Composition and variability of gaseous organic pollution in the port megacity of Istanbul: source attribution, emission ratios, and inventory evaluation

In the framework of the TRANSport Emissions and Mitigation in the East Mediterranean (TRANSEMED/ChArMEx) program; Volatile Organic Compound (VOC) measurements were performed for the first time in Istanbul (Turkey) at an urban site in September 2014. One commercial gas-chromatograph coupled to a flame ionization detector (GC-FID) and one proton transfer mass spectrometer (PTR-MS) were deployed. In addition, sorbent tubes and canisters were implemented within the megacity close to major emission sources. More than 70 species including non-methane hydrocarbons (NMHC), oxygenated VOCs (OVOC) and organic compounds of intermediate volatility (IVOC) have been quantified. Among these compounds, 23 anthropogenic and biogenic species were continuously collected at the urban site. VOC concentrations show a great variability with maxima exceeding 10 ppb (i.e. n-butane, toluene, methanol, and acetaldehyde) and mean values between 0.1 (methacrolein + methylvinylketone) to 4.9 ppb (methanol). OVOC represents 43.9 % of the total VOC concentrations followed by alkanes (26.3 %), aromatic compounds (20.7 %), alkenes (4.8 %), terpenes (3.4 %) and acetonitrile (0.8 %). However, on average, the atmospheric composition of anthropogenic alkanes and aromatics is similar to the ones of European megacities like Paris and London, suggesting the impact of traffic emissions for those compounds. Unusual diurnal profiles of anthropogenic VOC, different from the one of traffic derived products like NOx, reveal the complex interaction between emissions and meteorology. Multiple evidences of the impact of sources other than traffic like industrial activities under continental and south–southwesterly wind regimes or ship emissions on IVOC loads was found. Five factors have been extracted from the PMF model (EPA/PMF 5.0) and have been compared to source profiles established by near-field measurements and other external variables (meteorological parameters, NOx, CO, SO2 ...). Surprisingly, road transport is not the dominant source by only explaining 15.8 % of measured VOC concentrations contrary to the local emission inventory. Other factors are toluene from solvent use (14.2 %), biogenic terpenes (7.8 %), natural gas evaporation (25.9 %), composed of butanes, and a last factor characterized by mixed regional emissions and composed of most of the species (36.3 %). The PMF results point out the influence of industrial emissions while there is no clear evidence of the impact of ship emissions on the measured VOC distribution. One reason might be the absence of IVOC in the input matrix; these compounds should be considered in future studies dealing with coastal urban areas. The sensitivity of PMF results on input data (time resolution, meteorological period, peak episode, uncertainty) was tested. While some PMF run are statistically less performant than the reference run, sensitivity tests show that same factors (number and type) are found with slightly different factor contributions (up to 15 % of change). Finally, the emission ratios (ER) of VOC relative to carbon monoxide (CO) were established. These ratios are consistent with those observed in Los Angeles within a factor of 2. These ER and the road transport factor from PMF were used to estimate VOC emissions and to evaluate three downscaled global emissions inventories (EDGAR, ACCMIP and MACCity). It was found that OVOC emissions were underestimated by a factor of 10 to 26 depending on the inventory. NMHC emission estimations were most of the time within the same range or overestimated by a 3 to 26-fold. In the road transport emission evaluation, EDGAR inventory was found to be better than ACCMIP inventory with most of the compounds within a range of 3 except for Like in TRANSEMED–Beirut (Lebanon), our work stresses the inadequacy of global emission inventories in the East Mediterranean and discrepancies between emission inventories themselves. There is an urgent need to better represent VOC emissions in this region including non-traffic sources, OVOC and lower volatility organic compounds. VOC emissions are expected to be much larger than expected and larger than Europe and North America.