Mace Head Atmospheric Research Station Research Articles

IPB-MSA&SO4: a daily 0.25° resolution dataset of in situ-produced biogenic methanesulfonic acid and sulfate over the North Atlantic during 1998–2022 based on machine learning

Abstract. Accurate long-term marine-derived biogenic sulfur aerosol concentrations at high spatial and temporal resolutions are critical for a wide range of studies, including climatology, trend analysis, and model evaluation; this information is also imperative for the accurate investigation of the contribution of marine-derived biogenic sulfur aerosol concentrations to the aerosol burden, for the elucidation of their radiative impacts, and to provide boundary conditions for regional models. By applying machine learning algorithms, we constructed the first publicly available daily gridded dataset of in situ-produced biogenic methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO4=) concentrations covering the North Atlantic. The dataset is of high spatial resolution (0.25° × 0.25°) and spans 25 years (1998–2022), far exceeding what observations alone could achieve both spatially and temporally. The machine learning models were generated by combining in situ observations of sulfur aerosol data from Mace Head Atmospheric Research Station, located on the west coast of Ireland, and from the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES) cruises in the northwestern Atlantic with the constructed sea-to-air dimethylsulfide flux (FDMS) and ECMWF ERA5 reanalysis datasets. To determine the optimal method for regression, we employed five machine learning model types: support vector machines, decision tree, regression ensemble, Gaussian process regression, and artificial neural networks. A comparison of the mean absolute error (MAE), root-mean-square error (RMSE), and coefficient of determination (R2) revealed that Gaussian process regression (GPR) was the most effective algorithm, outperforming the other models with respect to simulating the biogenic MSA and nss-SO4= concentrations. For predicting daily MSA (nss-SO4=), GPR displayed the highest R2 value of 0.86 (0.72) and the lowest MAE of 0.014 (0.10) µg m−3. GPR partial dependence analysis suggests that the relationships between predictors and MSA and nss-SO4= concentrations are complex rather than linear. Using the GPR algorithm, we produced a high-resolution daily dataset of in situ-produced biogenic MSA and nss-SO4= sea-level concentrations over the North Atlantic, which we named “In-situ Produced Biogenic Methanesulfonic Acid and Sulfate over the North Atlantic” (IPB-MSA&SO4). The obtained IPB-MSA&SO4 data allowed us to analyze the spatiotemporal patterns of MSA and nss-SO4= as well as the ratio between them (MSA:nss-SO4=). A comparison with the existing Copernicus Atmosphere Monitoring Service ECMWF Atmospheric Composition Reanalysis 4 (CAMS-EAC4) reanalysis suggested that our high-resolution dataset reproduces the spatial and temporal patterns of the biogenic sulfur aerosol concentration with high accuracy and has high consistency with independent measurements in the Atlantic Ocean. IPB-MSA&SO4 is publicly available at https://doi.org/10.17632/j8bzd5dvpx.1 (Mansour et al., 2023b).

A 24-year record of high-frequency, in situ, observations of hydrogen at the Atmospheric Research Station at Mace Head, Ireland

Continuous high frequency in situ observations of hydrogen have been made at the Mace Head atmospheric research station on the Atlantic Ocean coastline of Ireland from April 1994 through to December 2017. These 40-minute observations represent one of the most comprehensive records of this trace gas carried out anywhere in the world. Hydrogen mixing ratios in northern hemisphere baseline air masses had a mean value of 508.81 ppb and exhibited a highly statistically significant upwards trend of +0.44 +0.16 -0.28 ppb year-1. Trends were strongest during the months of January, February and November and weakest during the months of May - July, inclusive. Monthly mean baseline mixing ratios exhibited a seasonal cycle with a spring maximum and an autumn minimum, the latter being relatively unusual at this baseline station. The transport of European regionally-polluted air masses to Mace Head historically brought elevated levels of hydrogen above baseline. Over the years of this study, these elevated levels have declined to the extent that the hydrogen levels in European regional pollution events are now almost indistinguishable from baseline levels. Photochemical Trajectory Model studies have confirmed that the decline in European excess hydrogen levels accurately reflects the widespread fitting of three-way catalysts and evaporative cannisters to petrol-engined motor vehicles across Europe and the reductions in emissions of carbon monoxide, oxides of nitrogen and volatile organic compounds that they have brought about.

