Ambient Mixing Ratios Research Articles

Measuring short-chain per- and polyfluoroalkyl substances in Central New Jersey air using chemical ionization mass spectrometry

ABSTRACT Real-time measurements of short-chain (C < 8) per- and polyfluoroalkyl substances (PFAS) were performed in Central New Jersey air using chemical ionization mass spectrometry (CIMS). The CIMS was calibrated for C2–C6 perfluorinated carboxylic acids, and 4:2 and 6:2 fluorotelomer alcohols. Of these, only trifluoroacetic acid (TFA) was detected in ambient air above instrumental detection limits. However, instrumental sensitivities (and thus ambient mixing ratios) were estimated for other detected PFAS including C3H2F6O and C6HF11O3. TFA mixing ratios reached up to 0.7 parts-per-trillion by volume (pptv). Estimated C3H2F6O and C6HF11O3 mixing ratios reached the single pptv level. These latter two formulas are consistent with hexafluoroisopropanol (HFIP) and hexafluoropropylene oxide dimer acid (HFPO-DA), respectively, though they may potentially represent multiple isomers. Diel profiles of detected PFAS along with local meteorological data can provide information on potential local sources of these compounds. However, only limited discussion of potential sources was provided here given the sparse detection of these compounds above instrument detection limits. These results demonstrate the potential of online CIMS instrumentation for measuring certain PFAS in ambient outdoor air in real time at or below the pptv level. This technique also has potential for fenceline monitoring and other near-source applications. Implications: Online chemical ionization mass spectrometry (CIMS) has potential for fast, real-time measurements of certain airborne per- and polyfluoroalkyl substances (PFAS). Three short-chain (C < 8) PFAS were detected by CIMS in Central New Jersey ambient air near or above the parts-per-trillion by volume (pptv) level. This technique also has potential for fenceline monitoring and other near-source applications for airborne PFAS.

Identification of volatile organic compounds and their sources driving ozone and secondary organic aerosol formation in NE Spain

Volatile organic compounds (VOCs) play a crucial role in the formation of ozone (O3) and secondary organic aerosol (SOA). We conducted measurements of VOC ambient mixing ratios during both summer and winter at two stations: a Barcelona urban background station (BCN) and the Montseny rural background station (MSY). Subsequently, we employed positive matrix factorization (PMF) to analyze the VOC mixing ratios and identify their sources. Our analysis revealed five common sources: anthropogenic I (traffic & industries); anthropogenic II (traffic & biomass burning); isoprene oxidation; monoterpenes; long-lifetime VOCs. To assess the impact of these VOCs on the formation of secondary pollutants, we calculated the ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAP) associated with each VOC. In conclusion, our study provides insights into the sources of VOCs and their contributions to the formation of ozone and SOA in NE Spain. The OFP was primarily influenced by anthropogenic aromatic compounds from the traffic & industries source at BCN (38–49 %) and during winter at MSY (34 %). In contrast, the summer OFP at MSY was primarily driven by biogenic contributions from monoterpenes and isoprene oxidation products (45 %). Acetaldehyde (10–35 %) and methanol (13–14 %) also made significant OFP contributions at both stations. Anthropogenic aromatic compounds originating from traffic, industries, and biomass burning played a dominant role (88–93 %) in SOA formation at both stations during both seasons. The only exception was during the summer at MSY, where monoterpenes became the primary driver of SOA formation (41 %). These findings emphasize the importance of considering both anthropogenic and biogenic VOCs in air quality management strategies.

Emission of volatile organic compounds from residential biomass burning and their rapid chemical transformations

Biomass combustion releases a complex array of Volatile Organic Compounds (VOCs) that pose significant challenges to air quality and human health. Although biomass burning has been extensively studied at ecosystem levels, understanding the atmospheric transformation and impact on air quality of emissions in urban environments remains challenging due to complex sources and burning materials. In this study, we investigate the VOC emission rates and atmospheric chemical processing of predominantly wood burning emissions in a small urban centre in Greece. Ioannina is situated in a valley within the Dinaric Alps and experiences intense atmospheric pollution accumulation during winter due to its topography and high wood burning activity. During pollution event days, the ambient mixing ratios of key VOC species were found to be similar to those reported for major urban centres worldwide. Positive matrix factorisation (PMF) analysis revealed that biomass burning was the dominant emission source (>50 %), representing two thirds of OH reactivity, which indicates a highly reactive atmospheric mixture. Calculated OH reactivity ranges from 5 s−1 to an unprecedented 278 s−1, and averages at 93 ± 66 s−1 at 9 PM, indicating the presence of exceptionally reactive VOCs. The highly pronounced photochemical formation of organic acids coincided with the formation of ozone, highlighting the significance of secondary formation of pollutants in poorly ventilated urban areas. Our findings underscore the pressing need to transition from wood burning to environmentally friendly sources of energy in poorly ventilated urban areas, in order to improve air quality and safeguard public health.

