ALBERT

Description: Surface concentrations of secondary inorganic particle components over the UK have been analysed for 2001–2010 using the EMEP4UK regional atmospheric chemistry transport model and evaluated against measurements. Gas/particle partitioning in the EMEP4UK model simulations used a bulk approach, which may lead to uncertainties in simulated secondary inorganic aerosol. However, model simulations were able to accurately represent both the long-term decadal surface concentrations of particle sulfate and nitrate and an episode in early 2003 of substantially elevated nitrate measured across the UK by the AGANet network. The latter was identified as consisting of three separate episodes, each of less than 1 month duration, in February, March and April. The primary cause of the elevated nitrate levels across the UK was meteorological: a persistent high-pressure system, whose varying location impacted the relative importance of transboundary versus domestic emissions. Whilst long-range transport dominated the elevated nitrate in February, in contrast it was domestic emissions that mainly contributed to the March episode, and for the April episode both domestic emissions and long-range transport contributed. A prolonged episode such as the one in early 2003 can have substantial impact on annual average concentrations. The episode led to annual concentration differences at the regional scale of similar magnitude to those driven by long-term changes in precursor emissions over the full decade investigated here. The results demonstrate that a substantial part of the UK, particularly the south and southeast, may be close to or exceeding annual mean limit values because of import of inorganic aerosol components from continental Europe under specific conditions. The results reinforce the importance of employing multiple year simulations in the assessment of emissions reduction scenarios on particulate matter concentrations and the need for international agreements to address the transboundary component of air pollution.

Description: This is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS) - malonic acid (MA) - water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA) of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25

Description: The phase transitions and hygroscopic growth of two humic acid aerosols (Aldrich sodium salt and Leonardite Standard (IHSS)) and their mixtures with ammonium sulphate have been investigated using a combination of two techniques, Fourier transform infra-red (FTIR) spectroscopy and tandem differential mobility analysis (TDMA). A growth factor of 1.16 at 85% relative humidity (RH) was found for the Aldrich humic acid which can be regarded as an upper limit for growth factors of humic-like substances (HULIS) found in atmospheric aerosol and is significantly smaller than that of typical atmospheric inorganics. We find that the humic acid aerosols exhibit water uptake over all relative humidities with no apparent phase changes, suggesting that these aerosols readily form supersaturated droplets. In the mixed particles, the humic acid component decreases the deliquescence relative humidity (DRH) and increases the efflorescence relative humidity (ERH) of the ammonium sulphate component, and there is some degree of water uptake prior to ammonium sulphate deliquescence. In addition, at low RH, the FTIR spectra show that the ammonium is present in a different chemical environment in the mixed aerosols than in crystalline ammonium sulphate, perhaps existing as a complex with the humic materials. The growth factors of the mixed aerosols are intermediate between those of the single-component aerosols and can be predicted assuming that the inorganic and organic fractions take up water independently.

Description: Biogenic influences on the composition and characteristics of aerosol were investigated on Bird Island (54°00' S, 38°03' W) in the South Atlantic during November and December 2010. This remote marine environment is characterised by large seabird and seal colonies. The chemical composition of the submicron particles, measured by an aerosol mass spectrometer (AMS), was 21% non-sea-salt sulfate, 2% nitrate, 8% ammonium, 22% organics and 47% sea salt including sea salt sulfate. A new method to isolate the sea spray signature from the high-resolution AMS data was applied. Generally, the aerosol was found to be less acidic than in other marine environments due to the high availability of ammonia, from local fauna emissions. By positive matrix factorisation five different organic aerosol (OA) profiles could be isolated: an amino acid/amine factor (AA-OA, 18% of OA mass), a methanesulfonic acid OA factor (MSA-OA, 25%), a marine oxygenated OA factor (M-OOA, 41%), a sea spray OA fraction (SS-OA, 7%) and locally produced hydrocarbon-like OA (HOA, 9%). The AA-OA was dominant during the first two weeks of November and found to be related with the hatching of penguins in a nearby colony. This factor, rich in nitrogen (N : C ratio = 0.13), has implications for the biogeochemical cycling of nitrogen in the area as particulate matter is often transported over longer distances than gaseous N-rich compounds. The MSA-OA was mainly transported from more southerly latitudes where phytoplankton bloomed. The bloom was identified as one of three sources for particulate sulfate on Bird Island, next to sea salt sulfate and sulfate transported from South America. M-OOA was the dominant organic factor and found to be similar to marine OA observed at Mace Head, Ireland. An additional OA factor highly correlated with sea spray aerosol was identified (SS-OA). However, based on the available data the type of mixture, internal or external, could not be determined. Potassium was not associated with sea salt particles during 19% of the time, indicating the presence of biogenic particles in addition to the MSA-OA and AA-OA factors.

