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Air pollution survey across the western Mediterranean Sea: overview on oxygenated volatile hydrocarbons (OVOCs) and other gaseous pollutants

  • Francesca VichiEmail author
  • Andrea Imperiali
  • Massimiliano Frattoni
  • Mattia Perilli
  • Paolo Benedetti
  • Giulio Esposito
  • Angelo Cecinato
Research Article
  • 38 Downloads

Abstract

Despite the Mediterranean Sea basin is among the most sensitive areas over the world for climate change and air quality issues, it still remains less studied than the oceanic regions. The domain investigated by the research ship Minerva Uno cruise in Summer 2015 was the Tyrrhenian Sea. An overview on the marine boundary layer (MBL) concentration levels of carbonyl compounds, ozone (O3), and sulfur dioxide (SO2) is reported. The north-western Tyrrhenian Sea samples showed a statistically significant difference in acetone and SO2 concentrations when compared to the south-eastern ones. Acetone and SO2 values were higher in the southern part of the basin; presumably, a blend of natural (including volcanism) and anthropogenic (shipping) sources caused this difference. The mean acetone concentration reached 5.4 μg/m3; formaldehyde and acetaldehyde means were equal to 1.1 μg/m3 and 0.38 μg/m3, respectively. Maximums of 3.0 μg/m3 for formaldehyde and 1.0 μg/m3 for acetaldehyde were detected along the route from Civitavecchia to Fiumicino. These two compounds were also present at levels above the average in proximity of petrol-refining plants on the coast; in fact, formaldehyde reached 1.56 μg/m3 and 1.60 μg/m3, respectively, near Milazzo and Augusta harbors; meanwhile, acetaldehyde was as high as 0.75 μg/m3 at both sites. The levels of formaldehyde agreed with previously reported measurements over Mediterranean Sea and elsewhere; besides, a day/night trend was observed, confirming the importance of photochemical formation for this pollutant. According to this study, Mediterranean Sea basin, which is a closed sea, was confirmed to suffer a high anthropic pressure impacting with diffuse emissions, while natural contribution to pollution could come from volcanic activity, particularly in the south-eastern Tyrrhenian Sea region.

Keywords

Oxygenated volatile organic compounds (OVOCs) Sulfur dioxide Ozone Mediterranean Sea Principal component analysis (PCA) Marine boundary layer (MBL) 

Notes

Acknowledgments

We gratefully acknowledge the staff of the RV MINERVA UNO vessel for technical assistance and our colleague dr. Francesca Sprovieri, responsible for the cruise planning and logistics, who shared the automatic analyzers dataset.

Funding

This work was carried out in the framework of the MED-OCEANOR project funded by the Italian National Research Council (CNR).