Spatially Resolved Source Apportionment of Industrial VOCs Using a Mobile Monitoring Platform

Industrial emissions of volatile organic compounds (VOCs) directly impact air quality downwind of facilities and contribute to regional ozone and secondary organic aerosol production. Positive matrix factorization (PMF) is often used to apportion VOCs to their respective sources using measurement data collected at fixed sites, for example air quality monitoring stations. Here, we apply PMF analysis to high time-resolution VOC measurement data collected both while stationary and while moving using a mobile monitoring platform. The stationary monitoring periods facilitated the extraction of representative industrial VOC source profiles while the mobile monitoring periods were critical for the spatial identification of VOC hotspots. Data were collected over five days in a heavily industrialized region of southwestern Ontario containing several refineries, petrochemical production facilities and a chemical waste disposal facility. Factors associated with petroleum, chemical waste and rubber production were identified and ambient mixing ratios of selected aromatic, unsaturated and oxygenated VOCs were apportioned to local and background sources. Fugitive emissions of benzene, highly localized and predominantly associated with storage, were found to be the dominant local contributor to ambient benzene mixing ratios measured while mobile. Toluene and substituted aromatics were predominantly associated with refining and traffic, while methyl ethyl ketone was linked to chemical waste handling. The approach described here facilitates the apportionment of VOCs to their respective local industrial sources at high spatial and temporal resolution. This information can be used to identify problematic source locations and to inform VOC emission abatement strategies.

Estimate of hydrochlorofluorocarbon emissions during 2011–2018 in the Yangtze River Delta, China

Hydrochlorofluorocarbons (HCFCs) are used as temporary substitutes for chlorofluorocarbons and other ozone-depleting substances because they have reduced ozone depletion and global warming potentials. The consumption and production of HCFCs are regulated via the Montreal Protocol and its amendments till 2013, with a complete phase-out being scheduled by 2030 for Article 5 parties (developing countries). To better understand the characteristics and emissions of HCFCs in the Yangtze River Delta (YRD), which is the largest metropolitan area in China, weekly flask samples were collected at the Lin'an regional background station located in the YRD from 2011 to 2018 and measured for four HCFCs (HCFC-22, HCFC-141b, HCFC-142b, and HCFC-124). The HCFC-132b and HCFC-133a measurements began in 2018. The ambient mixing ratios of the HCFCs exhibited higher concentrations and larger variabilities than those at the Shangri-la regional background station at similar latitudes in southwest China. The HCFC emissions in the YRD were estimated based on the tracer ratio method using CO and HFC-134a as tracers, and were comparable within the uncertainties. Our results are generally consistent with previous estimates obtained using top-down approaches. HCFC-22 and HCFC-141b contributed 52% ± 23% and 41% ± 24% of the total ODP-weighted (CFC-11-equivalent) HCFC emissions from the YRD, respectively, whereas HCFC-22 contributed the most (83% ± 36%) to the total CO2-equivalent HCFC emissions from the YRD. The cumulative ODP-weighted and CO2-equivalent emissions of HCFCs from the YRD accounted for 25% ± 15% and 20% ± 11% of the national corresponding totals, respectively, for 2011–2017. The HCFC-141b emissions from the YRD contributed approximately half of the total Chinese emissions. HCFC-133a emissions in the YRD accounted for approximately one-fifth of the global total in 2018. Thus, the YRD is an important contributor of HCFC emissions on national and global scales.

