Source Of Trace Gases Research Articles

Significant chlorine emissions from biomass burning affect the long-term atmospheric chemistry in Asia.

Biomass burning (BB) is a major source of trace gases and particles in the atmosphere, influencing air quality, radiative balance, and climate. Previous studies have mainly focused on the BB emissions of carbon and nitrogen species with less attention on chlorine. Reactive chlorine chemistry has significant effects on atmospheric chemistry and air quality. However, quantitative information on chlorine emissions from BB, particularly the long-term trend and associated atmospheric impacts, is limited both on regional and global scales. Here, we report a long-term (2001-2018) high-resolution BB emission inventory for the major chlorine-containing compounds (HCl, chloride, and CH3Cl) in Asia based on satellite observations. We estimate an average of 730 Gg yr-1 chlorine emitted from BB activity in Asia, with China contributing the largest share at 24.2% (177 Gg yr-1), followed by Myanmar at 18.7% and India at 18.3%. Distinct seasonal patterns and significant spatial and interannual variability are observed, mainly driven by human-mediated changes in agricultural activity. By incorporating the newly developed chlorine emission inventory into a global chemistry-climate model (CAM-Chem), we find that the BB-chlorine emissions lead to elevated levels of HCl and CH3Cl (monthly average up to 2062 and 1421 parts per trillion by volume (pptv), respectively), subsequently resulting in noticeable changes in oxidants (up to 3.1% in O3 and 17% in OH radicals). The results demonstrate that BB is not only a significant source of air pollutants but also of oxidants, suggesting a larger role of BB emissions in the atmospheric chemistry and oxidation process than previously appreciated. In light of the projected increase in BB activity toward the end of the century and the extensive control of anthropogenic emissions worldwide, the contribution of BB emissions may become fundamental to air quality composition in the future.

Stubble-burning activities in north-western India in 2021: Contribution to air pollution in Delhi

Stubble-burning in northern India is an important source of atmospheric particulate matter (PM) and trace gases, which significantly impact local and regional climate, in addition to causing severe health risks. Scientific research on assessing the impact of these burnings on the air quality over Delhi is still relatively sparse. The present study analyzes the satellite-retrieved stubble-burning activities in the year 2021, using the MODIS active fire count data for Punjab and Haryana, and assesses the contribution of CO and PM2.5 from such biomass-burning activities to the pollution load in Delhi. The analysis suggests that the satellite-retrieved fire counts in Punjab and Haryana were the highest among the last five years (2016–2021). Further, we note that the stubble-burning fires in the year 2021 are delayed by ∼1 week compared to that in the year 2016. To quantify the contribution of the fires to the air pollution in Delhi, we use tagged tracers for CO and PM2.5 emissions from fire emissions in the regional air quality forecasting system. The modeling framework suggests a maximum daily mean contribution of the stubble-burning fires to the air pollution in Delhi in the months of October–November 2021 to be around 30–35%. We find that the contribution from stubble burning activities to the air quality in Delhi is maximum (minimum) during the turbulent hours of late morning to afternoon (calmer hours of evening to early morning). The quantification of this contribution is critical from the crop-residue and air-quality management perspective for policymakers in the source and the receptors regions, respectively.

Emission of Terpenoid Compounds from Rice Plants

The global cultivation area of rice is equivalent to 4% of the world’s forest area and may be an important sink and source of trace gases. To produce a precise terpenoid emission inventory, it is essential to obtain reliable data of terpenoid emission from rice plants. In the present study, terpenoid emissions from various rice species were measured using flow-through chamber and tower flux measurement methods. In the flow-through chamber measurement, linalool was emitted from the above-ground parts of the three rice cultivars “Koshihikari”, “Nipponbare” and “IR72”. The emission rates gradually decreased (<0.1 µg gDW−1 h−1) within two days during the measurement periods. As the touching stimulus might have enhanced linalool emission, a non-contact measurement method, i.e., the tower flux measurement method, was applied to a “Koshihikari” paddy. Linalool was not detected, but α-pinene was detected in the atmosphere above the rice paddy. The α-pinene flux (mean ± 95% confidence interval) was 0.006 ± 0.004 nmol m−2 s−1 on a land-area basis. The flux was 1/200 of the previously reported monoterpene emission rate of the rice plants measured in a commercial chamber, but was not largely different from three other reports. We provide terpenoid flux data above a rice paddy for the first time, which is more reliable because the tower flux measurement method can avoid stimuli to rice leaves and stems. Although the obtained terpenoid emission rate is very low, the obtained values can contribute to the establishment of a precise BVOC inventory in Asia.

