ALBERT

Description: Ice formation in the atmosphere is important for regulating cloud lifetime, Earth's radiative balance and initiating precipitation. Due to the difference in the saturation vapor pressure over ice and water, in mixed-phase clouds (MPCs), ice will grow at the expense of supercooled cloud droplets. As such, MPCs, which contain both supercooled liquid and ice, are particularly susceptible to ice formation. However, measuring and quantifying the concentration of ice-nucleating particles (INPs) responsible for ice formation at temperatures associated with MPCs is challenging due to their very low concentrations in the atmosphere (∼1 in 105 at −30 ∘C). Atmospheric INP concentrations vary over several orders of magnitude at a single temperature and strongly increase as temperature approaches the homogeneous freezing threshold of water. To further quantify the INP concentration in nature and perform systematic laboratory studies to increase the understanding of the properties responsible for ice nucleation, a new drop-freezing instrument, the DRoplet Ice Nuclei Counter Zurich), is developed. The instrument is based on the design of previous drop-freezing assays and uses a USB camera to automatically detect freezing in a 96-well tray cooled in an ethanol chilled bath with a user-friendly and fully automated analysis procedure. Based on an in-depth characterization of DRINCZ, we develop a new method for quantifying and correcting temperature biases across drop-freezing assays. DRINCZ is further validated performing NX-illite experiments, which compare well with the literature. The temperature uncertainty in DRINCZ was determined to be ±0.9 ∘C. Furthermore, we demonstrate the applicability of DRINCZ by measuring and analyzing field-collected snow samples during an evolving synoptic situation in the Austrian Alps. The field samples fall within previously observed ranges for cumulative INP concentrations and show a dependence on air mass origin and upstream precipitation amount.

Description: Although elevated surface ozone (O3) concentrations are observed in many areas within southern Africa, few studies have investigated the regional atmospheric chemistry and dominant atmospheric processes driving surface O3 formation in this region. Therefore, an assessment of comprehensive continuous surface O3 measurements performed at four sites in continental South Africa was conducted. The regional O3 problem was evident, with O3 concentrations regularly exceeding the South African air quality standard limit, while O3 levels were higher compared to other background sites in the Southern Hemisphere. The temporal O3 patterns observed at the four sites resembled typical trends for O3 in continental South Africa, with O3 concentrations peaking in late winter and early spring. Increased O3 concentrations in winter were indicative of increased emissions of O3 precursors from household combustion and other low-level sources, while a spring maximum observed at all the sites was attributed to increased regional biomass burning. Source area maps of O3 and CO indicated significantly higher O3 and CO concentrations associated with air masses passing over a region with increased seasonal open biomass burning, which indicated CO associated with open biomass burning as a major source of O3 in continental South Africa. A strong correlation between O3 on CO was observed, while O3 levels remained relatively constant or decreased with increasing NOx, which supports a VOC-limited regime. The instantaneous production rate of O3 calculated at Welgegund indicated that ∼40 % of O3 production occurred in the VOC-limited regime. The relationship between O3 and precursor species suggests that continental South Africa can be considered VOC limited, which can be attributed to high anthropogenic emissions of NOx in the interior of South Africa. The study indicated that the most effective emission control strategy to reduce O3 levels in continental South Africa should be CO and VOC reduction, mainly associated with household combustion and regional open biomass burning.