The atmospheric concentrations and emissions of major halocarbons in China during 2009–2019

Due to the characteristics of ozone-depleting and high global warming potential, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) have been restricted by the Montreal Protocol and its amendments over the world. Considering that China is one of the main contributors to the emission of halocarbons, a long-term atmospheric observation on major substances including CFC-11 (CCl3F), CFC-12 (CCl2F2), HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HFC-134a (CH2FCF3) was conducted in five cities (Beijing, Hangzhou, Guangzhou, Lanzhou and Chengdu) of China during 2009–2019. The atmospheric concentrations of CFC-11, CFC-12, HCFC-141b and HCFC-142b all showed declining trends on the whole while those of HCFC-22 and HFC-134a were opposite. A paired sample t-test showed that the ambient mixing ratios of HCFC-22 and HFC-134a in cities were 41.9% and 25.7% higher on average than those in suburban areas, respectively, while the other substances did not show significant regional differences. The annual emissions of halocarbons were calculated using an interspecies correlation method and the results were generally consistent with the published estimates. Discrepancies between bottom-up inventories and the estimates in this study for CFCs emissions were found. Among the most consumed ozone depleting substances (ODSs) in China, CFCs accounted for 75.1% of the ozone depletion potential (ODP)-weighted emissions while HCFCs contributed a larger proportion (58.6%) of CO2-equivalent emissions in 2019. China's emissions of HCFC-141b and HCFC-142b contributed the most to the global emission (17.8%–48.0%). The elimination of HCFCs in China will have a crucial impact on the HCFCs phase-out in the world.

Monitoring Chlorofluorocarbons in Potential Source Regions in Eastern China

Recent studies have indicated that Eastern China might be a potential source region of increased atmospheric chlorofluorocarbons (CFCs). To investigate this possibility, a field measurement was carried out from October to December 2017 for identifying the ambient concentration levels of representative trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trifluorotrichloroethane (CFC-113), and tetrafluorodichloroethane (CFC-114) at the residential and municipal solid waste (MSW) landfills and industrial sites in Eastern China. The ambient mixing ratios of CFCs at residential sites were almost within 20% enhancements of the global background sites. The highest levels of CFCs were observed at the MSW landfill sites. Moreover, CFC-11 and CFC-113 concentrations at MSW landfill, which was in service, were two times higher than that at completed MSW landfill. Mean concentrations of 322 pptv for CFC-11, 791 pptv for CFC-12, 91 pptv for CFC-113, and 16 pptv for CFC-114 at various industrial sites were higher than those at residential sites, but they were obviously lower than that at MSW landfill in use. A poor intercorrelation between the CFCs indicated that they did not come from the same source. Higher concentrations measured in this study compared with background sites indicates that MSW landfills could be an unintentional emission source and there are still substantial amounts of CFCs being stored in banks that may discharge CFCs into the atmosphere in Eastern China.

Emission drivers and variability of ambient isoprene, formaldehyde and acetaldehyde in north-west India during monsoon season

Isoprene, formaldehyde and acetaldehyde are important reactive organic compounds which strongly impact atmospheric oxidation processes and formation of tropospheric ozone. Monsoon meteorology and the topography of Himalayan foothills cause surface emissions to get rapidly transported both horizontally and vertically, thereby influencing atmospheric processes in distant regions. Further in monsoon, Indo-Gangetic Plain is a major rice growing region of the world and daytime hourly ozone can frequently exceed phytotoxic dose of 40 ppb O3. However, the sources and ambient variability of these compounds which are potent ozone precursors are unknown. Here, we investigate the sources and photochemical processes driving their emission/formation during monsoon season from a sub-urban site at the foothills of the Himalayas. The measurements were performed in July, August and September using a high sensitivity mass spectrometer. Average ambient mixing ratios (±1σ variability) of isoprene, formaldehyde, acetaldehyde, and the sum of methyl vinyl ketone and methacrolein (MVK+MACR), were 1.4 ± 0.3 ppb, 5.7 ± 0.9 ppb, 4.5 ± 2.0 ppb, 0.75 ± 0.3 ppb, respectively, and much higher than summertime values in May. For isoprene these values were comparable to mixing ratios observed over tropical forests. Surprisingly, despite occurrence of anthropogenic emissions, biogenic emissions were found to be the major source of isoprene with peak daytime isoprene driven by temperature (r ≥ 0.8) and solar radiation. Photo-oxidation of precursor hydrocarbons were the main sources of acetaldehyde, formaldehyde and MVK+MACR. Ambient mixing ratios of all the compounds correlated poorly with acetonitrile (r ≤ 0.2), a chemical tracer for biomass burning suggesting negligible influence of biomass burning during monsoon season. Our results suggest that during monsoon season when radiation and rain are no longer limiting factors and convective activity causes surface emissions to be transported to upper atmosphere, biogenic emissions can significantly impact the remote upper atmosphere, climate and ozone affecting rice yields.

