Project Identification Details

Assessing the Anthropogenic and Biogenic Emissions Impact on Atmospheric Urban Fine Organic Particles in Eastern Romania. Solving the Challenge of the Aerosols Missing Mass as a One Step Forward Tool (acronym AI-FORECAST)

Evaluarea impactului emisiilor antropogene si biogene asupra particulelor organice fine dintr-un areal urban din estul României. Un pas înainte în rezolvarea provocărilor bilanţului masic neîncheiat

Project implementation period  12/07/2017-31/12/2019

Project financial value   850000.00 RON

                                                     ~185000 EUR

Project objective

The AI-FORECAST project was mainly aimed in addressing aspects related to the 7th Environment Action Program (EU), referring to a visionary approach for the 2020-2050 period in close relation to the climate change but also to the challenges related to ensuring the well-being of the environment and population. Through the activities carried out within the AI-FORECAST project, sustained efforts were made to improve the level of knowledge regarding the chemical composition of aerosol particles, discriminated by size, from long-term measurements undertaken in Iasi urban area, northeastern Romania.

The main objective of the AI-FORECAST project was to provide for the first time an adequate framework to respond correctly to the constraints of the current challenges and uncertainties related to the extremely complex organic entities, existing at the molecular level, in the fine particulate matter in the urban area of Iasi. To reach the general purpose and to ensure the project's sustainability, the problems of interest were addressed through 2 general objectives: i) chemical characterization of the inorganic and organic fraction of the fine aerosols, in order to improve the mass balance (for example for the fraction of 381 nm ~ 45 % of the total mass is not yet unidentified), and ii) sources apportionment by the use of appropriate statistical tools in order clearly to discriminate between the contributions made by the biogenic and anthropogenic sources to the atmospheric loading of inorganic and organic compounds from the fine aerosols in the urban area of Iasi.

Activities carried out within the project

The activities of the AI-FORECAST project focused mainly on:

-  continuous measurements at the Air Quality Monitoring Station (AMOS) of CERNESIM Center, "Alexandru Ioan Cuza" University of Iasi, to create a large database of aerosol samples segregated by size in the 0.0276 to 9.94 μm range with the help of a DEKATI low pressure operable impactor;

-    chemical speciation analyzes using techniques such as:

o   ion chromatography (IC) for the analysis of 16 water soluble ionic species, of which: 3 anionic species of organic nature (acetate, formate, oxalate), 7 anionic species of inorganic nature (fluoride, chloride, nitrite, bromide, nitrate, phosphate, sulfate) and 6 cationic species of inorganic nature (lithium, sodium, potassium, ammonium, magnesium and calcium);

o   inductive coupled plasma mass spectrometry (ICP-MS) for the analysis of specific isotopes for 26 water-soluble metal elements (9Be, 11B, 24Mg, 27Al, 51V, 52Cr, 55Mn, 56Fe, 59Co, 60Ni, 63Cu, 66Zn, 69Ga, 75As, 78Se, 85Rb, 88Sr, 95Mo, 107Ag, 114Cd, 125Te, 135Ba, 205Ti, 208Pb, 209Bi and 238U).

-      performing chemical analyzes using state-of-the-art techniques identified in the project methodology:

o   nuclear magnetic resonance (NMR) spectroscopy for identifying at qualitative level organic compounds present at molecular level in the aerosol samples collected and discriminated by size;

o    high performance liquid chromatography coupled with electrospray ionization source mass spectrometry and time of flight detection system (LC-ESI-ToF-MS);

o   online investigation of the chemical composition of aerosols in indoor / outdoor measurements by high-resolution time of flight mass spectrometry aerosol mass spectrometer (HR-ToF-AMS);

o testing of methods for the analysis of organic compounds present at molecular level in aerosol samples discriminated by size by mass spectrometry and gas chromatography techniques coupled with mass spectrometry.