Projections of fire emissions and the consequent impacts on air quality under 1.5 °C and 2 °C global warming

Fire is a major source of atmospheric aerosols and trace gases. Projection of future fire activities is challenging due to the joint impacts of climate, vegetation, and human activities. Here, we project global changes of fire-induced particulate matter smaller than 2.5 μm (PM2.5) and ozone (O3) under 1.5 °C/2 °C warming using a climate-chemistry-vegetation coupled model in combination with site-level and satellite-based observations. Compared to the present day, fire emissions of varied air pollutants increase by 10.0%–15.4% at the 1.5 °C warming period and 15.1%–22.5% at the 2 °C warming period, with the most significant enhancements in Amazon, southern Africa, and boreal Eurasia. The warmer climate promotes fuel dryness and the higher leaf area index increases fuel availability, leading to escalated fire flammability globally. However, moderate declines in fire emissions are predicted over the Sahel region, because the higher population density increases fire suppressions and consequently inhibits fire activities over central Africa. Following the changes in fire emissions, the population-weighted exposure to fire PM2.5 increases by 5.1% under 1.5 °C warming and 13.0% under 2 °C warming. Meanwhile, the exposure to fire O3 enhances by 10.2% and 16.0% in response to global warming of 1.5 °C and 2 °C, respectively. As a result, limiting global temperature increase to 1.5 °C can greatly reduce the risks of exposure to fire-induced air pollution compared to 2 °C.

Tropical peat fire emissions: 2019 field measurements in Sumatra and Borneo and synthesis with previous studies

Abstract. Peat fires in Southeast Asia are a major source of trace gases and particles to the regional-global atmosphere that influence atmospheric chemistry, climate, and air quality. During the November 2015 record-high Ocean Niño Index (ONI, 2.6) our mobile smoke sampling team made the first, or rare, field measurements of numerous trace gases, aerosol optical properties, and aerosol chemistry and mass emissions for fires burning only peat in the Indonesian province of Central Kalimantan (on the island of Borneo). The measurements used Fourier transform infrared spectroscopy (FTIR), whole air sampling (WAS), photoacoustic extinctiometers (PAX, 401 and 870 nm), and detailed off-line analyses of particulate matter (PM) collected on filters. In September–November 2019 we measured peat fire trace gas emissions again, using WAS only, under El Niño–Southern Oscillation (ENSO)-neutral conditions (ONI, 0.3) in more remote areas of Central Kalimantan and also the Indonesian provinces of Riau, Jambi, and South Sumatra, all on the island of Sumatra. The 2019 measurements significantly expanded the geographic range and climate conditions sampled. This paper presents the 2019 results and synthesizes them with the previous fieldwork to converge on more robust regional average emission factors (EFs; grams of compound per kilogram of biomass burned) for authentic peat fires. In addition, samples of peat imported from Indonesia were burned in US laboratories, and the EFs and optical properties were characterized in more detail than in the field by a larger suite of instrumentation. We use the improved knowledge of regional emissions based on the expanded field measurements to select the most representative lab data and compute a synthesized, more “chemically complete” set of EFs and aerosol optical properties for tropical peat fires. The modified combustion efficiency (MCE) values for the peat smoke sampled in 2019 were within the range of MCEs sampled in 2015, but with a lower average in 2019 (0.718±0.021, range 0.687–0.736) than 2015 (0.772±0.035, range 0.693–0.835). Averaging the new and older data together suggests an updated MCE for tropical peat fires of ∼0.76. Despite the difference in MCE, the study-average methane emission factors (EF CH4) were remarkably similar across the 2 years probing different regions: 9.42±2.51 g kg−1 in 2019 and 9.51±4.74 g kg−1 in 2015. When parsing the 2019 samples by province, the EFs for non-methane organic gases (NMOGs) were about 3 times higher in South Sumatra and Central Kalimantan than in Jambi and Riau, but the overall 2019 study average was only ∼15 % higher than the 2015 study average. South Sumatra peat fires emitted higher amounts of carbonyl and dimethyl sulfide, suggesting a volcanic or marine influence or effects of agricultural chemicals. The lab and fieldwork taken together provide EFs for 230 trace gases including CO2 (1544 g kg−1), CO (315 g kg−1), and CH4 (9.8 g kg−1). These are significant adjustments to IPCC-recommended EFs, −9 %, +50 %, and −53 %, respectively. We also report EFs for numerous NMOGs, 46 N-containing compounds, and 14 sulfur- or halogen-containing species. The use of high-resolution mass spectrometry in the lab allowed measurement of 82 % more NMOG mass than in the field. Gravimetrically measured EF PM2.5 in the field in 2015 (17.3±5.8 g kg−1) was ∼20 % lower than the average from lab studies (22.4±10.4 g kg−1), perhaps due to higher field temperatures. Taken together the lab and field data show that the single-scattering albedo (SSA) was largely independent of wavelength and MCE in the visible (∼0.998), but lower at low MCE at 401 and 405 nm with a value of 0.958 at the study-average MCE. The absorption Ångström exponent (AAE) at the average MCE was 5.7. By far the largest PM component was weakly absorbing insoluble organic carbon.