Establishing long-term measurements of halocarbons at Taunus Observatory

Abstract. In late 2013, a whole air flask collection programme was started at Taunus Observatory (TO) in central Germany. Being a rural site in close proximity to the Rhine–Main area, Taunus Observatory allows assessment of emissions from a densely populated region. Owing to its altitude of 825 m, the site also regularly experiences background conditions, especially when air masses approach from north-westerly directions. With a large footprint area mainly covering central Europe north of the Alps, halocarbon measurements at the site have the potential to improve the database for estimation of regional and total European halogenated greenhouse gas emissions. Flask samples are collected weekly for offline analysis using a GC/MS system simultaneously employing a quadrupole as well as a time-of-flight mass spectrometer. As background reference, additional samples are collected approximately once every 2 weeks at the Mace Head Atmospheric Research Station (MHD) when air masses approach from the site's clean air sector. Thus the time series at TO can be linked to the in situ AGAGE measurements and the NOAA flask sampling programme at MHD. An iterative baseline identification procedure separates polluted samples from baseline data. While there is good agreement of baseline mixing ratios between TO and MHD, with a larger variability of mixing ratios at the continental site, measurements at TO are regularly influenced by elevated halocarbon mixing ratios. Here, first time series are presented for CFC-11, CFC-12, HCFC-22, HFC-134a, HFC-227ea, HFC-245fa, and dichloromethane. While atmospheric mixing ratios of the chlorofluorocarbons (CFCs) decrease, they increase for the hydrochlorofluorocarbons (HCFCs) and the hydrofluorocarbons (HFCs). Small unexpected differences between CFC-11 and CFC-12 are found with regard to frequency and relative enhancement of high mixing ratio events and seasonality, although production and use of both compounds are strictly regulated by the Montreal Protocol, and therefore a similar decrease in atmospheric mixing ratios should occur. Dichloromethane, a solvent about which recently concerns have been raised regarding its growing influence on stratospheric ozone depletion, does not show a significant trend with regard to both baseline mixing ratios and the occurrence of pollution events at Taunus Observatory for the time period covered, indicating stable emissions in the regions that influence the site. An analysis of trajectories from the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model reveals differences in halocarbon mixing ranges depending on air mass origin.

Vertical wind velocity measurements using a five-hole probe with remotely piloted aircraft to study aerosol–cloud interactions

Abstract. The importance of vertical wind velocities (in particular positive vertical wind velocities or updrafts) in atmospheric science has motivated the need to deploy multi-hole probes developed for manned aircraft in small remotely piloted aircraft (RPA). In atmospheric research, lightweight RPAs (< 2.5 kg) are now able to accurately measure atmospheric wind vectors, even in a cloud, which provides essential observing tools for understanding aerosol–cloud interactions. The European project BACCHUS (impact of Biogenic versus Anthropogenic emissions on Clouds and Climate: towards a Holistic UnderStanding) focuses on these specific interactions. In particular, vertical wind velocity at cloud base is a key parameter for studying aerosol–cloud interactions. To measure the three components of wind, a RPA is equipped with a five-hole probe, pressure sensors, and an inertial navigation system (INS). The five-hole probe is calibrated on a multi-axis platform, and the probe–INS system is validated in a wind tunnel. Once mounted on a RPA, power spectral density (PSD) functions and turbulent kinetic energy (TKE) derived from the five-hole probe are compared with sonic anemometers on a meteorological mast. During a BACCHUS field campaign at Mace Head Atmospheric Research Station (Ireland), a fleet of RPAs was deployed to profile the atmosphere and complement ground-based and satellite observations of physical and chemical properties of aerosols, clouds, and meteorological state parameters. The five-hole probe was flown on straight-and-level legs to measure vertical wind velocities within clouds. The vertical velocity measurements from the RPA are validated with vertical velocities derived from a ground-based cloud radar by showing that both measurements yield model-simulated cloud droplet number concentrations within 10 %. The updraft velocity distributions illustrate distinct relationships between vertical cloud fields in different meteorological conditions.

