Changes in domestic heating fuel use in Greece : Effects on atmospheric chemistry and radiation

For the past 8 years, Greece has been experiencing a major financial crisis which, among other side effects, has led to a shift in the fuel used for residential heating from fossil fuel towards biofuels, primarily wood. This study simulates the fate of the residential wood burning aerosol plume (RWB smog) and the implications on atmospheric chemistry and radiation, with the support of detailed aerosol characterization from measurements during the winter of 2013–2014 in Athens. The applied model system (TNO-MACC_II emissions and COSMO-ART model) and configuration used reproduces the measured frequent nighttime aerosol spikes (hourly PM₁₀  >  75 µg m⁻³) and their chemical profile (carbonaceous components and ratios). Updated temporal and chemical RWB emission profiles, derived from measurements, were used, while the level of the model performance was tested for different heating demand (HD) conditions, resulting in better agreement with measurements for T$_{min}$ < 9 °C. Half of the aerosol mass over the Athens basin is organic in the submicron range, of which 80 % corresponds to RWB (average values during the smog period). Although organic particles are important light scatterers, the direct radiative cooling of the aerosol plume during wintertime is found low (monthly average forcing of –0.4 W m⁻² at the surface), followed by a minor feedback to the concentration levels of aerosol species. The low radiative cooling of a period with such intense air pollution conditions is attributed to the timing of the smog plume appearance, both directly (longwave radiation increases during nighttime) and indirectly (the mild effect of the residual plume on solar radiation during the next day, due to removal and dispersion processes

Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds: case study based on MINOS results

International audienceThe partitioning of reactive nitrogen compounds between the gas and the aerosol phase, as observed during the MINOS (Mediterranean INtensive Oxidant Study) campaign in Crete, Greece, in July and August 2001, has been studied with three thermodynamic gas-aerosol equilibrium models (EQMs) of different chemical complexity: ISORROPIA, which is limited to the ammonium sulfate-nitrate-sodium-chloride-water-system, SCAPE2, which also includes mineral elements (calcium, magnesium and potassium), and EQSAM2, which additionally accounts for organic acids. The different EQMs, as applied at the same level of complexity, generally produce comparable results within the range of measurement uncertainties (on average within ~10%), although they differ considerably in particular aspects. Model simulations of three distinct air pollution episodes during MINOS show that organic acids (lumped) and soluble mineral cations need to be included in EQMs to accurately simulate the gas-aerosol partitioning of ammonia and nitric acid

Atmospheric nutrient inputs to the northern levantine basin from a long-term observation: sources and comparison with riverine inputs

Aerosol and rainwater samples have been collected at a rural site located on the coastline of the Eastern Mediterranean, Erdemli, Turkey between January 1999 and December 2007. Riverine sampling was carried out at five Rivers (Ceyhan, Seyhan, Göksu, Berdan and Lamas) draining into the Northeastern Levantine Basin (NLB) between March 2002 and July 2007. Samples have been analyzed for macronutrients of phosphate, silicate, nitrate and ammonium (PO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;3&amp;minus;&lt;/sup&gt;, Si&lt;sub&gt;diss&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt;&lt;sup&gt;&amp;minus;&lt;/sup&gt; and NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;). Phosphate and silicate in aerosol and rainwater showed higher and larger variations during the transitional period when air flows predominantly originate from North Africa and Middle East/Arabian Peninsula. Deficiency of alkaline material have been found to be the main reason of the acidic rain events whilst high pH values (&gt;7) have been associated with high Si&lt;sub&gt;diss&lt;/sub&gt; concentrations due to sporadic dust events. In general, lowest nitrate and ammonium concentrations in aerosol and rainwater have been associated with air flow from the Mediterranean Sea. Comparison of atmospheric with riverine fluxes demonstrated that DIN and PO&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;3&amp;minus;&lt;/sup&gt; fluxes to NLB have been dominated by atmosphere (~90% and ~60% respectively) whereas the input of Si was mainly derived from riverine runoff (~90%). N/P ratios in the atmospheric deposition (233); riverine discharge (28) revealed that NLB receives excessive amounts of DIN and this unbalanced P and N inputs may provoke even more phosphorus deficiency. Observed molar Si/N ratio suggested Si limitation relative to nitrogen might cause a switch from diatom dominated communities to non-siliceous populations particularly at coastal NLB