Biogenic volatile organic compound ambient mixing ratios and emission rates in the Alaskan Arctic tundra.

Rapid Arctic warming, a lengthening growing season, and the increasing abundance of biogenic volatile-organic-compound-emitting shrubs are all anticipated to increase atmospheric biogenic volatile organic compounds (BVOCs) in the Arctic atmosphere, with implications for atmospheric oxidation processes and climate feedbacks. Quantifying these changes requires an accurate understanding of the underlying processes driving BVOC emissions in the Arctic. While boreal ecosystems have been widely studied, little attention has been paid to Arctic tundra environments. Here, we report terpenoid (isoprene, monoterpenes, and sesquiterpenes) ambient mixing ratios and emission rates from key dominant vegetation species at Toolik Field Station (TFS; 68°38′ N, 149°36′ W) in northern Alaska during two back-to-back field campaigns (summers of 2018 and 2019) covering the entire growing season. Isoprene ambient mixing ratios observed at TFS fell within the range of values reported in the Eurasian taiga (0–500 parts per trillion by volume – pptv), while monoterpene and sesquiterpene ambient mixing ratios were respectively close to and below the instrumental quantification limit (~ 2 pptv). Isoprene surface emission rates ranged from 0.2 to 2250 μgC m−2 h−1 (mean of 85 μgC m−2 h−1) and monoterpene emission rates remained, on average, below 1 μgC m−2 h−1 over the course of the study. We further quantified the temperature dependence of isoprene emissions from local vegetation, including Salix spp. (a known isoprene emitter), and compared the results to predictions from the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1). Our observations suggest a 180 %–215 % emission increase in response to a 3–4°C warming, and the MEGAN2.1 temperature algorithm exhibits a close fit with observations for enclosure temperatures in the 0–30°C range. The data presented here provide a baseline for investigating future changes in the BVOC emission potential of the under-studied Arctic tundra environment.

Dynamics and mechanisms of volatile organic compound exchanges in a winter wheat field

The understanding of biogenic volatile organic compound (BVOC) exchanges has become a key scientific issue because of their high reactivity and their impact in the atmosphere. However, so far, few studies have focused on BVOCs exchanged by agricultural species, and in particular by winter wheat, despite this species being the leading worldwide crop in terms of harvested area. This study for the first time investigated BVOC exchanges from winter wheat during most developmental stages of the plant. Fluxes were measured in Belgium at the ecosystem-scale using the disjunct eddy covariance by mass scanning technique, and a proton-transfer-reaction mass spectrometer for BVOC ambient mixing ratio measurements. As is usually observed for crops and grasses, the winter wheat field emitted mainly methanol, although bi-directional exchanges were observed. The second most exchanged compound was acetic acid which was captured during the entire growing season. Bi-directional exchanges of acetaldehyde and acetone were also reported. Terpene exchanges were 22 times smaller than oxygenated VOC (OVOC) exchanges. For all compounds, the exchanges were the most pronounced at the end of the growing season, i.e., under warm, dry and sunny conditions. Senescence-induced emissions were furthermore observed for methanol and acetaldehyde. For all investigated OVOCs, the exchanges very likely originated from both the soil and the plants. Despite their mixed origin, the MEGAN (Model of Emissions of Gases and Aerosols from Nature) v2.1 up-scaling model could adequately reproduce the methanol, acetaldehyde and acetone exchanges measured at this site during the mature and senescence phases of the plant, when the standard emission factor and the leaf age factor were adapted based on the measurements. In contrast, the model failed to reproduce the measured acetic acid exchanges. When the standard emission factor values currently assigned in MEGAN were applied, however, the exchanges were largely over-estimated for all compounds.

Quantum cascade laser based absorption spectroscopy for direct monitoring of atmospheric N2O isotopes

A compact high-resolution spectroscopic sensor using a thermoelectrically (TE) cooled continuous-wave (CW) room temperature (RT) quantum cascade laser (QCL) operating at 4.6 μm, is employed for simultaneous detection of three main isotopic species (14N15N16O, 15N14N16O and 14N14N16O). To enable a high-precision analysis of N2O isotopic species at ambient mixing ratios, a liquid nitrogen-free preconcentration unit is built to trap and load atmospheric N2O. The absorption spectra of 14N15N16O, 15N14N16O, and 14N14N16O between 2188.6 cm−1 and 2189 cm−1 are measured, and the respective ratios of the rare to the abundant isotopologues abundances are demonstrated. Moreover, spectroscopic parameters of pressure-broadening coefficient for selected absorption lines have been determined, and a good agreement is obtained by comparing with HITRAN database.