Long-term trends in ozone in baseline and European regionally-polluted air at Mace Head, Ireland over a 30-year period

Observations of surface ozone, O3, have been made at the Mace Head Atmospheric Research Station on the North Atlantic Ocean coastline of Ireland over a 30-year period from April 1987 through to April 2017. Using meteorological analyses and a sophisticated Lagrangian dispersion model, the hourly observations have been sorted by air mass histories to separate out the observations for northern hemisphere mid-latitude baseline air masses. Monthly average baseline levels showed a pronounced seasonal cycle with spring maxima and summer minima. Baseline levels have shown an increase during the 1980s and 1990s which has been stronger in the winter and spring and weaker in the summer. The rate of this increase has slowed to the extent that baseline levels have been relatively constant through the 2000s and started to decline in 2010s. The unsorted O3 data has shown different long-term trends from the baseline data because of the influence of European regional NOx and VOC emissions which have reduced wintertime O3 levels below the baseline levels and enhanced summertime O3 levels above them. Episodic peak O3 levels have declined steadily during the study period but 50 ppb 1 h exceedances are likely to continue for the foreseeable future.

Top-down and bottom-up aerosol–cloud closure: towards understanding sources of uncertainty in deriving cloud shortwave radiative flux

Abstract. Top-down and bottom-up aerosol–cloud shortwave radiative flux closures were conducted at the Mace Head Atmospheric Research Station in Galway, Ireland, in August 2015. This study is part of the BACCHUS (Impact of Biogenic versus Anthropogenic emissions on Clouds and Climate: towards a Holistic UnderStanding) European collaborative project, with the goal of understanding key processes affecting aerosol–cloud shortwave radiative flux closures to improve future climate predictions and develop sustainable policies for Europe. Instrument platforms include ground-based unmanned aerial vehicles (UAVs)1 and satellite measurements of aerosols, clouds and meteorological variables. The ground-based and airborne measurements of aerosol size distributions and cloud condensation nuclei (CCN) concentration were used to initiate a 1-D microphysical aerosol–cloud parcel model (ACPM). UAVs were equipped for a specific science mission, with an optical particle counter for aerosol distribution profiles, a cloud sensor to measure cloud extinction or a five-hole probe for 3-D wind vectors. UAV cloud measurements are rare and have only become possible in recent years through the miniaturization of instrumentation. These are the first UAV measurements at Mace Head. ACPM simulations are compared to in situ cloud extinction measurements from UAVs to quantify closure in terms of cloud shortwave radiative flux. Two out of seven cases exhibit sub-adiabatic vertical temperature profiles within the cloud, which suggests that entrainment processes affect cloud microphysical properties and lead to an overestimate of simulated cloud shortwave radiative flux. Including an entrainment parameterization and explicitly calculating the entrainment fraction in the ACPM simulations both improved cloud-top radiative closure. Entrainment reduced the difference between simulated and observation-derived cloud-top shortwave radiative flux (δRF) by between 25 and 60 W m−2. After accounting for entrainment, satellite-derived cloud droplet number concentrations (CDNCs) were within 30 % of simulated CDNC. In cases with a well-mixed boundary layer, δRF is no greater than 20 W m−2 after accounting for cloud-top entrainment and up to 50 W m−2 when entrainment is not taken into account. In cases with a decoupled boundary layer, cloud microphysical properties are inconsistent with ground-based aerosol measurements, as expected, and δRF is as high as 88 W m−2, even high (> 30 W m−2) after accounting for cloud-top entrainment. This work demonstrates the need to take in situ measurements of aerosol properties for cases where the boundary layer is decoupled as well as consider cloud-top entrainment to accurately model stratocumulus cloud radiative flux. 1The regulatory term for UAV is remotely piloted aircraft (RPA).