Size-resolved CCN distributions and activation kinetics of aged continental and marine aerosol

We present size-segregated measurements of cloud condensation nucleus (CCN) activity of aged aerosol sampled at Finokalia, Crete, during the Finokalia Aerosol Measurement Experiment of summer 2007 (FAME07). From analysis of the data, hygroscopicity and activation kinetics distributions are derived. The CCN are found to be highly hygroscopic, (expressed by a size- and time- averaged hygroscopicity parameter &amp;kappa; &amp;sim; 0.22), with the majority of particles activating at ~0.5–0.6 % supersaturation. Air masses originating from Central-Eastern Europe tend to be associated with higher CCN concentrations and slightly lower hygroscopicity (&amp;kappa; &amp;sim; 0.18) than for other airmass types. The particles were always well mixed, as reflected by the high activation ratios and narrow hygroscopicity distribution widths. Smaller particles (~40 nm) were found to be more hygroscopic (~0.1κ units higher) than the larger ones (~100 nm). The particles with diameters less than 80 nm exhibited a diurnal hygroscopicity cycle (with κ peaking at ~14 h local time), consistent with photochemical aging and volatilization of less hygroscopic material from the aerosol. Use of bulk chemical composition and the aerosol number distribution results in excellent CCN closure when applying Köhler theory in its simplest form. Using asymptotic and threshold droplet growth analysis, the "aged" organics present in the aerosol were found not to suppress or delay the water uptake kinetics of particles in this environment

Influence of phytoplankton taxonomic profile on the distribution of total and dissolved dimethylated sulphur (DMSx) species in the North Aegean Sea (Eastern Mediterranean)

The distribution of total and dissolved forms of DMSP and total DMSO was surveyed during two sampling cruises conducted in September 2003 and July 2004 in the North Aegean Sea. During the first cruise the surface concentrations of DMSPt, DMSPd and DMSOt in the coastal group of stations ranged from 20.92 to 23.71 nM, 15.46 to 15.53 nM and 14.90 to 18.73 nM respectively, while in the offshore group the mean concentrations were 27.41 nM (DMSPt) and 14.66 nM (DMSOt). Concerning the phytoplankton assemblage it was dominated by dinoflagellates. During the second cruise, the surface DMSPt, DMSPd and DMSOt concentrations in the coastal group were not significantly changed compared to the first cruise, while the offshore group presented more elevated values (DMSPt: 33.52 nM; DMSPd: 18.78 nM; DMSOt: 36.49 nM). Interestingly the vertical distribution and the phytoplankton abundance in this cruise were changed, with diatoms being the dominant group in the study area. On both cruises statistically significant correlations between small-sized dinoflagellates (≤ 20 μm) as well as coccolithophores and the concentrations of DMSx compounds obtained, suggesting the importance of the above phytoplankton groups in the production and distribution of the these sulphonic forms. At the same time, no significant correlations were observed between DMSx and diatom species. The strong correlation of DMSx species with the group of dinoflagellates coupled with their decorrelation with Chl-a may serve as indirect evidence of heterotrophic forms dominating dinoflagellate taxa thriving in the area during the stratified period.

Size-segregated mass distributions of aerosols over Eastern Mediterranean: seasonal variability and comparison with AERONET columnar size-distributions

International audienceThis work provides long-term (2004?2006) size segregated measurements of aerosol mass at a remote coastal station in the southern Europe, with the use of size-selective samplings (SDI impactor). Seven distinct modes were identified in the range 0?10 µm and the dominant were the "Accumulation 1" (0.25?0.55 µm) and the "Coarse 2" (3?7 µm) modes. The seasonal characteristics of each mode were thoroughly studied and different sources for submicron and supermicron particles were identified, the first being related to local/regional and transported pollution with maximum in summer and the latter to dust from deserted areas in Northern Africa maximizing in spring. On average, PM2.5 and PM1 accounted for 60% and 40% of PM10 mass, respectively.The representativity of the ground-based measurements for the total column was also investigated by comparing the measured aerosol mass distributions with the AERONET volume size distribution data. Similar seasonal patterns were revealed and AERONET was found adequate for the estimation of background levels of both fine and coarse particles near surface, with certain limitations in the case of pollution or dust abrupt episodes due to its low temporal coverage

Characterization of carbonaceous aerosols during the MINOS campaign in Crete, July–August 2001: a multi-analytical approach