Diurnal Variability and Emission Pattern of Decamethylcyclopentasiloxane (D5) from the Application of Personal Care Products in Two North American Cities.

Decamethylcyclopentasiloxane (D5) is a cyclic volatile methyl siloxane (cVMS) that is widely used in consumer products and commonly observed in urban air. This study quantifies the ambient mixing ratios of D5 from ground sites in two North American cities (Boulder, CO, USA, and Toronto, ON, CA). From these data, we estimate the diurnal emission profile of D5 in Boulder, CO. Ambient mixing ratios were consistent with those measured at other urban locations; however, the diurnal pattern exhibited similarities with those of traffic-related compounds such as benzene. Mobile measurements and vehicle experiments demonstrate that emissions of D5 from personal care products are coincident in time and place with emissions of benzene from motor vehicles. During peak commuter times, the D5/benzene ratio (w/w) is in excess of 0.3, suggesting that the mass emission rate of D5 from personal care product usage is comparable to that of benzene due to traffic. The diurnal emission pattern of D5 is estimated using the measured D5/benzene ratio and inventory estimates of benzene emission rates in Boulder. The hourly D5 emission rate is observed to peak between 6:00 and 7:00 AM and subsequently follow an exponential decay with a time constant of 9.2 h. This profile could be used by models to constrain temporal emission patterns of personal care products.

The changing ambient mixing ratios of long-lived halocarbons under Montreal Protocol in China

Abstract The varying trend of long-lived halocarbons demands close attention of their atmospheric climate impact. Chlorofluorocarbons (CFCs) were phased out in 2008 under the Montreal Protocol in China, and nowadays, hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are the main substitutes. Since 2000, studies on CFCs, HCFCs, and HFCs, with respect to their ambient mixing ratios and emissions, were intensively performed over China. CFCs declined evidently, while HCFCs and HFCs greatly increased in China due to the successful phase-out of CFCs under the Montreal Protocol. In the Pearl River Delta (PRD) region, the most developed region in China, the increasing and decreasing rates of CFC-11, CFC-12, HCFC-22, and HCFC-141b since 2000 were −3.6 ± 0.5 pptv/yr, −11.7 ± 3.3 pptv/yr, 17.9 ± 4.9 pptv/yr and 7.2 ± 2.0 pptv/yr, respectively. The increase of HCFC-141b in northern China was 1.1 ± 0.6 pptv/yr, much lower than the PRD region. The overall increase of HFC-134a in China was 5.6 ± 0.2 pptv/yr. These rates were significantly higher than those for their corresponding background averages in the northern hemisphere. Other HFCs excluding HFC-134a were of great global warming potentials, but their ambient mixing ratios were reportedly limited in China. The emission ratios between HCFC-22 and CFC-12, and HFC-134a and HCFC-22 were used as the measurements, showing virtual replacement occurring in China. The rapidly increasing contribution of HFCs to climate risk in China requires further observation.

Methanol exchange dynamics between a temperate cropland soil and the atmosphere

Soil methanol (CH3OH) exchange is often considered as several orders of magnitude smaller than plant methanol exchange. However, for some ecosystems, it is significant in regard with plant exchange and worth thus better consideration. Our study sought to gain a better understanding of soil exchange. Methanol flux was measured at the ecosystem scale on a bare agricultural soil over two contrasted periods using the disjunct eddy covariance by mass scanning technique. A proton-transfer-reaction mass spectrometer was used for the methanol ambient mixing ratio measurements. Bi-directional exchange dynamics were observed. Methanol emission occurred under dry and warm conditions and correlated best with soil surface temperature, whereas methanol uptake occurred under wet and mild conditions and correlated well with the methanol ambient concentration. After having tested a physical adsorption-desorption model and by confronting our data with the literature, we propose that the exchange was ruled by both a physical adsorption/desorption mechanism and by a methanol source, which still needs to be identified. The soil emission decreased when the vegetation developed. The reasons for the decrease still need to be determined. Overall, the dynamics observed at our site were similar to those reported by other studies for both cropland and forest ecosystems. The mechanism proposed in our work can thus be possibly applied to other sites or ecosystems. In addition, the methanol exchange rate was in the upper range of the exchange rates reported by other soil studies, suggesting that cropland soils are more important methanol exchangers than those in other ecosystems and should therefore be further investigated.