Six years of surface remote sensing of stratiform warm clouds in marine and continental air over Mace Head, Ireland

AbstractA total of 118 stratiform water clouds were observed by ground‐based remote sensing instruments at the Mace Head Atmospheric Research Station on the west coast of Ireland from 2009 to 2015. Microphysical and optical characteristics of these clouds were studied as well as the impact of aerosols on these properties. Microphysical and optical cloud properties were derived using the algorithm SYRSOC (SYnergistic Remote Sensing Of Clouds). Ground‐based in situ measurements of aerosol concentrations and the transport path of air masses at cloud level were investigated as well. The cloud properties were studied in dependence of the prevailing air mass at cloud level and season. We found higher cloud droplet number concentrations (CDNC) and smaller effective radii (reff) with greater pollution. Median CDNC ranged from 60 cm−3 in marine air masses to 160 cm−3 in continental air. Median reff ranged from 8 μm in polluted conditions to 10 μm in marine air. Effective droplet size distributions were broader in marine than in continental cases. Cloud optical thickness (COT) and albedo were lower in cleaner air masses and higher in more polluted conditions, with medians ranging from 2.1 to 4.9 and 0.22 to 0.39, respectively. However, calculation of COT and albedo was strongly affected by liquid water path (LWP) and departure from adiabatic conditions. A comparison of SYRSOC results with MODIS (Moderate‐Resolution Imaging Spectroradiometer) observations showed large differences for LWP and COT but good agreement for reff with a linear fit with slope near 1 and offset of −1 μm.

A versatile, refrigerant- and cryogen-free cryofocusing–thermodesorption unit for preconcentration of traces gases in air

Abstract. We present a compact and versatile cryofocusing–thermodesorption unit, which we developed for quantitative analysis of halogenated trace gases in ambient air. Possible applications include aircraft-based in situ measurements, in situ monitoring and laboratory operation for the analysis of flask samples. Analytes are trapped on adsorptive material cooled by a Stirling cooler to low temperatures (e.g. −80 °C) and subsequently desorbed by rapid heating of the adsorptive material (e.g. +200 °C). The set-up involves neither the exchange of adsorption tubes nor any further condensation or refocusing steps. No moving parts are used that would require vacuum insulation. This allows for a simple and robust design. Reliable operation is ensured by the Stirling cooler, which neither contains a liquid refrigerant nor requires refilling a cryogen. At the same time, it allows for significantly lower adsorption temperatures compared to commonly used Peltier elements. We use gas chromatography – mass spectrometry (GC–MS) for separation and detection of the preconcentrated analytes after splitless injection. A substance boiling point range of approximately −80 to +150 °C and a substance mixing ratio range of less than 1 ppt (pmol mol−1) to more than 500 ppt in preconcentrated sample volumes of 0.1 to 10 L of ambient air is covered, depending on the application and its analytical demands. We present the instrumental design of the preconcentration unit and demonstrate capabilities and performance through the examination of analyte breakthrough during adsorption, repeatability of desorption and analyte residues in blank tests. Examples of application are taken from the analysis of flask samples collected at Mace Head Atmospheric Research Station in Ireland using our laboratory GC–MS instruments and by data obtained during a research flight with our in situ aircraft instrument GhOST-MS (Gas chromatograph for the Observation of Tracers – coupled with a Mass Spectrometer).

Diurnal, seasonal, and annual trends in atmospheric CO2 at southwest London during 2000–2012: Wind sector analysis and comparison with Mace Head, Ireland

In-situ measurements of atmospheric CO2 have been made at Royal Holloway University of London (RHUL) in Egham (EGH), Surrey, UK from 2000 to 2012. The data were linked to the global scale using NOAA-calibrated gases. Measured CO2 varies on time scales that range from minutes to inter-annual and annual cycles. Seasonality and pollution episodes occur each year. Diurnal cycles vary with daylight and temperature, which influence the biological cycle of CO2 and the degree of vertical mixing. Anthropogenic emissions of CO2 dominate the variability during weekdays when transport cycles are greater than at weekends. Seasonal cycles are driven by temporal variations in biological activity and changes in combustion emissions. Maximum mole fractions (μmol/mol) (henceforth referred to by parts per million, ppm) occur in winter, with minima in late summer. The smallest seasonal amplitude observed, peak to trough, was 17.0 ppm CO2 in 2003, whereas the largest amplitude observed was 27.1 ppm CO2 in 2008.Meteorology can strongly modify the CO2 mole fractions at different time scales. Analysis of eight 45° wind sectors shows that the highest CO2 mole fractions were recorded from the E and SE sectors. Lowest mole fractions were observed for air masses from the S and SW. Back-trajectory and meteorological analyses of the data confirm that the dominant sources of CO2 are anthropogenic emissions from London and SE England. The largest annual rate of increase in the annual average of CO2, 3.26 ppm yr−1 (p < 0.05), was for the W sector with a smaller increase, 2.56 ppm yr−1 (p < 0.05), for the E sector. Calm winds showed an annual growth rate of 1.16 ppm yr−1 CO2 (p < 0.05) implying declining local sources. The EGH site shows an average growth rate of 2.5 ppm yr−1 CO2 (p < 0.05) over the measured period, which exceeds the observed global trend and contrasts with the decrease in CO2 emissions reported in UK greenhouse gas inventories. This is presumably because the region has had higher growth in combustion emissions than the global average, though the low growth rate in calm weather implies the local emissions have grown more slowly. The seasonal cycle at EGH had larger amplitudes than those recorded at the Mace Head Atmospheric Research Station (MHD) on the W coast of Ireland. Overall, the growth rate observed in annual average CO2 at EGH was larger than that at MHD by about 0.5 ppm yr−1.