A Collection of Airborne Measurements and Analyses of Trace Gases Emitted From Multiple Fires in California

AbstractBiomass burning is an important source of trace gases and particles, and can influence air quality on local, regional, and global scales. With the threat of wildfire events increasing due to changes in land use, increasing population, and climate change, the importance of characterizing wildfire emissions is vital. In this work we characterize trace gas emissions from 12 wildfires and 1 prescribed fire in California between 2013 and 2017, in some cases with multiple measurements performed during different burn periods of a specific fire. Airborne measurements of carbon dioxide, methane, ozone, formaldehyde, water vapor, temperature, and three‐dimensional winds were made by the Alpha Jet Atmospheric eXperiment and have been published at NASA's Atmospheric Science Data Center (https://doi.org/10.5067/ASDC/AJAX/wildfire, Iraci et al., 2021). The majority of these measurements were made as close as possible to each fire and represent fresh emissions from known fire sources. This set of observations from 13 different fires offers the opportunity to explore trace gas emissions over a range of meteorology, fire conditions, and to a lesser extent, vegetation type and drought, and adds to the body of knowledge collected by other investigators and field campaigns.

环境介质中左旋葡聚糖记录与植被火燃烧变化研究进展

<p indent="0mm">Vegetation fire, also called biomass burning, wildfire, landscape fire, bushfire, forest fire, scrub fire, crop residue burning, peat bog fire, savanna fire and grass fire, are spontaneous combustion of plants in a natural setting. Vegetation fires began soon after the appearance of terrestrial plants in the Silurian about 420 million years ago. The regime of vegetation fire has varied with long-term changes in global climate and shorter-term regional changes in climate and vegetation since then, and human beings have altered fire activity since the mid-Holocene, especially in recent years. Vegetation fire affects vegetation distribution, ecological structure, biogeochemical and hydrologic cycles, geophysical processes, and the climate system at local to global scales. Vegetation fire is one of the largest sources of trace gases and aerosols in the Earth’s atmosphere. It contributes more than half of black carbon and about 80% of primary organic aerosol worldwide. Besides, smoke aerosol from vegetation fire is composed of hundreds of chemical components, and many of which (e.g., polycyclic aromatic hydrocarbons) are known to be harmful to human health. Fire smoke causes more than 600000 premature deaths annually worldwide. Therefore, understanding the spatial-temporal changes of vegetation fire is of great importance. Using some specific biomarkers for tracing changes and emissions of vegetation fire has become a research focus in recent years. Among various chemical components, anhydro-sugars are mainly emitted by pyrolysis of cellulose and hemicellulose when burning temperature exceeds 300°C, whereas the contribution of fossil fuel emissions seems to be negligible. Levoglucosan accounts for more than 90% of anhydro-sugars in the nature. Levoglucosan has been reported with a lifetime longer than ten days under most atmospheric conditions, and thus could be transported far from the fire sources. The annual total levoglucosan emission is estimated at about 3.8 Tg (million ton) per year worldwide, however, when atmospheric degradation is considered, the atmospheric budget of levoglucosan is only about 1.9 Gg (kiloton) as calculated by the GEOS-Chem global 3-D chemical transport model. Eventually, levoglucosan is scavenged out the atmosphere to be deposited on earth surfaces by precipitation or gravitational processes. Its presence has been detected in various environmental medias including atmospheric aerosols, precipitation, lake/sea water, snowfall, glacier snow/ice, lake/marine sediments. High levoglucosan concentration/flux is usually found in middle and low latitudes where intense fire sources are nearby. In comparison, extreme low concentration/flux are found on highmountains, polar regions and marine sites where levoglucosan can only arrive by long distance transportation. Levoglucosan has been widely used as a biomarker for tracing fire emissions ranging from event to glacial-inter glacial timescales. For example, levoglucosan has been detected in lake sediments older than 430 ka years before present under anoxic environmental conditions. This work summarized the recent progress of levoglucosan records and vegetation fire changes in various environmental media. Levoglucosan in atmospheric aerosols can reflect fire emissions from event to seasonal scales, and levoglucosan records in glacial ice and lake/marine sediments can reveal fire evolution from seasonal to glacial-interglacial timescales. Overall, the current knowledge supports that levoglucosan should be an ideal biomarker for tracing vegetation fire changes on Earth’s surface. However, more evidences are needed in the near future to better understand its stability, interpret its records in ice core and sediments, as well as its relation with other proxies.