Seasonal and diurnal variations in methane and carbon dioxide in the Kathmandu Valley in the foothills of the central Himalayas

Abstract. The SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley–Atmospheric Brown Clouds) international air pollution measurement campaign was carried out from December 2012 to June 2013 in the Kathmandu Valley and surrounding regions in Nepal. The Kathmandu Valley is a bowl-shaped basin with a severe air pollution problem. This paper reports measurements of two major greenhouse gases (GHGs), methane (CH4) and carbon dioxide (CO2), along with the pollutant CO, that began during the campaign and were extended for 1 year at the SusKat-ABC supersite in Bode, a semi-urban location in the Kathmandu Valley. Simultaneous measurements were also made during 2015 in Bode and a nearby rural site (Chanban) ∼ 25 km (aerial distance) to the southwest of Bode on the other side of a tall ridge. The ambient mixing ratios of methane (CH4), carbon dioxide (CO2), water vapor, and carbon monoxide (CO) were measured with a cavity ring-down spectrometer (G2401; Picarro, USA) along with meteorological parameters for 1 year (March 2013–March 2014). These measurements are the first of their kind in the central Himalayan foothills. At Bode, the annual average mixing ratios of CO2 and CH4 were 419.3 (±6.0) ppm and 2.192 (±0.066) ppm, respectively. These values are higher than the levels observed at background sites such as Mauna Loa, USA (CO2: 396.8 ± 2.0 ppm, CH4: 1.831 ± 0.110 ppm) and Waliguan, China (CO2: 397.7 ± 3.6 ppm, CH4: 1.879 ± 0.009 ppm) during the same period and at other urban and semi-urban sites in the region, such as Ahmedabad and Shadnagar (India). They varied slightly across the seasons at Bode, with seasonal average CH4 mixing ratios of 2.157 (±0.230) ppm in the pre-monsoon season, 2.199 (±0.241) ppm in the monsoon, 2.210 (±0.200) ppm in the post-monsoon, and 2.214 (±0.209) ppm in the winter season. The average CO2 mixing ratios were 426.2 (±25.5) ppm in the pre-monsoon, 413.5 (±24.2) ppm in the monsoon, 417.3 (±23.1) ppm in the post-monsoon, and 421.9 (±20.3) ppm in the winter season. The maximum seasonal mean mixing ratio of CH4 in winter was only 0.057 ppm or 2.6 % higher than the seasonal minimum during the pre-monsoon period, while CO2 was 12.8 ppm or 3.1 % higher during the pre-monsoon period (seasonal maximum) than during the monsoon (seasonal minimum). On the other hand, the CO mixing ratio at Bode was 191 % higher during the winter than during the monsoon season. The enhancement in CO2 mixing ratios during the pre-monsoon season is associated with additional CO2 emissions from forest fires and agro-residue burning in northern South Asia in addition to local emissions in the Kathmandu Valley. Published CO∕CO2 ratios of different emission sources in Nepal and India were compared with the observed CO∕CO2 ratios in this study. This comparison suggested that the major sources in the Kathmandu Valley were residential cooking and vehicle exhaust in all seasons except winter. In winter, brick kiln emissions were a major source. Simultaneous measurements in Bode and Chanban (15 July–3 October 2015) revealed that the mixing ratios of CO2, CH4, and CO were 3.8, 12, and 64 % higher in Bode than Chanban. The Kathmandu Valley thus has significant emissions from local sources, which can also be attributed to its bowl-shaped geography that is conducive to pollution build-up. At Bode, all three gas species (CO2, CH4, and CO) showed strong diurnal patterns in their mixing ratios with a pronounced morning peak (ca. 08:00), a dip in the afternoon, and a gradual increase again through the night until the next morning. CH4 and CO at Chanban, however, did not show any noticeable diurnal variations. These measurements provide the first insights into the diurnal and seasonal variation in key greenhouse gases and air pollutants and their local and regional sources, which is important information for atmospheric research in the region.