Missing SO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; oxidant in the coastal atmosphere? – observations from high-resolution measurements of OH and atmospheric sulfur compounds

Abstract. Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4) and methane sulfonic acid (MSA) were measured in NE Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected-ion chemical ionization mass spectrometry (SI/CIMS) with a detection limit for both compounds of 4.3 × 104 cm−3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analyzed in conjunction with the condensational sink for both compounds derived from 3 nm to 10 μm (aerodynamic diameter) aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed, leading to estimated atmospheric lifetimes on the order of 7 and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH) signal, evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s), its ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated H2SO4 concentrations were consistently lower than the measured concentrations by a factor of 4.7 ± 2.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D), and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s), OH chemistry, and the atmospheric photolysis and photooxidation of biogenic iodine compounds. As to the identity of the atmospheric SO2 oxidant(s), we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on {ab initio} calculations. Nevertheless, IO could contribute significantly to the observed CIMS background signal. A detailed analysis of this CIMS background signal in context with recently published kinetic data currently suggests that Criegee intermediates (CIs) produced from ozonolysis of alkenes play no significant role for SO2 oxidation in the marine atmosphere at Mace Head. On the other hand, SO2 oxidation by small CIs such as CH2OO produced photolytically or possibly in the photochemical degradation of methane is consistent with our observations. In addition, H2SO4 formation from dimethyl sulfide oxidation via SO3 as an intermediate instead of SO2 also appears to be a viable explanation. Both pathways need to be further explored.

Analysis and interpretation of 18 years of mercury observations since 1996 at Mace Head, Ireland

Observations of atmospheric mercury at the Mace Head Atmospheric Research Station on the Atlantic coast of Ireland made from February 1996 to December 2013 are analyzed. Using meteorological analysis and a sophisticated Lagrangian dispersion model, the hourly averaged mercury concentrations were attributed to four different air mass types: baseline, local, European polluted, and sub-tropical maritime. Monthly median Hg concentrations of all types decreased over the analyzed period but the trend for sub-tropical maritime air masses was with −0.016 ± 0.002 ng m−3 yr−1 in absolute terms significantly smaller than the trends for all other classes which varied between −0.021 and −0.023 ng m−3 yr−1. The seasonal variation for sub-tropical maritime air masses is also shallower than for all other classes. This is most likely due to shallower seasonal variation of oxidant concentrations at lower latitudes. The north-south gradient of the trend is qualitatively consistent with the GEOS-Chem model predictions based on decrease of mercury concentrations in surface waters of the North Atlantic but the trends are smaller than predicted. Tests for temporal change of the trends indicate that the decreasing trends of mercury concentrations are leveling off for all air masses with possible exception of the sub-tropical maritime air mass. Quantitative assessment of the trend changes, however, will require a longer time series of the mercury measurements at Mace Head.