Photochemical method for removing methane interference for improved gas analysis

Abstract. The development of laser spectroscopy has made it possible to measure minute changes in the concentrations of trace gases and their isotopic analogs. These single or even multiply substituted species occur at ratios from percent to below parts per million and contain important information concerning trace gas sources and transformations. Due to their low abundance, minimizing spectral interference from other gases in a mixture is essential. Options including traps and membranes are available to remove many specific impurities. Methods for removing CH4, however, are extremely limited as methane has low reactivity and adsorbs poorly to most materials. Here we demonstrate a novel method for CH4 removal via chlorine-initiated oxidation. Our motivation in developing the technique was to overcome methane interference in measurements of N2O isotopic analogs when using a cavity ring-down spectrometer. We describe the design and validation of a proof-of-concept device and a kinetic model to predict the dependence of the methane removal efficiency on the methane concentration [CH4], chlorine photolysis rate JCl2, chlorine concentration [Cl2] and residence time tR. The model was validated by comparison to experimental data and then used to predict the possible formation of troublesome side products and by-products including CCl4 and HCl. The removal of methane could be maintained with a peak removal efficiency &gt;98 % for ambient levels of methane at a flow rate of 7.5 mL min−1 with [Cl2] at 50 ppm. These tests show that our method is a viable option for continuous methane scrubbing. Additional measures may be needed to avoid complications due to the introduction of Cl2 and formation of HCl. Note that the method will also oxidize most other common volatile organic compounds. The system was tested in combination with a cavity ring-down methane spectrometer, and the developed method was shown to be successful at removing methane interference.

Assessing JUICE's ability of in situ plume detection in Europa's atmosphere

ESA's upcoming JUpiter Icy moons Explorer (JUICE) is scheduled to perform two flybys of Jupiter's moon Europa. Here, we present the results of our investigation into JUICE's capability to detect plumes and to separate them from the background water in the atmosphere as a function of their source's location and mass flux on the Europan surface using the neutral mass spectrometer NIM. For both of the currently planned flybys we evaluate different scenarios to estimate how feasible such a detection is, using a Monte Carlo particle tracing model of a plume. We also incorporate the putative plume candidates reported by Roth et al. (2014b), Sparks et al. (2016), Sparks et al. (2017), Jia et al. (2018), Arnold et al. (2019) and Sparks et al. (2019) into this investigation. We come to the conclusion that the first flyby trajectory is better suited to detect the potential plume candidates listed above as they are detectable down to mass fluxes of approx. 100 ​kg/s. The second flyby requires mass fluxes between 100 ​kg/s and 500 ​kg/s for all suggested plume candidates to be detectable. This discrepancy is caused by the first flyby's closer proximity to the locations of the suggested plume sources which lie mainly on the southern hemisphere. Separation of water plumes from the atmospheric water vapour density is dependent on the mass flux of the respective plume source. The only plume separable from the background water in the atmosphere at the lowest investigated plume source mass flux of 1 ​kg/s is the one suggested by Roth et al. (2014b). It is therefore the most likely plume to be detected by JUICE. Furthermore, we investigate the detectability of trace gas contents in a plume and analyse how these impact upon plume detection. The spacecraft will be able to detect whether lighter-than-water trace gas species are present within the plume down to trace gas source mass fluxes of 0.1 ​kg/s. Provided this is the case, such species constitute a means to identifying plumes in the Europan atmosphere. Finally, the effects of lowering the flyby altitude are examined. We find that lowering the altitude of the CA does not increase the region of separability. Therefore, lowering the second flyby trajectory will not suffice for the spacecraft to be able to identify plumes that originate from the locations of the candidates mentioned above. Considering that the second flyby is the most likely to be lowered, this case study provides an example of the importance of arranging the second trajectory in a manner such that its ground track lies in close proximity to the locations of the suggested plume candidates listed above. This approach to the mission planning maximises the chance of separating the presumptive plumes from the atmospheric background water even at the lowest plume source mass fluxes.