Description: An organic aerosol particle has a lifetime of approximately 1 week in the atmosphere during which it will be exposed to sunlight. However, the effect of photochemistry on the propensity of organic matter to participate in the initial cloud-forming steps is difficult to predict. In this study, we quantify on a molecular scale the effect of photochemical exposure of naturally occurring dissolved organic matter (DOM) and of a fulvic acid standard on its cloud condensation nuclei (CCN) and ice nucleation (IN) activity. We find that photochemical processing, equivalent to 4.6 d in the atmosphere, of DOM increases its ability to form cloud droplets by up to a factor of 2.5 but decreases its ability to form ice crystals at a loss rate of −0.04 ∘CT50 h−1 of sunlight at ground level. In other words, the ice nucleation activity of photooxidized DOM can require up to 4 ∘C colder temperatures for 50 % of the droplets to activate as ice crystals under immersion freezing conditions. This temperature change could impact the ratio of ice to water droplets within a mixed-phase cloud by delaying the onset of glaciation and by increasing the supercooled liquid fraction of the cloud, thereby modifying the radiative properties and the lifetime of the cloud. Concurrently, a photomineralization mechanism was quantified by monitoring the loss of organic carbon and the simultaneous production of organic acids, such as formic, acetic, oxalic and pyruvic acids, CO and CO2. This mechanism explains and predicts the observed increase in CCN and decrease in IN efficiencies. Indeed, we show that photochemical processing can be a dominant atmospheric ageing process, impacting CCN and IN efficiencies and concentrations. Photomineralization can thus alter the aerosol–cloud radiative effects of organic matter by modifying the supercooled-liquid-water-to-ice-crystal ratio in mixed-phase clouds with implications for cloud lifetime, precipitation patterns and the hydrological cycle.Highlights. During atmospheric transport, dissolved organic matter (DOM) within aqueous aerosols undergoes photochemistry. We find that photochemical processing of DOM increases its ability to form cloud droplets but decreases its ability to form ice crystals over a simulated 4.6 d in the atmosphere. A photomineralization mechanism involving the loss of organic carbon and the production of organic acids, CO and CO2 explains the observed changes and affects the liquid-water-to-ice ratio in clouds.

Description: Ice-nucleating particles (INPs) produce ice from supercooled water droplets through heterogeneous freezing in the atmosphere. INPs have often been collected at the Jungfraujoch research station (at 3500 m a.s.l.) in central Switzerland; yet spatially diverse data on INP occurrence in the Swiss Alps are scarce and remain uncharacterized. We address this scarcity through our Swiss alpine snow sample study which took place during the winter of 2018. We collected a total of 88 fallen snow samples across the Alps at 17 different locations and investigated the impact of altitude, terrain, time since last snowfall and depth upon freezing temperatures. The INP concentrations were measured using the home-built DRoplet Ice Nuclei Counter Zurich (DRINCZ) and were then compared to spatial, temporal and physicochemical parameters. Boxplots of the freezing temperatures showed large variability in INP occurrence, even for samples collected 10 m apart on a plain and 1 m apart in depth. Furthermore, undiluted samples had cumulative INP concentrations ranging between 1 and 200 INP mL−1 of snowmelt over a temperature range of −5 to −19 ∘C. From this field-collected dataset, we parameterized the cumulative INP concentrations per cubic meter of air as a function of temperature with the following equation cair*(T)=e-0.7T-7.05, comparing well with previously reported precipitation data presented in Petters and Wright (2015). When assuming (1) a snow precipitation origin of the INPs, (2) a cloud water content of 0.4 g m−3 and (3) a critical INP concentration for glaciation of 10 m−3, the majority of the snow precipitated from clouds with glaciation temperatures between −5 and −20 ∘C. Based on the observed variability in INP concentrations, we conclude that studies conducted at the high-altitude research station Jungfraujoch are representative for INP measurements in the Swiss Alps. Furthermore, the INP concentration estimates in precipitation allow us to extrapolate the concentrations to a frozen cloud fraction. Indeed, this approach for estimating the liquid water-to-ice ratio in mixed-phase clouds compares well with aircraft measurements, ground-based lidar and satellite retrievals of frozen cloud fractions. In all, the generated parameterization for INP concentrations in snowmelt could help estimate cloud glaciation temperatures.