Analysis and interpretation of 25 years of ozone observations at the Mace Head Atmospheric Research Station on the Atlantic Ocean coast of Ireland from 1987 to 2012

Observations of surface ozone have been made at the Mace Head Atmospheric Research Station on the Atlantic Ocean coastline of Ireland from April 1987 through to December 2012. Using meteorological analyses and a sophisticated Lagrangian dispersion model, the hourly observations have been sorted into baseline northern hemisphere mid-latitude, European regionally-polluted and southerly sub-tropical maritime air masses. Baseline monthly average levels showed a pronounced seasonal cycle with spring maxima and summer minima. Baseline levels have shown an average annual increase of +0.25 ± 0.09 ppb year−1 which has been stronger in the winter and spring and weaker in the summer months. The rate of this annual increase has slowed over the last decade to the extent that annual levels have been relatively constant through the 2000s. Annual mean O3 levels in European air masses have shown much reduced upwards trends compared with baseline air masses. European levels show a seasonal cycle with a spring maxima and a winter minima. Policy actions to reduce European regional-scale NOx emissions have led to an increase in wintertime O3 levels and a decrease in summertime peak levels. Levels in southerly sub-tropical maritime air masses have shown different seasonal cycles, different seasonal trends and systematically lower levels compared with baseline air masses. The baseline observations have been compared against a number of policy-relevant O3 metrics and these have demonstrated the potential importance of the growing northern hemisphere O3 baseline levels over the 25 year study period.

The seaweeds &amp;lt;i&amp;gt;Fucus vesiculosus&amp;lt;/i&amp;gt; and &amp;lt;i&amp;gt;Ascophyllum nodosum&amp;lt;/i&amp;gt; are significant contributors to coastal iodine emissions

Abstract. Based on the results of a pilot study in 2007, which found high mixing ratios of molecular iodine (I2) above the intertidal macroalgae (seaweed) beds at Mweenish Bay (Ireland), we extended the study to nine different locations in the vicinity of Mace Head Atmospheric Research Station on the west coast of Ireland during a field campaign in 2009. The mean values of I2 mixing ratio found above the macroalgae beds at nine different locations ranged from 104 to 393 ppt, implying a high source strength of I2. Such mixing ratios are sufficient to result in photochemically driven coastal new-particle formation events. Mixing ratios above the Ascophyllum nodosum and Fucus vesiculosus beds increased with exposure time: after 6 h exposure to ambient air the mixing ratios were one order of magnitude higher than those initially present. This contrasts with the emission characteristics of Laminaria digitata, where most I2 was emitted within the first half hour of exposure. Discrete in situ measurements (offline) of I2 emission from ambient air-exposed chamber experiments of L. digitata, A. nodosum and F. vesiculosus substantially supported the field observations. Further online and time-resolved measurements of the I2 emission from O3-exposed macroalgal experiments in a chamber confirmed the distinct I2 emission characteristics of A. nodosum and F. vesiculosus compared to those of L. digitata. The emission rates of A. nodosum and F. vesiculosus were comparable to or even higher than L. digitata after the initial exposure period of ~20–30 min. We suggest that A. nodosum and F. vesiculosus may provide an important source of photolabile iodine in the coastal boundary layer and that their impact on photochemistry and coastal new-particle formation should be reevaluated in light of their longer exposure at low tide and their widespread distribution.

Ground-based retrieval of continental and marine warm cloud microphysics

Abstract. A technique for retrieving warm cloud microphysics using synergistic ground based remote sensing instruments is presented. The SYRSOC (SYnergistic Remote Sensing Of Cloud) technique utilises a Ka-band Doppler cloud RADAR, a LIDAR (or ceilometer) and a multichannel microwave radiometer. SYRSOC retrieves the main microphysical parameters such as cloud droplet number concentration (CDNC), droplets effective radius (reff), cloud liquid water content (LWC), and the departure from adiabatic conditions within the cloud. Two retrievals are presented for continental and marine stratocumulus advected over the Mace Head Atmospheric Research Station. Whilst the continental case exhibited high CDCN (N = 382 cm−3; 10th-to-90th percentile [9.4–842.4] cm−3) and small mean effective radius (reff = 4.3; 10th-to-90th percentile [2.9–6.5] μm), the marine case showed low CDNC and large mean effective radius (N = 25 cm−3, 10th-to-90th percentile [1.5–69] cm−3; reff = 28.4 μm, 10th-to-90th percentile [11.2–42.7] μm) as expected since continental air at this location is typically more polluted than marine air. The mean LWC was comparable for the two cases (continental: 0.19 g m−3; marine: 0.16 g m−3) but the 10th–90th percentile range was wider in marine air (continental: 0.11–0.22 g m−3; marine: 0.01–0.38 g m−3). The calculated algorithm uncertainty for the continental and marine case for each variable was, respectively, σN = 161.58 cm−3 and 12.2 cm−3, σreff = 0.86 μm and 5.6 μm, σLWC = 0.03 g m−3 and 0.04 g m−3. The retrieved CDNC are compared to the cloud condensation nuclei concentrations and the best agreement is achieved for a supersaturation of 0.1% in the continental case and between 0.1%–0.75% for the marine stratocumulus. The retrieved reff at the top of the clouds are compared to the MODIS satellite reff: 7 μm (MODIS) vs. 6.2 μm (SYRSOC) and 16.3 μm (MODIS) vs. 17 μm (SYRSOC) for continental and marine cases, respectively. The combined analysis of the CDNC and the reff, for the marine case shows that the drizzle modifies the droplet size distribution and reff especially if compared to reffMOD. The study of the cloud subadiabaticity and the LWC shows the general sub-adiabatic character of both clouds with more pronounced departure from adiabatic conditions in the continental case than in the marine.