References

  1. Arnold SR, Chipperfield MP, Blitz MA (2005) A three-dimensional model study of the effect of new temperature-dependent quantum yields for acetone photolysis. J Geophys Res 110:D22305.  https://doi.org/10.1029/2005JD005998 Google Scholar
  2. Bottenheim JW, Barrie LA, Atlas E, Heidt LE, Niki H, Rasmussen RA, Shepson PB (1990) Depletion of lower tropospheric ozone during arctic spring - the polar sunrise experiment 1988. J Geophys Res Atmos 95(D11):18555–18568Google Scholar
  3. Braeken J, van Assen MALM (2017) An empirical Kaiser criterion. Psychol Methods 22(3):450–466Google Scholar
  4. Castagna J, Bencardino M, D’Amore F, Esposito G, Pirrone N, Sprovieri F (2018) Atmospheric mercury species measurements across the Western Mediterranean region: behaviour and variability during a 2015 research cruise campaign. Atmos Environ 173:108–126Google Scholar
  5. Cesari D, Genga A, Ielpo P, Siciliano M, Mascolo G, Grasso FM, Contini D (2014) Source apportionment of PM2.5 in the harbor-industrial area of Brindisi (Italy): identification and estimation of the contribution of in-port ship emissions. Sci Total Environ 497:392–400Google Scholar
  6. Ciuraru R, Fine L, van Pinxteren M, D’Anna B, Herrmann H, George C (2015) Unravelling new processes at interfaces: photochemical isoprene production at the sea surface. Environ Sci Technol 49(22):13199–13205Google Scholar
  7. de Laat ATJ, de Gouw JA, Lelieveld J, Hansel A (2001) Model analysis of trace gas measurements and pollution impact during INDOEX. J Geophys Res 106(D22):28469–28480Google Scholar
  8. Derstroff B, Sander R, Hueser I, Parchatka U, Bourtsoukidis E, Crowley JN, Fischer H, Phillips GJ, Schuladen J, Mallik C, Harder H, Sauvage C, Stönner C, Kesselmeier J, Lelieveld J, Williams J (2016) Volatile organic compounds (VOCs) in photochemically aged air the Eastern and Western Mediterranean. Atmos Chem Phys Discuss in preparationGoogle Scholar
  9. Doche C, Dufour G, Foret G, Eremenko M, Cuesta J, Beekmann M, Kalabokas P (2014) Summertime tropospheric-ozone variability over the Mediterranean basin observed with IASI. Atmos Chem Phys 14:10589–10600Google Scholar
  10. Economou C, Mihalopoulos N (2002) Formaldehyde in the rainwater in the eastern Mediterranean: occurrence, deposition and contribution to organic carbon budget. Atmos Environ 36(8):1337–1347Google Scholar
  11. EU Directive 2005/33/EC of the European Parliament and of the Council of 6 July 2005 amending Directive 1999/32/EC. Official Journal of the European Union L191/59Google Scholar
  12. EU Directive 2016/802/EU of the European Parliament and of the Council of 11 May 2016 relating to a reduction in the sulphur content of certain liquid fuels (codification). Official Journal of the European Union L132/58Google Scholar
  13. EU Drective 2012/33/EU of the European Parliament and of the Council of 21 November 2012 amending Directive 1999/32/EC as regards the sulphur content of marine fuels L 327/1Google Scholar
  14. Feng Y, Wen S, Chen Y, Wang X, Lü H, Bi X, Sheng G, Fu J (2005) Ambient levels of carbonyl compounds and their sources in Guangzhou, China. Atmos Environ 39:1789–1800Google Scholar
  15. Fleming ZL, Monks PS, Manning AJ (2012) Review: untangling the influence of air-mass history in interpreting observed atmospheric composition. Atmos Res 104–105:1–39Google Scholar
  16. Gencarelli CN, Hedgecock IM, Sprovieri F, Schürmann GJ, Pirrone N (2014) Importance of ship emissions to local summertime ozone production in the Mediterranean marine boundary layer: a modeling study. Atmosphere 5(4):937–958Google Scholar
  17. Giovannoni SJ, Hayakawa DH, Tripp HJ, Stingl U, Givan SA, Cho JC, Oh HM, Kitner JB, Vergin KL, Rappe MS (2008) The small genome of an abundant coastal ocean methylotroph. Environ Microbiol 10(7):1771–1782Google Scholar
  18. Hedgecock IM, Gencarelli CN, Schürmann GJ, Sprovieri F, Pirrone N (2012) Measurements and modelling of ozone in the Mediterranean MBL: an investigation of the importance of ship emissions to local ozone production. Atmos Chem Phys Discuss 12:16557–16602Google Scholar
  19. Ho SSH, Chow JC, Watson JG, Ip HSS, Ho KF, Dai WT, Cao J (2014) Biases in ketone measurements using DNPH-coated solid sorbent cartridges anal. Methods 2014(6):967–974Google Scholar
  20. Jacob DJ, Field BD, Jin EM, Bey I, Li Q, Logan JA, Yantosca R, Singh HB (2002) Atmospheric budget of acetone. J Geophys Res 107(D10):1–17Google Scholar