Nitrogen oxides and ozone fluxes from an oilseed-rape management cycle: the influence of cattle slurry application

Abstract. This study reports NO, NO2 and O3 mixing ratios and flux measurements using the eddy covariance method during a 7-month period over an oilseed-rape field, spanning an organic and a mineral fertilisation event. Cumulated NO emissions during the whole period were in agreement with previous studies and showed quite low emissions of 0.26 kg N ha−1 with an emission factor of 0.27 %, estimated as the ratio between total N emitted in the form of NO and total N input. The NO emissions were higher following organic fertilisation in August due to conditions favouring nitrification (soil water content around 20 % and high temperatures), while mineral fertilisation in February did not result in high emissions. The ozone deposition velocity increased significantly after organic fertilisation. The analysis of the chemical and turbulent transport times showed that reactions between NO, NO2 and O3 below the measurement height occurred constantly throughout the 7-month period. Following organic fertilisation, the NO ground fluxes were 30 % larger than the NO fluxes at the measurement height (3.2 m), while the NO2 fluxes switched from deposition to emission during certain periods, being negative at the surface and positive at the measurement height. This phenomenon of apparent NO2 emissions appears to be significant during strong NO emissions and high O3 ambient mixing ratios, even on a bare soil during August.

Ambient mixing ratios of atmospheric halogenated compounds at five background stations in China

High precision measurements of three chlorofluorocarbons (CFCs), three hydrochlorofluorocarbons (HCFCs), six hydrofluorocarbons (HFCs), three perfluorocarbons (PFCs), and sulfur hexafluoride (SF6) were made at five Chinese background stations from January 2011 to December 2012. Their station means in the background air were 239.5 ± 0.69 parts-per-trillion dry-air mole fraction mixing ratios (ppt) for CFC-11, 536.5 ± 1.49 ppt for CFC-12, 74.66 ± 0.09 ppt for CFC-113, 232.1 ± 4.77 ppt for HCFC-22, 23.78 ± 0.29 ppt for HCFC-141b, 22.92 ± 0.42 ppt for HCFC-142b, 11.75 ± 0.43 ppt for HFC-125, 71.32 ± 1.35 ppt for HFC-134a, 13.62 ± 0.43 ppt for HFC-143a, 9.10 ± 1.26 ppt for HFC-152a, 25.45 ± 0.1 ppt for HFC-23, 7.28 ± 0.48 ppt for HFC-32, 4.32 ± 0.03 ppt for PFC-116, 0.63 ± 0.04 ppt for PFC-218, 1.36 ± 0.01 ppt for PFC-318, and 7.67 ± 0.03 ppt for SF6, respectively, which were comparable with those measured at the two Northern Hemisphere (NH) AGAGE stations: Mace Head, Ireland (MHD) and Trinidad Head, California, USA (THD). Compared with our results for earlier years from in-situ measurement at SDZ, background-air mixing ratios of CFCs are now declining, while those for HCFCs, HFCs, PFCs, and SF6 are still increasing. The ratios of the number of sampling events in which measured mixing ratios were elevated above background (pollution events) relative to the total sample frequency (POL/SUM) for CFCs, HCFCs, and HFCs were found to be station dependent, generally LAN > SDZ > LFS > XGL > WLG. The enhancement (△, polluted mixing ratios minus background mixing ratios) generally show distinct patterns, with HCFCs (40.7–175.4 ppt) > HFCs (15.8–66.3 ppt)> CFCs (15.8–33.8 ppt)> PFCs (0.1–0.9 ppt) at five stations, especially for HCFC-22 ranging from 36.9 ppt to 138.2 ppt. Combining with the molecular weights, our findings imply biggest emissions of HCFCs in the regions around these Chinese sites compared to HFCs and CFCs, while the smallest of PFCs, consistent with CFCs being phased out and replaced with HCFCs in China. In addition, relative emission strengths (emission was expressed by mole fractions) of these halocarbons in China were inferred as HCFC-22 > HCFC-141b > HFC-134a > HCFC-142b for the Yangtze River Delta (YRD) and as HCFC-22 > HCFC-142b > HCFC-141b ≈ HFC-134a in the North China Plain (NCP).

Continuous measurement of atmospheric reduced sulphur compounds as key tracers between odour complaints and source apportionment.