A Statistical Evaluation of WRF-LES Trace Gas Dispersion Using Project Prairie Grass Measurements

AbstractIn recent years, new measurement systems have been deployed to monitor and quantify methane emissions from the natural gas sector. Large-eddy simulation (LES) has complemented measurement campaigns by serving as a controlled environment in which to study plume dynamics and sampling strategies. However, with few comparisons to controlled-release experiments, the accuracy of LES for modeling natural gas emissions is poorly characterized. In this paper, we evaluate LES from the Weather Research and Forecasting (WRF) model against Project Prairie Grass campaign measurements and surface layer similarity theory. Using WRF-LES, we simulate continuous emissions from 30 near-surface trace gas sources in two stability regimes: strong and weak convection. We examine the impact of grid resolutions ranging from 6.25 m to 52 m in the horizontal dimension on model results. We evaluate performance in a statistical framework, calculating fractional bias and conducting Welch’s t-tests. WRF-LES accurately simulates observed surface concentrations at 100 m and beyond under strong convection; simulated concentrations pass t-tests in this region irrespective of grid resolution. However, in weakly convective conditions with strong winds, WRF-LES substantially overpredicts concentrations – the magnitude of fractional bias often exceeds 30%, and all but one C-test fails. The good performance of WRF-LES under strong convection correlates with agreement with local free convection theory and a minimal amount of parameterized turbulent kinetic energy. The poor performance under weak convection corresponds to misalignment with Monin-Obukhov similarity theory and a significant amount of parameterized turbulent kinetic energy.

Long-range transport of Siberian biomass burning emissions to North America during FIREX-AQ

Biomass burning from wildfires is a significant global source of aerosol and trace gases which impact air quality, tropospheric and stratospheric composition, and climate. During the summer of 2019, wildfire activity in central and eastern Siberia occurred during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign conducted in the United States between July 24 and September 6, 2019. Ground-based lidar observations from the Autonomous Mobile Ozone Lidar for Tropospheric Experiments (AMOLITE) system in Alberta, Canada retrieved frequent ozone (O3) and aerosol lamina in the free troposphere during the campaign. Simulated data from NASA's GEOS Composition Forecast (GEOS-CF) coupled chemistry meteorology model, TROPOspheric Monitoring Instrument (TROPOMI), and ground-based in situ measurements were applied to define the trans-Pacific and trans-Arctic transport pathways of Siberian biomass burning emissions resulting in the enhanced O3 and aerosol lamina observed by AMOLITE in western Canada. Siberian wildfires had some influence on North American air quality resulting in enhancements of surface carbon monoxide (CO) and fine particulate matter (PM2.5) concentrations in western Canada; however, minimal increases in surface-level O3 were measured as well as modeled by GEOS-CF. The impact in western Canada was larger in the free troposphere, demonstrated by GEOS-CF modeled and AMOLITE observed O3 lamina >20 ppb above background values and coincident model-predicted PM2.5 lamina >30 μg m−3. This study demonstrated that the Siberian biomass burning emissions in the summer of 2019 impacted tropospheric composition in western Canada, and potentially could have influenced areas in the vicinity of FIREX-AQ airborne and ground-based measurements in the United States, and should be considered in future studies.