Description: Ice nucleating particles (INPs) produce ice from supercooled water droplets through heterogeneous freezing in the atmosphere. Since the concentration of ice crystals affects the radiative properties of clouds as well as precipitation, constraining the liquid water to ice ratio could help reduce aerosol-cloud interaction uncertainties. INPs have been collected at the Jungfraujoch research station (at 3500 m a.s.l.) in central Switzerland; yet spatially diverse data on INP occurrence in the Swiss Alps are scarce and remain uncharacterized. We address this scarcity through our Swiss Alpine snow sample study which took place during the winter of 2018. We collected a total of 88 fallen snow samples across the Alps at different locations, altitudes, terrains, times since last snowfall and depths. The INP concentrations were measured using the homebuilt DRoplet Ice Nuclei Counter Zurich (DRINCZ) and were then compared to spatial, meteorological and physiochemical parameters. We also extend an alternative way of displaying frozen fraction (FF) versus temperature data through visualizing freezing temperatures as a boxplot to field collected samples. This plotting method displays the freezing temperature in one dimension, instead of the former two dimensions of FF vs temperature, allowing a condensed display of freezing temperature measurements. In the collected snow samples, large variability in INP occurrence was found, even for samples collected 10 m apart on a plain and 1 m apart in depth. Furthermore, undiluted samples had INP concentrations ranging between 1 and 100 INP ml−1 of snow water over a temperature range of −5 to −19 °C. From this field-collected data set, we parameterize the INP concentrations per milliliter of meltwater as a function of temperature with the following equation c*air (T)=e(−0.7T–7.05), comparing well with previously reported precipitation data presented in Petters and Wright, 2015. When assuming a cloud water content of 0.4 g−3 and a critical INP concentration for glaciation of 10 m−3, the majority of the snow precipitated from clouds with glaciation temperatures between −5 and −20 °C. Based on the observed variability in INP concentrations, we conclude that studies conducted at the high-altitude research station Jungfraujoch are representative for INP measurements in the Swiss Alps. Furthermore, the INP concentration precipitation estimates allow us to extrapolate the concentrations to a cloud frozen fraction. Indeed, this approach for estimating the liquid water to ice ratio in mixed phase clouds compares well with aircraft measurements, ground-based lidar and satellite retrievals of cloud frozen fractions. In all, the generated parameterization for INP concentrations in meltwater could help estimate cloud glaciation temperatures.

Description: Ice formation in the atmosphere is important for regulating cloud lifetime, Earth's radiative balance and initiating precipitation. Due to the difference in the saturation vapor pressure over ice and water, in mixed-phase clouds (MPCs), ice will grow at the expense of supercooled cloud droplets. As such, MPCs, which contain both supercooled liquid and ice, are particularly susceptible to ice formation. However, measuring and quantifying the concentration of ice nucleating particles (INPs) responsible for ice formation at temperatures associated with MPCs is challenging due to their very low concentrations in the atmosphere (~ 1 in 105 at − 30 °C). Atmospheric INP concentrations vary over several orders of magnitude at a single temperature and strongly increase as temperature approaches the homogeneous freezing threshold of water. To further quantify the INP concentration in nature and perform systematic laboratory studies to increase the understanding of the properties responsible for ice nucleation, a new drop freezing instrument, the DRoplet Ice Nuclei Counter Zurich (DRINCZ) is developed. The instrument is based on the design of previous drop freezing assays and uses a USB camera to automatically detect freezing in a 96-well tray cooled in an ethanol chilled bath with an automated analysis procedure. Based on an in-depth characterization of DRINCZ, we develop a new method for quantifying and correcting temperature biases across drop freezing assays. DRINCZ is further validated performing NX illite experiments, which compare well with the literature. The temperature uncertainty in DRINCZ was determined to be ± 0.9 ˚C. Furthermore, we demonstrate the applicability of DRINCZ by measuring and analyzing field collected snow samples during an evolving synoptic situation in the Austrian Alps. The field samples fall within previously observed ranges for cumulative INP concentrations and show a dependence on air mass origin and upstream precipitation amount.