The Eyjafjallajökull ash plume – Part I: Physical, chemical and optical characteristics

The Eyjafjallajökull ash plume was detected at the Mace Head Atmospheric Research Station numerous times from April 19th till 18th May 2010 following subsidence into, and dilution in, the boundary layer. The three strongest of these events, lasting 12–18 h, are analysed in detail in terms of physical, chemical and optical properties. The ash size distribution was bimodal with a supermicron mode of 2.5 μm diameter for the one case where it was measured. The submicron mode varied from 185 nm during the high-explosive phase to 395 nm during the low-explosive phase. Non-sea-salt (nss)-sulphate mass was 2.5 times higher during the low-explosive phase. Total particle concentrations ranged from 760 cm −3 to 1247 cm −3 and were typical of clean air in the region. Between 30% and 39% of submicron chemical mass (i.e. exclusive of water content) was ash primarily composed of silicon dioxide while accounting for the water content, the submicron aerosol was composed of primary ash (15%), nss-sulphate (25%) and water (55%). Hygroscopic growth factors were characteristic of sulphate aerosol but revealed an internally-mixed aerosol pointing to a mix of predominantly primary ash, nss-sulphate and water. For the majority of the ash plumes, all condensation nuclei (CN, diameter > 10 nm) were activated into cloud condensation nuclei (CCN) at a supersaturation of 0.25%. Aerosol absorption increased by about a factor of two in the plume, compared to background levels, while aerosol scattering coefficients increased by an order of magnitude. ► The physico-chemical characteristics of the Eyjafjallajökull ash plume are reported. ► The submicron ash particles are composed of sulphuric acid, water and silicon dioxide. ► The ash particles are highly water soluble with a very high CCN efficiency.

Seasonal Variation of the Aerosol Light Scattering Coefficient in Marine Air of the Northeast Atlantic

Aerosol light scattering measurements were carried out using a TSI 3563 Nephelometer at the Mace Head Atmospheric Research Station, on the west coast of Ireland from year 2001–2010. A strong seasonal trend in the aerosol light scattering coefficient at 550 nm (), for clean marine air masses, is observed with a high value, [average (geometric mean)] of 35.3 Mm−1(29.5 Mm−1), in January and a low value of 13.7 Mm−1(10.2 Mm−1), in July. This near threefold increase in the value during the winter season is because of the large contribution of wind-speed generated sea-salt particles in the marine boundary layer. A high positive correlation coefficient of 0.82 was found between the percentage occurrence of relatively large Ångström exponent (Å) values (&gt;1.2) and the percentage occurrence of lower values (5–15 Mm−1) in the summer season. and wind-speed have a high positive correlation coefficient of 0.88 whereas Å and wind-speed have a negative correlation coefficient of −0.89. Å values during the summer months indicate the dominance of sub-m particles thus indicating the contribution of non-sea-salt sulphate and organics towards the as these species show an enhanced concentration during the summer months.