APIFLAME v2.0 biomass burning emissions model: impact of refined input parameters on atmospheric concentration in Portugal in summer 2016

Abstract. Biomass burning emissions are a major source of trace gases and aerosols. Wildfires being highly variable in time and space, calculating emissions requires a numerical tool able to estimate fluxes at the kilometer scale and with an hourly time step. Here, the APIFLAME model version 2.0 is presented. It is structured to be modular in terms of input databases and processing methods. The main evolution compared to version 1.0 is the possibility of merging burned area and fire radiative power (FRP) satellite observations to modulate the temporal variations of fire emissions and to integrate small fires that may not be detected in the burned area product. Accounting for possible missed detection due to small fire results in an increase in burned area ranging from ∼5 % in Africa and Australia to ∼30 % in North America on average over the 2013–2017 time period based on the Moderate-Resolution Imaging Spectroradiometer (MODIS) Collection 6 fire products. An illustration for the case of southwestern Europe during the summer of 2016, marked by large wildfires in Portugal, is presented. Emissions calculated using different possible configurations of APIFLAME show a dispersion of 80 % on average over the domain during the largest wildfires (8–14 August 2016), which can be considered as an estimate of uncertainty of emissions. The main sources of uncertainty studied, by order of importance, are the emission factors, the calculation of the burned area, and the vegetation attribution. The aerosol (PM10) and carbon monoxide (CO) concentrations simulated with the CHIMERE regional chemistry transport model (CTM) are consistent with observations (good timing for the beginning and end of the events, ±1 d for the timing of the peak values) but tend to be overestimated compared to observations at surface stations. On the contrary, vertically integrated concentrations tend to be underestimated compared to satellite observations of total column CO by the Infrared Atmospheric Sounding Interferometer (IASI) instrument and aerosol optical depth (AOD) by MODIS. This underestimate is lower close to the fire region (5 %–40 % for AOD depending on the configuration and 8 %–18 % for total CO) but rapidly increases downwind. For all comparisons, better agreement is achieved when emissions are injected higher into the free troposphere using a vertical profile as estimated from observations of aerosol plume height by the Multi-angle Imaging SpectroRadiometer (MISR) satellite instrument (injection up to 4 km). Comparisons of aerosol layer heights to observations by the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) show that some parts of the plume may still be transported at too low an altitude. The comparisons of the different CTM simulations to observations point to uncertainties not only on emissions (total mass and daily variability) but also on the simulation of their transport with the CTM and mixing with other sources. Considering the uncertainty of the emission injection profile and of the modeling of the transport of these dense plumes, it is difficult to fully validate emissions through comparisons between model simulations and atmospheric observations.

The impacts of ocean acidification on marine trace gases and the implications foratmospheric chemistry andclimate.

Surface ocean biogeochemistry and photochemistry regulate ocean–atmosphere fluxes of trace gases critical for Earth's atmospheric chemistry and climate. The oceanic processes governing these fluxes are often sensitive to the changes in ocean pH (or pCO2) accompanying ocean acidification (OA), with potential for future climate feedbacks. Here, we review current understanding (from observational, experimental and model studies) on the impact of OA on marine sources of key climate-active trace gases, including dimethyl sulfide (DMS), nitrous oxide (N2O), ammonia and halocarbons. We focus on DMS, for which available information is considerably greater than for other trace gases. We highlight OA-sensitive regions such as polar oceans and upwelling systems, and discuss the combined effect of multiple climate stressors (ocean warming and deoxygenation) on trace gas fluxes. To unravel the biological mechanisms responsible for trace gas production, and to detect adaptation, we propose combining process rate measurements of trace gases with longer term experiments using both model organisms in the laboratory and natural planktonic communities in the field. Future ocean observations of trace gases should be routinely accompanied by measurements of two components of the carbonate system to improve our understanding of how in situ carbonate chemistry influences trace gas production. Together, this will lead to improvements in current process model capabilities and more reliable predictions of future global marine trace gas fluxes.

Ambient air quality in the Kathmandu Valley, Nepal, during the pre-monsoon: concentrations and sources of particulate matter and trace gases

Abstract. The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM2.5 and PM10, respectively), online PM1, inorganic trace gases (NH3, HNO3, SO2, and HCl), and carbon-containing gases (CO2, CO, CH4, and 93 non-methane volatile organic compounds; NMVOCs) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated origins primarily from poorly maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those 2 weeks, daily average PM2.5 concentrations ranged from 30 to 207 µg m−3, which exceeded the World Health Organization 24 h guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas–aerosol phase partitioning of NH3, HNO3, and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (averaging 1230±1154 ng m−3), 1,3,5-triphenylbenzene (0.8±0.6 ng m−3), cholesterol (2.9±6.6 ng m−3), stigmastanol (1.0 ±0.8 ng m−3), and cis-pinonic acid (4.5±1.9 ng m−3) indicate contributions from biomass burning, garbage burning, food cooking, cow dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18±5 %), biomass burning (17±10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18±9 %). Model sensitivity tests with newly developed source profiles indicated contributions from biomass burning within a factor of 2 of previous estimates but greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM2.5 OC included those originating from anthropogenic precursors such as naphthalene (10±4 %) and methylnaphthalene (0.3±0.1 %) and biogenic precursors for monoterpenes (0.13±0.07 %) and sesquiterpenes (5±2 %). An average of 25 % of the PM2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) and/or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil fuel combustion) were the greatest contributors to PM2.5 and, as such, should be considered primary targets for controlling ambient PM pollution.

