ALBERT

Description: Perfluorocarbons (PFCs) are potent greenhouse gases with global warming potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes of the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been analytically separated according to their isomers: c-octafluorobutane (c-C4F8), n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14), and n-hexadecafluoroheptane (n-C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro-2-methylpentane (i-C6F14). The existence and significance of PFC isomers have not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several data sets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote “background” Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6 % and 27 % higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23 % of which has been emitted since 2010. Almost two-thirds of the CO2 equivalent emissions within the last decade are attributable to c-C4F8, which currently also has the highest emission rates that continue to grow. Sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere.

Description: This study quantifies the present-day global and regional distributions (2010–2014) and trends (2000–2014) for five ozone metrics relevant for short-term and long-term human exposure. These metrics, calculated by the Tropospheric Ozone Assessment Report, are: 4thhighest daily maximum 8-hour ozone (4MDA8); number of days with MDA8 〉 70 ppb (NDGT70), SOMO35 (annual Sum of Ozone Means Over 35 ppb) and two seasonally averaged metrics (3MMDA1; AVGMDA8). These metrics were explored at ozone monitoring sites worldwide, which were classified as urban or non-urban based on population and nighttime lights data. Present-day distributions of 4MDA8 and NDGT70, determined predominantly by peak values, are similar with highest levels in western North America, southern Europe and East Asia. For the other three metrics, distributions are similar with North–South gradients more prominent across Europe and Japan. Between 2000 and 2014, significant negative trends in 4MDA8 and NDGT70 occur at most US and some European sites. In contrast, significant positive trends are found at many sites in South Korea and Hong Kong, with mixed trends across Japan. The other three metrics have similar, negative trends for many non-urban North American and some European and Japanese sites, and positive trends across much of East Asia. Globally, metrics at many sites exhibit non-significant trends. At 59% of all sites there is a common direction and significance in the trend across all five metrics, whilst 4MDA8 and NDGT70 have a common trend at ~80% of all sites. Sensitivity analysis shows AVGMDA8 trends differ with averaging period (warm season or annual). Trends are unchanged at many sites when a 1995–2014 period is used; although fewer sites exhibit non-significant trends. Over the longer period 1970–2014, most Japanese sites exhibit positive 4MDA8/SOMO35 trends. Insufficient data exist to characterize ozone trends for the rest of Asia and other world regions.

Description: The atmosphere contains a rich variety of reactive organic compounds, including gaseous volatile organic carbon (VOCs), carbonaceous aerosols, and other organic compounds at varying volatility. Here we present a novel and simple approach to measure atmospheric non-methane total organic carbon (TOC) based on catalytic oxidation of organics in bulk air to carbon dioxide. This method shows little sensitivity towards humidity and near 100 % oxidation efficiencies for all VOCs tested. We estimate a best-case hourly precision of 8 ppb C during times of low ambient variability in carbon dioxide, methane, and carbon monoxide (CO). As proof of concept of this approach, we show measurements of TOC+CO during August–September 2016 from a coastal city in the southwest United Kingdom. TOC+CO was substantially elevated during the day on weekdays (occasionally over 2 ppm C) as a result of local anthropogenic activity. On weekends and holidays, with a mean (standard error) of 102 (8) ppb C, TOC+CO was lower and showed much less diurnal variability. TOC+CO was significantly lower when winds were coming off the Atlantic Ocean than when winds were coming off land if we exclude the weekday daytime. By subtracting the estimated CO from TOC+CO, we constrain the mean (uncertainty) TOC in Atlantic-dominated air masses to be around 23 (±≥8) ppb C during this period. A proton-transfer-reaction mass spectrometer (PTR-MS) was deployed at the same time, detecting a large range of organic compounds (oxygenated VOCs, biogenic VOCs, aromatics, dimethyl sulfide). The total speciated VOCs from the PTR-MS, denoted here as Sum(VOC), amounted to a mean (uncertainty) of 12 (±≤3) ppb C in marine air. Possible contributions from a number of known organic compounds present in marine air that were not detected by the PTR-MS are assessed within the context of the TOC budget. Finally, we note that the use of a short, heated sample tube can improve the transmission of organics to the analyzer, while operating our system alternately with and without a particle filter should enable a better separation of semi-volatile and particulate organics from the VOCs within the TOC budget. Future concurrent measurements of TOC, CO, and a more comprehensive range of speciated VOCs would enable a better characterization and understanding of the atmospheric organic carbon budget.