Estimation of hydrogen deposition velocities from 1995-2008 at Mace Head, Ireland using a simple box model and concurrent ozone depositions

During stable nocturnal inversions with low wind speeds, we observed strong depletions of both hydrogen and ozone caused by deposition to the peat bogs in the vicinity of the Mace Head Atmospheric Research Station, Connemara, County Galway, Ireland. From these temporally correlated fluxes and using a simple box model, we have estimated the strength of the molecular hydrogen soil sink over a 14-yr period (1995-2008). Over this entire period 269 nocturnal deposition events were identified that satisfied the strict selection criteria. The average hydrogen deposition velocity determined from these events was 0.53 mm s-1, covering a range of 0.18-1.29 mm s-1, which is in agreement with the range of deposition velocities reported in the literature for similar peaty biomes. By annually averaging all of the nocturnal inversion events over the most seasonally active period from April-September we reveal a positive correlation with ambient temperature in the relative deposition velocities of hydrogen and ozone, which is not readily apparent in all of the individual events. Furthermore, average hydrogen deposition velocities and accumulated rainfall from 48 h before and during each event were to a reasonable extent anti-correlated. However, due to the large uncertainties in determining monthly mean H2 deposition velocities there is no statistically significant trend in the hydrogen deposition velocities over time.

Light scattering enhancement factors in the marine boundary layer (Mace Head, Ireland)

Direct climate aerosol radiative forcing is influenced by the light scattering of atmospheric aerosols. The chemical composition, the size distribution, and the ambient relative humidity (RH) determine the amount of visible light scattered by aerosols. We measured the aerosol light scattering coefficients at RH varying from 30% to 90% of the marine atmosphere at the Mace Head Atmospheric Research Station on the west coast of Ireland. At this site, two major air mass types can be distinguished: clean marine and polluted air. In this paper, we present measurements of light scattering enhancement factors f(RH) = σsp(RH)/σsp(dry) from a 1 month field campaign (January–February 2009). At this site in winter, the mean f(RH = 85%) (standard deviation) for marine air masses at the wavelength of 550 nm was 2.22 (±0.17) and 1.77 (±0.31) for polluted air. Measured σsp(RH) and f(RH) agreed well with calculations from Mie theory using measurements of the size distribution and hygroscopic diameter growth factors as input. In addition, we investigated the RH influence on additional intensive optical properties: the backscatter fraction and the single scattering albedo. The backscatter fraction decreased by about 20%, and the single scattering albedo increased on average by 1%–5% at 85% RH compared to dry conditions.

Growth rates during coastal and marine new particle formation in western Ireland

Growth rates of new particles during coastal and marine secondary aerosol particle formation events were studied in western Ireland, both at the Mace Head atmospheric research station and onboard the R/V Celtic Explorer as part of the Marine Aerosol Production project. Strong new particle formation events are frequently detected at Mace Head caused by the emission of precursor gases from exposed seaweed during low tide. Although these events were usually only detected as a mode of particles at a certain size, we were able to link the size of the mode to the growth time of these particles after the initial formation by combining data from several events measured between January 2006 and November 2007 with an air ion spectrometer. Typically, the early growth rates were extremely high, reaching values of several hundred nanometers per hour during the first seconds. The growth rates rapidly decreased and reached values below 1 nm h−1 within 1 h after nucleation. Our results were reproduced with box model calculations. All the obtained growth rates could be explained by the model either by varying the precursor formation time (typically a few seconds) or allowing multiple precursor vapor additions. From the ship‐borne measurements, we report the first observations of purely open ocean new particle formation detected in this region. In total, four events were detected during this period, with three having a variable continental influence. An estimated average growth rate in marine conditions was 3 nm h−1 for these events.

Aerosol properties associated with air masses arriving into the North East Atlantic during the 2008 Mace Head EUCAARI intensive observing period: an overview

Abstract. As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June, 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the N. E. Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm−3, while background marine air aerosol concentrations were between 400–600 cm−3. The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm−3, was observed and attributed to open ocean particle formation. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40–50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were highest in marine tropical air – even higher than in continental air. MSA was present at twice the concentrations of previously-reported concentrations at the same location and the same season. Both continental and marine air exhibited aerosol GFs significantly less than ammonium sulphate aerosol pointing to a significant organic contribution to all air mass aerosol properties.