Observations of ozone formation in southern African savanna and grassland fire plumes

Open biomass burning is one of the largest sources of aerosols and reactive trace gases into the atmosphere, having a significant effect on earth's radiative budget and air quality. Biomass burning degrades air quality by increasing both particulate matter and ozone levels. Unlike aerosols, ozone is not directly emitted in fires but it is frequently formed in ageing plumes. This is not surprising, as many of the reactive trace gases emitted in biomass burning including nitrogen oxides, carbon monoxide and volatile organic compounds, act as precursors for ozone formation. Geographically, Africa is the most significant source region of biomass burning emissions. Here, we report rapid ozone formation in daytime savanna and grassland fire plumes observed in South Africa. We observed higher ozone production in more flaming cases for plumes fresher than 1.5h. However, in plumes aged >1.5h combustion characteristics have no effect, but ozone production is positively correlated with nitrogen oxides. Furthermore, the plumes with highest ozone production also had the strongest secondary aerosol formation during plume ageing. Additionally, we report emission factors of nitric oxide and sulphur dioxide for southern African savanna and grassland fires. SO2 emission factor was on average 1.1 g kg−1, which is two to three times higher than previous observations for savanna and grassland. On the other hand, the average NO emission factor (2.6 g kg−1) agrees well with previous observations.

Sensitive detection of atmospheric N2O isotopomers using a quantum cascade laser based spectrometer

Stable isotope analytical techniques have a crucial role to play in the study of atmospheric pollutant and trace gas sources, sinks and transport processes. Quantum cascade laser absorption spectroscopy (QCLAS) allows the site-selective and high-precision analysis of many isotopic species at trace levels, yet not sensitive enough for atmospheric N2O mixing ratios. In this study, a quantum cascade laser based spectrometer combining with a liquid nitrogen-free preconcentration unit was developed to demonstrate the applicability of high sensitivity and high precision measurement of atmospheric N2O isotopomers. Primary laboratory tests have been performed for simultaneous determination of the mixing ratios of the most abundant nitrous oxide isotopic species: 14N15N16O, 15N14N16O and 14N216O. The experiment results showed that site-selective 15N/14N can be measured with the precision of 0.59‰ with an optimal averaging time of 258 s at 100 ppm. Details of spectral absorption line pairs selection and N2O adsorption/desorption processes are also discussed.

Production of methane and ethylene from plastic in the environment.

Mass production of plastics started nearly 70 years ago and the production rate is expected to double over the next two decades. While serving many applications because of their durability, stability and low cost, plastics have deleterious effects on the environment. Plastic is known to release a variety of chemicals during degradation, which has a negative impact on biota. Here, we show that the most commonly used plastics produce two greenhouse gases, methane and ethylene, when exposed to ambient solar radiation. Polyethylene, which is the most produced and discarded synthetic polymer globally, is the most prolific emitter of both gases. We demonstrate that the production of trace gases from virgin low-density polyethylene increase with time, with rates at the end of a 212-day incubation of 5.8 nmol g-1 d-1 of methane, 14.5 nmol g-1 d-1 of ethylene, 3.9 nmol g-1 d-1 of ethane and 9.7 nmol g-1 d-1 of propylene. Environmentally aged plastics incubated in water for at least 152 days also produced hydrocarbon gases. In addition, low-density polyethylene emits these gases when incubated in air at rates ~2 times and ~76 times higher than when incubated in water for methane and ethylene, respectively. Our results show that plastics represent a heretofore unrecognized source of climate-relevant trace gases that are expected to increase as more plastic is produced and accumulated in the environment.

