the future.

Implications: Atmospheric CO₂ has long been modeled and studied on continental to global scales to understand the global carbon cycle. This work demonstrates the potential of modeling and studying CO₂ variability at fine spatiotemporal scales with CMAQ, which has been applied extensively, to study traditionally regulated air pollutants. The abundant observational records of these air pollutants and successful experience in studying and reducing their emissions may be useful for verifying CO₂ emissions. Although there remains much more to further investigate, this work opens up a discussion on whether and how to study CO₂ as an air pollutant.     

Real-world in-use activity, fuel use, and emissions for nonroad construction vehicles: a case study for excavators

A study design was developed and demonstrated for deployment of a portable emission measurement system (PEMS) for excavators. Excavators are among the most commonly used vehicles in construction activities. The PEMS measured nitric oxide, carbon monoxide, hydrocarbons, carbon dioxide, and opacity-based particulate matter. Data collection, screening, processing, and analysis protocols were developed to assure data quality and to quantify variability in vehicle fuel consumption and emissions rates. The development of data collection procedures was based on securing the PEMS while avoiding disruption to normal vehicle operations. As a result of quality assurance, approximately 90% of the attempted measurements resulted in valid data. On the basis of field data collected for three excavators, an average of 50% of the total nitric oxide emissions was associated with 29% of the time of operation, during which the average engine speed and manifold absolute pressure were significantly higher than corresponding averages for all data. Mass per time emission rates during non-idle modes (i.e., moving and using bucket) were on average 7 times greater than for the idle mode. Differences in normalized average rates were influenced more by intercycle differences than intervehicle differences. This study demonstrates the importance of accounting for intercycle variability in real-world in-use emissions to develop more accurate emission inventories. The data collection and analysis methodology demonstrated here is recommended for application to more vehicles to better characterize real-world vehicle activity, fuel use, and emissions for nonroad construction equipment.     

Effects of biochar on the emissions,soil distribution,and nematode control of 1,3-dichloropropene

Emissions of volatile soil fumigant 1,3-dichloropropene (1,3-D) from soil to air are a significant concern in relation to air quality, and cost-effective strategies to reduce such emissions are urgently required by growers to help them comply with increasingly stringent regulations. In this work, application of a rice husk-derived biochar to the surface of a sandy loam soil chamber reduced soil–air emissions of 1,3-D from 42% in a control (no biochar) to 8% due to adsorption onto the biochar. This adsorbed 1,3-D showed a potential for re-volatilization into air and solubilization into the soil–liquid phase. Biochar at the soil surface also reduced soil–gas concentrations in the upper soil; based on the determination of concentration–time values, this may limit 1,3-D-induced nematode control in the upper soil. In batch studies, the mixing of biochar into the soil severely limited nematode control; 1,3-D application rates around four times greater than the maximum permissible limit would be required to give nematode control under such conditions. Therefore, the use of biochar as a surface amendment, while showing an emission reduction benefit, may limit pest control during subsequent fumigations if, as seems probable, it is plowed into the soil.     

Pollution events over the East Mediterranean: Synergistic use of GOME,ground-based and sonde observations and models

The behaviour of ozone (O₃) and two important precursors, nitrogen dioxide (NO₂) and formaldehyde (HCHO), over the East Mediterranean in spring from 1996 to 2002 is studied in order to characterise the buildup of tropospheric O₃. The vertical distribution of O₃ observed over Crete during the Photochemical Activity and Solar Ultraviolet Radiation (PAUR II) campaign in May 1999 has been used for validation of satellite-derived data. Retrievals of O₃ columns from measurements of backscattered radiation by Global Ozone Monitoring Experiment (GOME) are compared with Total Ozone Mapping Spectrometer (TOMS), balloon, Systeme d’Analyse par Observation Zenithale (SAOZ) and LIDAR observations. The total O₃ vertical columns vary between 270 and 402 DU and correlate well with changes in air circulation patterns. The total observed variability in tropospheric O₃ is about 25 DU. Chemical box model calculations associate the GOME-observed NO₂ and HCHO tropospheric columns with a potential of daily photochemical enhancement in the tropospheric O₃ columns of about 0.8–1 DU over Crete and estimate the daily potential of regional photochemical buildup within upwind polluted air masses at about 2–8 DU. A Langrangian analysis attributes at most 10–20 DU of tropospheric O₃ to stratosphere–troposphere exchange (STE). The remainder is attributed to long-range transport of O₃ from industrial regions in Central Europe. From 1996 to 2002, in May no significant inter-annual variation in the tropospheric NO₂ and HCHO columns over Crete has been observed by GOME suggesting no detectable increase in regionally produced tropospheric O₃.     

Modeling non-linear changes in an urban setting: From pro-environmental affordances to responses in behavior,emissions and air quality

Interactions in urban environment were investigated using a multidisciplinary model combination, with focus on traffic, emissions and atmospheric particles. An agent-based model was applied to simulate the evolution of unsustainable human behavior (usage of combustion-based personal vehicles) as a function of pro-environmental affordances (opportunities for sustainable choices). Scenarios regarding changes in multi-pollutant emissions were derived, and the non-linear implications to atmospheric particles were simulated with a box model. Based on the results for a Nordic city, increasing pro-environmental affordances by 10%, 50% or 100% leads to emission reductions of 15%, 30% and 40% within 2 years. To reduce ambient particle mass, emissions from traffic should decrease by > 15%, while the lung deposited surface area decreases in all scenarios (-23%, -32% and -36%, correspondingly). The presented case is representative of one season, but the approach is generic and applicable to simulating a full year, given meteorological and pollution data that reflects seasonal variation. This work emphasizes the necessity to consider feedback mechanisms and non-linearities in both human behavior and atmospheric processes, when predicting the outcomes of changes in an urban system.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-022-01827-8.