  21. Jiang Z, Grosselin B, Daële V, Mellouki A, Mu Y (2016) Seasonal, diurnal and nocturnal variations of carbonyl compounds in the semi-urban environment of Orléans, France. J Environ Sci 40:84–91Google Scholar
  22. Johansson L, Jalkanen J-P, Kukkonen J (2017) Global assessment of shipping emissions in 2015 on a high spatial and temporal resolution. Atmos Environ 167:403–415Google Scholar
  23. Kettle AJ, Andreae MO, Amouroux D, Andreae TW, Bates TS, Berresheim H, Bingemer H, Boniforti R, Curran MAJ, DiTullio GR, Helas G, Jones GB, Keller MD, Kiene RP, Leck C, Levasseur M, Malin G, Maspero M, Matrai P, McTaggart AR, Mihalopoulos N, Nguyen BC, Novo A, Putaud JP, Rapsomanikis S, Roberts G, Schebeske G, Sharma S, Simo R, Staubes R, Turner S, Uher G (1999) A global database of sea surface dimethylsulfide (DMS) measurements and a procedure to predict sea surface DMS as a function of latitude, longitude, and month. Glob Biogeochem Cycles 13:399–444Google Scholar
  24. Kieber DJ, McDaniel J, Mopper K (1989) Photochemicl source of biological substrates in sea water: implications for carbon cycling. Nature 341:637–639Google Scholar
  25. Kieber RJ, Rhines MF, Willey JD, Avery GB (1999) Rainwater formaldehyde: concentration, deposition and photochemical formation. Atmos Environ 33(22):3659–3667Google Scholar
  26. Lelieveld J, Berresheim H, Borrmann S, Crutzen PJ, Dentener FJ, Fischer H, Feichter J, Flatau PJ, Heland J, Holzinger R, Korrmann R, Lawrence MG, Levin Z, Markowicz KM, Mihalopoulos N, Minikin A, Ramanathan V, de Reus M, Roelofs GJ, Scheeren HA, Sciare J, Schlager H, Schultz M, Siegmund P, Steil B, Stephanou EG, Stier P, Traub M, Warneke C, Williams J, Ziereis H (2002) Global air pollution crossroads over the Mediterranean. Science 298:794–799Google Scholar
  27. Lewis AC, Hopkins JR, Carpenter LJ, Stanton J, Read KA, Pilling MJ (2005) Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic marine air. Atmos Chem Phys 5:1963–1974Google Scholar
  28. Lui KH, Ho SSH, Louie PKK, Chan CS, Lee SC, Hu D, Chan PW, Lee JCW, Ho KF (2017) Seasonal behaviour of carbonyls and source characterization of formaldehyde (HCHO) in ambient air. Atmos Environ 152:51–60Google Scholar
  29. Marandino CA, De Bruyn WJ, Miller SD, Prather MJ, Saltzman ES (2005) Oceanic uptake and the global atmospheric acetone budget. Geophys Res Lett 32(15):L15806 1–4Google Scholar
  30. Merico E, Gambaro A, Argiriou A, Alebic-Juretic A, Barbaro E, Cesari D, Chasapidis L, Dimopoulos S, Dinoi A, Donateo A, Giannaros C, Gregoris E, Karagiannidis A, Konstandopoulos AG, Ivošević T, Liora N, Melas D, Mifka B, Orlić I, Poupkou A, Sarovic K, Tsakis A, Giua R, Pastore T, Nocioni A, Contini D (2017) Atmospheric impact of ship traffic in four Adriatic-Ionian port-cities: comparison and harmonization of different approaches. Transp Res Part D: Transp Environ 50:431–445Google Scholar
  31. Michoud V, Sciare J, Sauvage S, Dusanter S, Léonardis T, Gros V, Kalogridis C, Zannoni N, Féron A, Petit J-E, Crenn V, Baisnée D, Sarda-Estève R, Bonnaire N, Marchand N, DeWitt HL, Pey J, Colomb A, Gheusi F, Szidat S, Stavroulas I, Borbon A, Locoge N (2017) Organic carbon at a remote site of the western Mediterranean Basin:sources and chemistry during the ChArMExSOP2 field experiment. Atmos Chem Phys 17:8837–8865Google Scholar
  32. Millan MM, Salvador R, Mantilla E, Kallos G (1997) Photooxidant dynamics in the Mediterranean basin in summer: results from European research projects. J Geophys Res 102(D7):8811–8823Google Scholar
  33. Millet DB, Guenther A, Siegel DA, Nelson NB, Singh HB, de Gouw JA, Warneke C, Williams J, Eerdekens G, Sinha V, Karl T, Flocke F, Apel E, Riemer DD, Palmer PI, Barkley M (2010) Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations. Atmos Chem Phys 10:3405–3425.  https://doi.org/10.5194/acp-10-3405-2010 Google Scholar
  34. Mopper K, Stahovec WL (1986) Sources and sinks of low molecular weight organic carbonyl compounds in seawater. Mar Chem 19(4):305–321Google Scholar
  35. Mopper K, Zhou XL, Kieber RJ, Kieber DJ, Sikorski RJ, Jones RD (1991) Photochemical degradation of dissolved organic carbon and its impact on the oceanic carbon cycle. Nature 353:60–62Google Scholar
  36. Nemecek-Marshall M, Wojciechowski C, Kuzma J, Silver GM, Fall R (1995) Marine Vibrio species produce the volatile organic compound acetone. Appl Environ Microbiol 61(1):44–47Google Scholar