-    use of appropriate statistical tools (multiple linear regression analysis, cluster analysis, principal component analysis) and ISORROPIA-II, PARGAN, HYSPLIT models, positive matrix factorization (PMF), Concentration Weighted Trajectory (CWT) and Bivariate Polar Plot (BPP)) for an in-depth analysis of the factors that control the levels of the particular matter in the investigated area:

o      the ISORROPIA-II thermodynamic equilibrium model was used to predict the pH of analyzed aerosol particles;

o  positive matrix factorization (PMF) analysis was used to identify the contributions of the various sources to the abundance of the particulate matter at the investigated location;

o methods associated with the analysis of air mass trajectories and, respectively, meteorological parameters, concentration weighted trajectory (CWT) and bivariate polar plot (BPP), were used to investigate the geographical origins of the air pollution in the urban area of Iasi, by ZeFir v.3.70 an Igor instrument based program;

o  RAIS health risk model was used to investigate the non-carcinogenic and carcinogenic risks to human health exerted by a series of water-soluble toxic heavy metals present in the PM2.5 fraction;

o   PARGAN (PARticle Growth and Nucleation) model was used to study the experimental dynamics of the aerosol population in close relation to the processes of nucleation and growth of aerosol particles.

Results

-    generation of a comprehensive long-term database on the chemical characteristics (ions, water soluble metals, organic compounds at molecular level) of the aerosols discriminated by size, collected in the urban area of Iasi, northeastern Romania;

-      identification of some critical parameters involved in the chemical processes responsible on the formation of new ultrafine particles and in the interconversion of some volatile species between the particulate and gas phases, processes governing the chemical composition of the aerosols from the atmosphere of the urban area of Iasi;

-     assigned emission sources responsible for the chemical composition of the water soluble fraction of the fine particulate matter in the area of interest. Five major sources contributing to the abundance of the particulate matter to the location of interest have been identified and attributed, in this case: secondary formation (factor 1, mainly ammonium sulphate), mineral and road dust + resuspended soil (factor 2), nitrate (factor 3, most probably in the predominant form of ammonium nitrate), traffic + industrial (factor 4) and combustion of biomass + NaCl / sea salt (factor 5);

-    correlation between the contributions of the identified sources with the meteorological parameters through concentration weighted trajectory (CWT) and bivariate polar plot (BPP) analyzes;

-    identification and demonstration of the role of pollution phenomenon as a result of transport processes from long distances (especially from areas that have global influences such as the Sahara desert, arid areas near the Black Sea and Mediterranean coasts, heavily industrialized areas, etc.);

-       evaluation for the first time of the non-carcinogenic and carcinogenic risks for human health, with a high carcinogenic risk for the As and Cr (VI) metals present in the fine particles at the location of interest;

-   development and optimization of a method for the identification and quantification for a series of organic compounds existing at the molecular level in the atmospheric aerosol particles in the urban area of Iasi (terebic acid, terpenyl acid, trans-norpinic acid, camphor-10-sulfonic acid, pinic acid, norpinonic acid, diatherebic acid acetate, camphoric acid, cis-pinonic acid, octylsulfate; 2-methylresorcinol, catechol, 5-methylresorcinol, 4-methylcatechol, 4-nitrocatechol, vanillin, benzoic acid, 2,6-dinitrophenol, 4-nitrophenol, 2,4-dinitrophenol, etc.) using high performance liquid chromatography coupled with time-of-flight mass spectrometry and electrospray ionization source (HPLC-ESI-ToF-MS);

-   determination of performance parameters (detection limits, quantification limits, recovery factors, linearity domains) specific to the chromatographic separations for the organic compounds identified in the analyzed aerosol sample matrices.