Description: Measurements of the concentration and variability of ice nucleating particles in the subtropical maritime boundary layer are reported. Filter samples collected in Cabo Verde over the period 2009–2013 are analyzed with a drop freezing experiment with sensitivity to detect the few rare ice nuclei active at low supercooling. The data set is augmented with continuous flow diffusion chamber measurements at temperatures below −24 ∘C from a 2-month field campaign in Cabo Verde in 2016. The data set is used to address the following questions: what are typical concentrations of ice nucleating particles active at a certain temperature? What affects their concentration and where are their sources? Concentration of ice nucleating particles is found to increase exponentially by 7 orders of magnitude from −5 to −38 ∘C. Sample-to-sample variation in the steepness of the increase indicates that particles of different origin, with different ice nucleation properties (size, composition), contribute to the ice nuclei concentration at different temperatures. The concentration of ice nuclei active at a specific temperature varies over a range of up to 4 orders of magnitude. The frequency with which a certain ice nuclei concentration is measured within this range is found to follow a lognormal distribution, which can be explained by random dilution during transport. To investigate the geographic origin of ice nuclei, source attribution of air masses from dispersion modeling is used to classify the data into seven typical conditions. While no source could be attributed to the ice nuclei active at temperatures higher than −12 ∘C, concentrations at lower temperatures tend to be elevated in air masses originating from the Sahara.

Description: We demonstrate, for the first time, continuous real-time observations of airborne bio-fluorescent aerosols recorded at the British Antarctic Survey's Halley VI Research Station, located on the Brunt Ice Shelf close to the Weddell Sea coast (lat 75°34′59′′ S, long 26°10′0′′ W) during Antarctic summer, 2015. As part of the NERC MAC (Microphysics of Antarctic Clouds) aircraft aerosol cloud interaction project, observations with a real-time ultraviolet-light-induced fluorescence (UV-LIF) spectrometer were conducted to quantify airborne biological containing particle concentrations along with dust particles as a function of wind speed and direction over a 3-week period. Significant, intermittent enhancements of both non- and bio-fluorescent particles were observed to varying degrees in very specific wind directions and during strong wind events. Analysis of the particle UV-induced emission spectra, particle sizes and shapes recorded during these events suggest the majority of particles were likely a subset of dust with weak fluorescence emission responses. A minor fraction, however, were likely primary biological particles that were very strongly fluorescent, with a subset identified as likely being pollen based on comparison with laboratory data obtained using the same instrument. A strong correlation of bio-fluorescent particles with wind speed was observed in some, but not all, periods. Interestingly, the fraction of fluorescent particles to total particle concentration also increased significantly with wind speed during these events. The enhancement in concentrations of these particles could be interpreted as due to resuspension from the local ice surface but more likely due to emissions from distal sources within Antarctica as well as intercontinental transport. Likely distal sources identified by back trajectory analyses and dispersion modelling were the coastal ice margin zones in Halley Bay consisting of bird colonies with likely associated high bacterial activity together with contributions from exposed ice margin bacterial colonies but also long-range transport from the southern coasts of Argentina and Chile. Dispersion modelling also demonstrated emissions from shipping lanes, and therefore marine anthropogenic sources cannot be ruled out. Average total concentrations of total fluorescent aerosols were found to be 1.9 ± 2.6 L−1 over a 3-week period crossing over from November into December, but peak concentrations during intermittent enhancement events could be up to several tens per litre. While this short pilot study is not intended to be generally representative of Antarctic aerosol, it demonstrates the usefulness of the UV-LIF measurement technique for quantification of airborne bioaerosol concentrations and to understand their dispersion. The potential importance for microbial colonisation of Antarctica is highlighted.

Description: Mercury is a chemical with widespread anthropogenic emissions that is known to be highly toxic to humans, ecosystems and wildlife. Global anthropogenic emissions are around 20 % higher than natural emissions and the amount of mercury released into the atmosphere has increased since the industrial revolution. In 2005 the European Union and the United States adopted measures to reduce mercury use, in part to offset the impacts of increasing emissions in industrialising countries. The changing regional emissions of mercury have impacts on a range of spatial scales. Here we report 4 years (December 2011–December 2015) of total gaseous mercury (TGM) measurements at the Cape Verde Observatory (CVO), a global WMO-GAW station located in the subtropical remote marine boundary layer. Observed total gaseous mercury concentrations were between 1.03 and 1.33 ng m−3 (10th, 90th percentiles), close to expectations based on previous interhemispheric gradient measurements. We observe a decreasing trend in TGM (−0.05 ± 0.04 ng m−3 yr−1, −4.2 % ± 3.3 % yr−1) over the 4 years consistent with the reported decrease of mercury concentrations in North Atlantic surface waters and reductions in anthropogenic emissions. The decrease was more visible in the summer (July–September) than in the winter (December–February), when measurements were impacted by air from the African continent and Sahara/Sahel regions. African air masses were also associated with the highest and most variable TGM concentrations. We suggest that the less pronounced downward trend inclination in African air may be attributed to poorly controlled anthropogenic sources such as artisanal and small-scale gold mining (ASGM) in West Africa.