Description: An organic aerosol particle has a lifetime of approximately one week in the atmosphere during which it will be exposed to sunlight. Yet, the effect of photochemistry on the propensity of organic matter to participate in the initial cloud-forming steps is difficult to predict. In this study, we quantify on a molecular scale the effect of photochemical exposure of naturally occurring dissolved organic matter (DOM) and of a fulvic acid standard on its ability to form mixed-phase clouds, by acting as cloud condensation nuclei (CCN) and by acting as ice nucleating particles (INPs). We find that photochemical processing, equivalent to 4.6 days in the atmosphere, of DOM increases its ability to form cloud droplets by up to a factor of 2.5 but decreases its ability to form ice crystals at a loss rate of −0.04°CT50 h−1 of sunlight at ground level. In other words, the ice nucleation activity of photooxidized DOM can require up to 4 degrees colder temperatures for 50 % of the droplets to activate as ice crystals under immersion freezing conditions. This temperature change could impact the ratio of ice to water droplets within a mixed phase cloud by delaying the onset of glaciation and by increasing the supercooled liquid fraction of the cloud, thereby modifying the radiative properties and the lifetime of the cloud. Concurrently, a photomineralization mechanism was quantified by monitoring the loss of organic carbon and the simultaneous production of organic acids, such as formic, acetic, oxalic and pyruvic acids, CO and CO2. This mechanism explains and predicts the observed increase in CCN and decrease in INP efficiencies. Indeed, we show that photochemical processing can be a dominant atmospheric aging process, impacting CCN and INP efficiencies and concentrations. Photomineralization can thus alter the aerosol-cloud radiative effects of organic matter by modifying the supercooled liquid water-to-ice crystal ratio in mixed-phase clouds with implications for cloud lifetime, precipitation patterns and the hydrological cycle.

Description: Although elevated ozone (O3) concentrations are observed in many areas within continental southern Africa, few studies have investigated the regional atmospheric chemistry and dominant atmospheric processes driving surface O3 formation in this region. The aim of this study was to conduct an assessment of comprehensive continuous surface O3 measurements performed at four sites located in continental South Africa. These sites were representative of regional background (Welgegund and Botsalano) and industrial regions (Marikana and Elandsfontein) in the north-eastern interior in South Africa as indicated by comparison with other sites in this region. The regional O3 problem was also shown with O3 concentrations being higher than 40 ppb at many sites in the north-eastern interior, while the South African air quality standard limit for O3 was regularly exceeded at the four sites in this study. O3 levels were generally lower at other background sites in the Southern Hemisphere compared to the South African sites, while similar seasonal patterns were observed. The temporal O3 patterns observed at the four sites resembled typical trends for O3 in continental South Africa, i.e. O3 concentration peaking in late winter and early spring, and daytime O3 peaks associated with increased photochemical production. The seasonal O3 trends observed in continental South Africa were mainly attributed to the seasonal changes in emissions of O3 precursor species and changes in meteorological conditions. Increased O3 concentrations in winter were indicative of increased emissions of O3 precursors from household combustion for space heating and the concentration of low-level pollutants near the surface. A spring maximum was observed at all the sites, which was attributed to increased regional biomass burning during this time. Source area maps of O3 and CO indicated significantly higher O3 and CO concentrations associated with air masses passing over a region where a large number of seasonal open biomass burning occurred in southern Africa, which indicated CO associated with open biomass burning as a major source of O3 in continental South Africa. The relationship between O3, NOx and CO indicated a strong dependence of O3 on CO, while O3 levels remained relatively constant or decreased with increasing NOx. The seasonal changes in the relationship between O3 and precursors species also reflected the seasonal changes in sources of precursors. The instantaneous production rate of O3, P(O3), calculated at Welgegund indicated that at least 40 % of O3 production occurred in the VOC-limited regime. These relationships between O3 concentrations and P(O3) with O3 precursor species revealed that large parts of the regional background in continental South Africa can be considered CO- or VOC-limited, which can be attributed to high anthropogenic emissions of NOx in the interior of South Africa. It was indicated that the appropriate emission control strategy should be CO (and VOC) reduction associated with household combustion and regional open biomass burning to effectively reduce O3 pollution in continental South Africa.