Conclusions

Determining the chemical composition of atmospheric particulate matter is essential for understanding its effects on climate change and human health in any location of the globe. Within the AI-FORECAST project for the particulate matter discriminated by size and collected in the urban area of Iasi, northeastern Romania, for the first time:

-       an exhaustive study was performed to characterize the chemical composition of PM2.5 and PM10 fractions;

-     the ionic balance was correctly interpreted by including in it, together with the experimentally determined variables, also of some parameters estimated using dedicated models (ISORROPIA-II);

-     predominant size modes in the 0.0276–9.94 μm equivalent aerodynamic diameter range, with maximum at 381 nm for the PM2.5 fraction and 1.6–2.39 μm for the PM10 fraction, were highlighted;

-    clear evidences were obtained on the role played by the meteorological factors (temperature, humidity, thickness of the mixing layer) in the chemical processing of the water-soluble ionic and metallic species existing in the investigated aerosol particles, but also in the process of forming new aerosols particles;

-    clear evidences were obtained on the importance of the contributions made by the transport of air masses over long distances for a series of air pollutants in relation to the potential local contributions;

-      the non-carcinogenic and carcinogence risks exerted by a series of toxic elements from the fine particulate matter in the area of interest on the human health were evaluated, with As and Cr (VI) being identified as critical elements in terms of carcinogenic risk;

-    a method has been developed for quantifying 21 possible compounds in atmospheric aerosol particles (terebic acid, 3-methyl-1,2,3 tricarboxylic butane, terpenyl acid, trans-norpinic acid, camphor-10-sulfonic acid, pinic acid, norpinonic acid, diatherebic acid acetate, camphoric acid, cis-pinonic acid, octylsulfate; 2-methylresorcinol, catechol, 5-methylresorcinol, 4-methylcatechol, 4-nitrocatechol, vanillin, benzoic acid, 2,6-dinitrophenol, 4 -nitrophenol, 2,4-dinitrophenol) using high performance liquid chromatography coupled with time-of-flight mass spectrometry and electrospray ionization source (HPLC-ESI-ToF-MS);

-    the elution conditions for the separation of the interest species, as well as the ionization source parameters were optimized to improve the sensitivity of the method;

-    tests were performed for the extraction of compounds from atmospheric aerosol samples and a number of performance parameters for the optimized method were estimated;

-  NMR analyzes were performed for a series of particulate matter samples extracted in deuterated solvents (water, methanol, acetonitrile, chloroform);

-    measurements have been made on the chemical composition of the aerosol particles existent in indoor environments using a high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS), after calibration of the sampling rate, particle size and of the ionization efficiency.

The activities undertaken within the AI-FORECAST project have significantly contributed to increase in the understanding of the impact exerted by the aerosol particles on the environmental conditions in the investigated area. The entire pool of generated data might constitute an excellent platform to be taken into account when developing environmental policies or when monitoring more precise climate changes at global level.

Keywords: aerosols, urban area, Iasi, northeastern Romania, ion chromatography, liquid chromatography, NMR, ICP-MS.

Note: The detailed description of the activities within the project is presented in the scientific activity reports related to each unique reporting stage.

Contributions with acknowledgments to the PN-III-P4-ID-PCE-2016-0299 / Contract no. 37/2017 (the project members are shown in blue in the presented contributions)

The activities carried out between 12.07.2017 – 31.12.2019, in accordance with the objectives of the project, have led to a series of results that have been the subject of articles published in international ISI quoted journals which have been disseminated through participation in national and international conferences. The table given below shows the number of publications and contributions that resulted directly from the AI-FORECAST project activities.

The project team included as staff: prof. dr. habil. Cecilia Arsene (coordinator), prof. dr. habil. Romeo-Iulian Olariu (member), assoc. prof. dr. Iustinian Gabriel Bejan, assoc. prof. dr. Simona Maria Cucu Man (member), dr. Violeta Mangalagiu (member), dr. Catalina Ciobanu, PhD student Alina Giorgiana Galon-Negru, PhD student Cornelia Amarandei. The team members have made significant contributions to the project activities.

Taking into account the proposed objectives and the results of the activities carried out, a 100% achievement degree is assigned for the 12.07.2017 - 31.12.2019 implementation period of the AI-FORECAST project.