Description: For three austral summer seasons (2013–2016, each from December to February) aerosol particles arriving at the Belgian Antarctic research station Princess Elisabeth (PE) in Dronning Maud Land in East Antarctica were characterized. This included number concentrations of total aerosol particles (NCN) and cloud condensation nuclei (NCCN), the particle number size distribution (PNSD), the aerosol particle hygroscopicity, and the influence of the air mass origin on NCN and NCCN. In general NCN was found to range from 40 to 6700 cm−3, with a median of 333 cm−3, while NCCN was found to cover a range between less than 10 and 1300 cm−3 for supersaturations (SSs) between 0.1 % and 0.7 %. It is shown that the aerosol is dominated by the Aitken mode, being characterized by a significant amount of small, and therefore likely secondarily formed, aerosol particles, with 94 % and 36 % of the aerosol particles smaller than 90 and ≈35 nm, respectively. Measurements of the basic meteorological parameters as well as the history of the air masses arriving at the measurement station indicate that the station is influenced by both marine air masses originating from the Southern Ocean and coastal areas around Antarctica (marine events – MEs) and continental air masses (continental events – CEs). CEs, which were defined as instances when the air masses spent at least 90 % of the time over the Antarctic continent during the last 10 days prior to arrival at the measurements station, occurred during 61 % of the time during which measurements were done. CEs came along with rather constant NCN and NCCN values, which we denote as Antarctic continental background concentrations. MEs, however, cause large fluctuations in NCN and NCCN, with low concentrations likely caused by scavenging due to precipitation and high concentrations likely originating from new particle formation (NPF) based on marine precursors. The application of HYSPLIT back trajectories in form of the potential source contribution function (PSCF) analysis indicate that the region of the Southern Ocean is a potential source of Aitken mode particles. On the basis of PNSDs, together with NCCN measured at an SS of 0.1 %, median values for the critical diameter for cloud droplet activation and the aerosol particle hygroscopicity parameter κ were determined to be 110 nm and 1, respectively. For particles larger than ≈110 nm the Southern Ocean together with parts of the Antarctic ice shelf regions were found to be potential source regions. While the former may contribute sea spray particles directly, the contribution of the latter may be due to the emission of sea salt aerosol particles, released from snow particles from surface snow layers, e.g., during periods of high wind speed, leading to drifting or blowing snow. The region of the Antarctic inland plateau, however, was not found to feature a significant source region for aerosol particles in general or for cloud condensation nuclei measured at the PE station in the austral summer.

Description: During austral summer 2015, the Microphysics of Antarctic Clouds (MAC) field campaign collected unique and detailed airborne and ground-based in situ measurements of cloud and aerosol properties over coastal Antarctica and the Weddell Sea. This paper presents the first results from the experiment and discusses the key processes important in this region, which is critical to predicting future climate change. The sampling was predominantly of stratus clouds, at temperatures between −20 and 0 °C. These clouds were dominated by supercooled liquid water droplets, which had a median concentration of 113 cm−3 and an interquartile range of 86 cm−3. Both cloud liquid water content and effective radius increased closer to cloud top. The cloud droplet effective radius increased from 4 ± 2 µm near cloud base to 8 ± 3 µm near cloud top. Cloud ice particle concentrations were highly variable with the ice tending to occur in small, isolated patches. Below approximately 1000 m, glaciated cloud regions were more common at higher temperatures; however, the clouds were still predominantly liquid throughout. When ice was present at temperatures higher than −10 °C, secondary ice production most likely through the Hallett–Mossop mechanism led to ice concentrations 1 to 3 orders of magnitude higher than the number predicted by commonly used primary ice nucleation parameterisations. The drivers of the ice crystal variability are investigated. No clear dependence on the droplet size distribution was found. The source of first ice in the clouds remains uncertain but may include contributions from biogenic particles, blowing snow or other surface ice production mechanisms. The concentration of large aerosols (diameters 0.5 to 1.6 µm) decreased with altitude and were depleted in air masses that originated over the Antarctic continent compared to those more heavily influenced by the Southern Ocean and sea ice regions. The dominant aerosol in the region was hygroscopic in nature, with the hygroscopicity parameter κ having a median value for the campaign of 0.66 (interquartile range of 0.38). This is consistent with other remote marine locations that are dominated by sea salt/sulfate.