Odour complaints are frequent nowadays, particularly nearby industrial facilities emitting odorous compounds. Among all compounds susceptible of causing odour annoyance, reduced sulphur compounds (RSC) were studied, due to their unpleasant odour and low odour threshold. RSC ambient air mixing ratios, meteorological conditions and population complaints were analysed in an area of complex topography in order to identify their potential sources. Mixing ratios of three compounds, dimethyl sulphide (DMS), carbon disulphide (CDS) and dimethyl disulphide (DMDS), were continuously monitored using an online gas chromatograph coupled with a mass spectrometer detector (GC-MSD), which was placed in a mobile air quality monitoring unit. Measurement campaigns were performed during 2012 and 2013 for periods of 7-25days in an urban area (four campaigns, N=1368) and an urban area surrounded by industrial activities (three campaigns, N=564). During such campaigns, RSC mixing ratios were frequently above their odour thresholds, which did not always involve citizen complaints. Average RSC ambient air mixing ratios tended to be lower in the urban area (DMS 0.06-0.33, CDS 0.05-0.10, DMDS 0.07-0.30μgm-3) than in the industry surrounded one (DMS 0.30-2.39, 0.05-0.18, DMDS 0.09-0.62μgm-3). The DMS/DMDS mixing ratio was frequently above 1, being a paper mill one of the main sources of RSC in the area. DMS/DMDS ratios below 1 were also recorded, suggesting a waste treatment plant as the RSC source or older air masses coming from the paper mill.

Using in situ GC-MS for analysis of C&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;–C&amp;lt;sub&amp;gt;7&amp;lt;/sub&amp;gt; volatile organic acids in ambient air of a boreal forest site

Abstract. An in situ method for studying gas-phase C2–C7 monocarboxylic volatile organic acids (VOAs) in ambient air was developed and evaluated. Samples were collected directly into the cold trap of the thermal desorption unit (TD) and analysed in situ using a gas chromatograph (GC) coupled to a mass spectrometer (MS). A polyethylene glycol column was used for separating the acids. The method was validated in the laboratory and tested on the ambient air of a boreal forest in June 2015. Recoveries of VOAs from fluorinated ethylene propylene (FEP) and heated stainless steel inlets ranged from 83 to 123 %. Different VOAs were fully desorbed from the cold trap and well separated in the chromatograms. Detection limits varied between 1 and 130 pptv and total uncertainty of the method at mean ambient mixing ratios was between 16 and 76 %. All straight chain VOAs except heptanoic acid in the ambient air measurements were found with mixing ratios above the detection limits. The highest mixing ratios were found for acetic acid and the highest relative variations for hexanoic acid. In addition, mixing ratios of acetic and propanoic acids measured by the novel GC-MS method were compared with proton-mass-transfer time-of-flight mass spectrometer (PTR-TOFMS) data. Both instruments showed similar variations, but differences in the mixing ratio levels were significant.

Twin-cuvette measurement technique for investigation of dry deposition of O&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; and PAN to plant leaves under controlled humidity conditions

Abstract. We present a dynamic twin-cuvette system for quantifying the trace-gas exchange fluxes between plants and the atmosphere under controlled temperature, light, and humidity conditions. Compared with a single-cuvette system, the twin-cuvette system is insensitive to disturbing background effects such as wall deposition. In combination with a climate chamber, we can perform flux measurements under constant and controllable environmental conditions. With an Automatic Temperature Regulated Air Humidification System (ATRAHS), we are able to regulate the relative humidity inside both cuvettes between 40 and 90 % with a high precision of 0.3 %. Thus, we could demonstrate that for a cuvette system operated with a high flow rate (&gt; 20 L min−1), a temperature-regulated humidification system such as ATRAHS is an accurate method for air humidification of the flushing air. Furthermore, the fully automatic progressive fill-up of ATRAHS based on a floating valve improved the performance of the entire measurement system and prevented data gaps. Two reactive gas species, ozone (O3) and peroxyacetyl nitrate (PAN), were used to demonstrate the quality and performance of the twin-cuvette system. O3 and PAN exchange with Quercus ilex was investigated over a 14 day measurement period under controlled climate chamber conditions. By using O3 mixing ratios between 32 and 105 ppb and PAN mixing ratios between 100 and 350 ppt, a linear dependency of the O3 flux as well as the PAN flux in relation to its ambient mixing ratio could be observed. At relative humidity (RH) of 40 %, the deposition velocity ratio of O3 and PAN was determined to be 0.45. At that humidity, the deposition of O3 to the plant leaves was found to be only controlled by the leaf stomata. For PAN, an additional resistance inhibited the uptake of PAN by the leaves. Furthermore, the formation of water films on the leaf surface of plants inside the chamber could be continuously tracked with our custom built leaf wetness sensors. Using this modified leaf wetness sensor measuring the electrical surface conductance on the leaves, an exponential relationship between the ambient humidity and the electrical surface conductance could be determined.