Major secondary aerosol formation in southern African open biomass burning plumes

Open biomass burning contributes significantly to air quality degradation and associated human health impacts over large areas. It is one of the largest sources of reactive trace gases and fine particles to Earth’s atmosphere and consequently a major source of cloud condensation nuclei on a global scale. However, there is a large uncertainty in the climate effect of open biomass burning aerosols due to the complexity of their constituents. Here, we present an exceptionally large dataset on southern African savannah and grassland fire plumes and their atmospheric evolution, based on 5.5 years of continuous measurements from 2010 to 2015. We find that the mass of submicrometre aerosols more than doubles on average, in only three hours of daytime ageing. We also evaluate biomass burning aerosol particle size distributions and find a large discrepancy between the observations and current model parameterizations, especially in the 30–100 nm range. We conclude that accounting for near-source secondary organic aerosol formation and using measurement-based size distribution parameterizations in smoke plumes is essential to better constrain the climate and air quality effects of savannah and grassland fires. A substantial amount of secondary aerosols form within hours of biomass burning in southern African savannah and grassland fires, according to analyses of 5.5 years of continuous field measurements.

Bootstrap inversion technique for atmospheric trace gas source detection and quantification using long open-path laser measurements

Abstract. Advances in natural gas extraction technology have led to increased activity in the production and transport sectors in the United States and, as a consequence, an increased need for reliable monitoring of methane leaks to the atmosphere. We present a statistical methodology in combination with an observing system for the detection and attribution of fugitive emissions of methane from distributed potential source location landscapes such as natural gas production sites. We measure long (&gt; 500 m), integrated open-path concentrations of atmospheric methane using a dual frequency comb spectrometer and combine measurements with an atmospheric transport model to infer leak locations and strengths using a novel statistical method, the non-zero minimum bootstrap (NZMB). The new statistical method allows us to determine whether the empirical distribution of possible source strengths for a given location excludes zero. Using this information, we identify leaking source locations (i.e., natural gas wells) through rejection of the null hypothesis that the source is not leaking. The method is tested with a series of synthetic data inversions with varying measurement density and varying levels of model–data mismatch. It is also tested with field observations of (1) a non-leaking source location and (2) a source location where a controlled emission of 3.1 × 10−5 kg s−1 of methane gas is released over a period of several hours. This series of synthetic data tests and outdoor field observations using a controlled methane release demonstrates the viability of the approach for the detection and sizing of very small leaks of methane across large distances (4+ km2 in synthetic tests). The field tests demonstrate the ability to attribute small atmospheric enhancements of 17 ppb to the emitting source location against a background of combined atmospheric (e.g., background methane variability) and measurement uncertainty of 5 ppb (1σ), when measurements are averaged over 2 min. The results of the synthetic and field data testing show that the new observing system and statistical approach greatly decreases the incidence of false alarms (that is, wrongly identifying a well site to be leaking) compared with the same tests that do not use the NZMB approach and therefore offers increased leak detection and sizing capabilities.

Airborne DOAS retrievals of methane, carbon dioxide, and water vapor concentrations at high spatial resolution: application to AVIRIS-NG

Abstract. At local scales, emissions of methane and carbon dioxide are highly uncertain. Localized sources of both trace gases can create strong local gradients in its columnar abundance, which can be discerned using absorption spectroscopy at high spatial resolution. In a previous study, more than 250 methane plumes were observed in the San Juan Basin near Four Corners during April 2015 using the next-generation Airborne Visible/Infrared Imaging Spectrometer (AVIRIS-NG) and a linearized matched filter. For the first time, we apply the iterative maximum a posteriori differential optical absorption spectroscopy (IMAP-DOAS) method to AVIRIS-NG data and generate gas concentration maps for methane, carbon dioxide, and water vapor plumes. This demonstrates a comprehensive greenhouse gas monitoring capability that targets methane and carbon dioxide, the two dominant anthropogenic climate-forcing agents. Water vapor results indicate the ability of these retrievals to distinguish between methane and water vapor despite spectral interference in the shortwave infrared. We focus on selected cases from anthropogenic and natural sources, including emissions from mine ventilation shafts, a gas processing plant, tank, pipeline leak, and natural seep. In addition, carbon dioxide emissions were mapped from the flue-gas stacks of two coal-fired power plants and a water vapor plume was observed from the combined sources of cooling towers and cooling ponds. Observed plumes were consistent with known and suspected emission sources verified by the true color AVIRIS-NG scenes and higher-resolution Google Earth imagery. Real-time detection and geolocation of methane plumes by AVIRIS-NG provided unambiguous identification of individual emission source locations and communication to a ground team for rapid follow-up. This permitted verification of a number of methane emission sources using a thermal camera, including a tank and buried natural gas pipeline.