Description: A comprehensive assessment of nitrogen (N) flows at the landscape scale is fundamental to understand spatial interactions in the N cascade and to inform the development of locally optimised N management strategies. To explore this interactions, complete N budgets were estimated for two contrasting hydrological catchments (dominated by agricultural grassland vs. semi-natural peat-dominated moorland), forming part of an intensively studied landscape in southern Scotland. Local scale atmospheric dispersion modelling and detailed farm and field inventories provided high resolution estimations of input fluxes. Agricultural inputs (i.e. grazing excreta, organic and synthetic fertiliser) accounted for most of the catchment N inputs with 80% in the grassland and 57% in the moorland catchment, while atmospheric deposition made a significant contribution, particularly in the moorland catchment with 38% of the N inputs. The estimated catchment N budgets highlighted areas of key uncertainty, particularly N2 emissions from denitrification and stream N export. The resulting N balances suggest that the study catchments have a limited capacity to store N within soils, vegetation and groundwater. The "catchment N retention", i.e. the amount of N which is either stored within the catchment or lost through atmospheric emissions, was estimated to be 3% of the net anthropogenic input in the moorland and 55% in the grassland catchment. These values contrast with regional scale estimates: catchment retentions of net anthropogenic input estimated within Europe at the regional scale range from 50% to 90% with an average of 82% (Billen et al., 2011). This study emphasises the need for detailed budget analyses to identify the N status of European landscapes.

Description: Leaf nitrogen and leaf surface area influence the exchange of gases between terrestrial ecosystems and the atmosphere, and they play a significant role in the global cycles of carbon, nitrogen and water. Remote sensing data from satellites can be used to estimate leaf area index (LAI), leaf chlorophyll (CHLl) and leaf nitrogen density (Nl). However, methods are often developed using plot scale data and not verified over extended regions that represent a variety of soil spectral properties and canopy structures. In this paper, field measurements and high spatial resolution (10–20 m) remote sensing images acquired from the HRG and HRVIR sensors aboard the SPOT satellites were used to assess the predictability of LAI, CHLl and Nl. Five spectral vegetation indices (SVIs) were used (the Normalized Difference Vegetation index, the Simple Ratio, the Enhanced Vegetation Index-2, the Green Normalized Difference Vegetation Index, and the green Chlorophyll Index) together with the image-based inverse canopy radiative transfer modelling system, REGFLEC (REGularized canopy reFLECtance). While the SVIs require field data for empirical model building, REGFLEC can be applied without calibration. Field data measured in 93 fields within crop- and grasslands of five European landscapes showed strong vertical CHLl gradient profiles in 20% of fields. This affected the predictability of SVIs and REGFLEC. However, selecting only homogeneous canopies with uniform CHLl distributions as reference data for statistical evaluation, significant (p 〈 0.05) predictions were achieved for all landscapes, by all methods. The best performance was achieved by REGFLEC for LAI (r2=0.7; rmse = 0.73), canopy chlorophyll content (r2=0.51; rmse = 439 mg m−2) and canopy nitrogen content (r2 = 0.53; rmse = 2.21 g m−2). Predictabilities of SVIs and REGFLEC simulations generally improved when constrained to single land use categories (wheat, maize, barley, grass) across the European landscapes, reflecting sensitivity to canopy structures. Predictability further improved when constrained to local (10 × 10 km2) landscapes, thereby reflecting sensitivity to local environmental conditions. All methods showed different predictabilities for land use categories and landscapes. Combining the best methods, LAI, canopy chlorophyll content (CHLc) and canopy nitrogen content (CHLc) for the five landscapes could be predicted with improved accuracy (LAI rmse = 0.59; CHLc rmse = 346 g m−2; Ncrmse = 1.49 g m−2). Remote sensing-based results showed that the vegetation nitrogen pools of the five agricultural landscapes varied from 0.6 to 4.0 t km−2. Differences in nitrogen pools were attributed to seasonal variations, extents of agricultural area, species variations, and spatial variations in nutrient availability. Information on Nl and total Nc pools within the landscapes is important for the spatial evaluation of nitrogen and carbon cycling processes. The upcoming Sentinel-2 satellite mission will provide new multiple narrow-band data opportunities at high spatio-temporal resolution which are expected to further improve remote sensing predictabilities of LAI, CHLl and Nl.