International audienceDuring the major part of the Mediterranean Intensive Oxidant Study (MINOS) campaign (summer 2001, Crete Isl.), the Marine Boundary Layer (MBL) air was influenced by long range transport of biomass burning from the northern and western part of the Black Sea. During this campaign, carbonaceous aerosols were collected on quartz filters at a Free Tropospheric (FT) site, and at a MBL site together with size-resolved distribution of aerosols. Three Evolution Gas Analysis (EGA) protocols have been tested in order to better characterize the collected aged biomass burning smoke: A 2-step thermal method (Cachier et al., 1989) and a thermo-optical technique using two different temperature programs. The later temperature programs are those used for IMPROVE (Interagency Monitoring of Protected Visual Environments) and NIOSH 5040 (National Institute of Occupational Safety and Health). Artifacts were observed using the NIOSH temperature program and identified as interactions between carbon and dust deposited on the filter matrix at high temperature (T>550ºC) under the pure helium step of the analysis. During the MINOS campaign, Black Carbon (BC) and Organic Carbon (OC) mass concentrations were on average respectively 1.19±0.56 and 3.62±1.08 mgC/m3 for the IMPROVE temperature program, and 1.09±0.36 and 3.75±1.24 mgC/m3 for the thermal method. Though these values compare well on average and the agreement between the Total Carbon (TC) measurements sample to sample was excellent (slope=1.00, r2=0.93, n=56), important discrepancies were observed in determining BC concentrations from these two methods (average error of 33±22%). BC from the IMPROVE temperature program compared well with non-sea-salt potassium (nss-K) pointing out an optical sensitivity to biomass burning. On the other hand, BC from the thermal method showed a better agreement with non-sea-salt sulfate (nss-SO4), considered as a tracer for fossil fuel combustion during the MINOS campaign. The coupling between these two methods for determining BC brings here new insights on the origin of carbonaceous aerosols in a complex mixture of different sources. It brings also to our attention that important deviations in BC levels are observed using three widely used EGA's techniques and most probably none of the EGA tested here are well adapted to fully characterize this aerosol mixture. Spherical, smooth and silico-aluminated fly-ash observed by an Analytical Scanning Electron Microscope (ASEM) confirm the influence of coal combustion on the carbonaceous aerosol load throughout the campaign. A rough calculation based on a BC/nss-SO4 mass ratio suggests that biomass burning could be responsible for half of the BC concentration recorded during the MINOS campaign. From the plot of BC as a function of TC, two linear correlations were observed corresponding to 2 times series (before and after 12 August). Such good correlations suggest, from a first look, that both BC and OC have similar origin and atmospheric transport. On the other hand, the plot of BC as a function of TC obtained from the 2-step thermal method applied to DEKATI Low Pressure Cascade Impactor samples does not show a similar correlation and points out a non conservative distribution of this ratio with 2 super micron modes enriched in OC, correlated with sea salt aerosols and probably originating from gas-to-particle conversion

Characterisation and improvement of j(O¹D) filter radiometers

Atmospheric O3 → O(1D) photolysis frequencies j(O1D) are crucial parameters for atmospheric photochemistry because of their importance for primary OH formation. Filter radiometers have been used for many years for in situ field measurements of j(O1D). Typically the relationship between the output of the instruments and j(O1D) is non-linear because of changes in the shape of the solar spectrum dependent on solar zenith angles and total ozone columns. These non-linearities can be compensated for by a correction method based on laboratory measurements of the spectral sensitivity of the filter radiometer and simulated solar actinic flux density spectra. Although this correction is routinely applied, the results of a previous field comparison study of several filter radiometers revealed that some corrections were inadequate. In this work the spectral characterisations of seven instruments were revised, and the correction procedures were updated and harmonised considering recent recommendations of absorption cross sections and quantum yields of the photolysis process O3 → O(1D). Previous inconsistencies were largely removed using these procedures. In addition, optical interference filters were replaced to improve the spectral properties of the instruments. Successive determinations of spectral sensitivities and field comparisons of the modified instruments with a spectroradiometer reference confirmed the improved performance. Overall, filter radiometers remain a low-maintenance alternative of spectroradiometers for accurate measurements of j(O1D) provided their spectral properties are known and potential drifts in sensitivities are monitored by regular calibrations with standard lamps or reference instruments