Description: Biogenic influences on the composition and characteristics of aerosol were investigated on Bird Island (54°00' S, 38°03' W) in the South Atlantic during November and December 2010. This remote marine environment is characterised by large seabird and seal colonies. The chemical composition of the submicron particles, measured by an aerosol mass spectrometer (AMS), was 21% non-sea salt sulfate 2% nitrate, 7% ammonium, 22% organics and 47% sea salt including sea salt sulfate. A new method to isolate the sea salt signature from the high-resolution AMS data was applied. Generally, the aerosol was found to be less acidic than in other marine environments due to the high availability of ammonia, from local fauna emissions. By positive matrix factorisation five different organic aerosol (OA) profiles could be isolated: an amino acids/amine factor (AA-OA, 18% of OA mass), a methanesulfonic acid OA factor (MSA-OA, 25%), a marine oxygenated OA factor (M-OOA, 40%), a sea salt OA fraction (SS-OA, 7%) and locally produced hydrocarbon-like OA (HOA, 9%). The AA-OA was dominant during the first two weeks of November and found to be related with the hatching of penguins in a nearby colony. This factor, rich in nitrogen (C : N ratio = 0.13), has implications for the biogeochemical cycling of nitrogen in the area as particulate matter is often transported over longer distances than gaseous N-rich compounds. The MSA-OA was mainly transported from more southerly latitudes where phytoplankton bloomed. The bloom was identified as one of three sources for particulate sulfate on Bird Island, next to sea salt sulfate and sulfate transported from South America. M-OOA was the dominant organic factor and found to be similar to marine OA observed at Mace Head, Ireland. An additional OA factor highly correlated with sea salt aerosol was identified (SS-OA). However, based on the available data the type of mixture, internal or external, could not be determined. Potassium was not associated to sea salt particles during 19% of the time, indicating the presence of biogenic particles in addition to the MSA-OA and AA-OA factors.

Description: Analyses have been undertaken of the trends and drivers of the distributions of ground-level O3 concentrations associated with potential impacts on human health and vegetation using measurements at the two UK EMEP supersites of Harwell and Auchencorth. These two sites provide representation of rural O3 over the wider geographic areas of south-east England and northern UK, respectively. The O3 exposures associated with health and vegetation impacts were quantified, respectively, by the SOMO10 and SOMO35 metrics, and by the flux-based PODY metrics for wheat, potato, beech and Scots pine. Statistical analyses of measured O3 and NOx concentrations was supplemented by analyses of meteorological data and NOx emissions along air-mass back trajectories. The findings highlight the differing responses of impact metrics to the decreasing contribution of regional O3 episodes in determining O3 concentrations at Harwell between 1990 and 2013, associated with European NOx emission reductions. An improvement in human health-relevant O3 exposure observed when calculated by SOMO35, which decreased significantly, was not observed when quantified by SOMO10. The decrease in SOMO35 is driven by decreases in regionally-produced O3 which makes a larger contribution to SOMO35 than to SOMO10. For the O3 vegetation impacts at Harwell, no significant trend was observed for the PODY metrics of the four species, in contrast to the decreasing trend in vegetation-relevant O3 exposure perceived when calculated using the crop AOT40 metric. The decreases in regional O3 production have not decreased PODY as climatic and plant conditions reduced stomatal conductance and uptake of O3 during regional O3 production. Ozone concentrations at Auchencorth (2007–2013) were more influenced by hemispheric background concentrations than at Harwell. For health-related O3 exposures this resulted in lower SOMO35 but similar SOMO10 compared with Harwell; for vegetation PODY values, this resulted in greater impacts at Auchencorth for vegetation types with lower exceedance ("Y") thresholds and longer growing seasons (i.e. beech and Scots pine). Additionally, during periods influenced by regional O3 production, a greater prevalence of plant conditions which enhance O3 uptake (such as higher soil water potential) at Auchencorth compared to Harwell resulted in exacerbation of vegetation impacts at Auchencorth, despite being further from O3 precursor emissions sources. These analyses indicate that quantifications of future improvement in health-relevant O3 exposure achievable from pan-European O3 mitigation strategies is highly dependent on the choice of O3 concentration cut-off threshold, and reduction in potential health impact associated with more modest O3 concentrations requires reductions in O3 precursors on a larger (hemispheric) spatial scale. Additionally, while further reduction in regional O3 is more likely to decrease O3 vegetation impacts within the spatial domains of Auchencorth compared to Harwell, larger reductions in vegetation impact could be achieved across the UK from reduction of hemispheric background O3 concentrations.