  37. Nemecek-Marshall M, Wojciechowski C, Wagner WP, Fall R (1999) Acetone formation in the Vibrio family: a new pathway for bacterial leucine catabolism. J Bacteriol 181(24):7493–7499Google Scholar
  38. Nuccio J, Seaton PJ, Kieber RJ (1995) Biological production of formaldehyde in the marine environment. Limnol Oceanogr 40(3):521–527Google Scholar
  39. Obernosterer I, Kraay G, de Ranitz E, Herndl GJ (1999) Concentrations of low molecular weight carboxylic acids and carbonyl compounds in the Aegean Sea (Eastern Mediterranean) and the turnover of pyruvate. Aquat Microb Ecol 20(2):147–156Google Scholar
  40. Olmer N, Comer B, Roy B, Mao X, Rutherford D (2017) ICCT report: greenhouse gas emissions from global shipping, 2013–2015Google Scholar
  41. Pang X, Mu Y (2006) Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air. Atmos Environ 40:6313–6320Google Scholar
  42. Possanzini M, Tagliacozzo G, Cecinato A (2007) Ambient levels and sources of lower carbonyls at Montelibretti, Rome (Italy). Water Air Soil Pollut 183:447–454Google Scholar
  43. Read KA, Carpenter LJ, Arnold SR, Beale R, Nightingale PD, Hopkins JR, Lewis AC, Lee J, Mendes DL, Pickering SJ (2012) Multiannual observations of acetone, methanol, and acetaldehyde in remote tropical Atlantic air: implications for atmospheric OVOC budgets and oxidative capacity. Environ Sci Technol 12(46):11028–11039Google Scholar
  44. Riemer DD, Milne PJ, Zika RG, Pos WH (2000) Photoproduction of nonmethane hydrocarbons (NMHCs) in seawater. Mar Chem 71(3–4):177–198Google Scholar
  45. Romagnoli P, Balducci C, Perilli M, Perreca E, Cecinato A (2016) Particulate PAHs and n-alkanes in the air over Southern and Eastern Mediterranean Sea. Chemosphere 159:516–525Google Scholar
  46. Romagnoli P, Vichi F, Balducci C, Imperiali A, Perilli M, Paciucci L, Petracchini F, Cecinato A (2017) Air quality study in the coastal city of Crotone (Southern Italy) hosting a small-size harbor. Environ Sci Pollut Res Int 24(32):25260–25275Google Scholar
  47. Salisbury G, Williams J, Holzinger R, Gros V, Mihalopoulos N, Vrekoussis M, Sarda-Esteve R, Berresheim H, von Kuhlmann R, Lawrence M, Lelieveld J (2003) Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July-August 2001. Atmos Chem Phys 3:925–940Google Scholar
  48. Sartin JH, Halsall CJ, Robertson LA, Gonard RG, MacKenzie AR (2002) Temporal patterns, sources, and sinks of C8-C16 hydrocarbons in the atmosphere of Mace Head, Ireland. J Geophys Res 107(D19):8099.  https://doi.org/10.1029/2000JD000232 Google Scholar
  49. Schwandner FM, Seward TM, Gize AP, Hall PA, Dietrich VJ (2004) Diffuse emission of organic trace gases from the flank and crater of a quiescent active volcano (Vulcano, Aeolian Islands, Italy). J Geophys Res 109:D04301.  https://doi.org/10.1029/2003JD003890 Google Scholar
  50. Shepson PB, Hastie DR, Schiff HI, Polizzi M, Bottenheim JW, Anlauf K, Mackay GI, Karecki DR (1991) Atmospheric concentrations and temporal variations of C1-C3 carbonyl compounds at two rural sites in central Ontario. Atmos Environ 25A:2001–2015Google Scholar
  51. Shepson PB, Sirju A-P, Hopper JR, Barrie LA, Young V, Niki H, Dryfhout H (1996) Sources and sinks of carbonyl compounds in the Arctic Ocean boundary layer: polar ice floe experiment. J Geophys Res 101(D15):21081–21089Google Scholar
  52. Singh H, Chen Y, Staudt A, Jacob D, Blake D, Heikes B, Snow J (2001) Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds. Nature 410:1078–1081Google Scholar
  53. Singh HB, Tabazadeh A, Evans MJ, Field BD, Jacob DJ, Sachse G, Crawford JH, Shetter R, Brune WH (2003) Oxygenated volatile organic chemicals in the oceans: Inferences and implications based on atmospheric observations and air-sea exchange models. Geophys Res Lett 30(16):13-1Google Scholar
  54. Solberg S, Dye C, Schmidbauer N, Herzog A, Gehrig R (1996) Carbonyls and nonmethane hydrocarbons at rural European sites from the Mediterranean to the Arctic. J Atmos Chem 25:33–66Google Scholar
  55. Stein AF, Draxler RR, Rolph GD, Stunder BJB, Cohen MD, Ngan F (2015) NOAA’s HYSPLIT atmospheric transport and dispersion modeling system. Bull Am Meteorol Soc 96:2059–2077Google Scholar
  56. Tanner RL, Zielinska B, Uberna E, Harshfield G (1996) Concentrations of carbonyl compounds and the carbon isotopy of formaldehyde at a coastal site in Nova Scotia during the NARE summer intensive. J Geophys Res 101(D22):28,961–28,970Google Scholar
  57. Wang C, Huang X-F, Han Y, Zhu B, He L-Y (2017) Sources and potential photochemical roles of formaldehyde in an urban atmosphere in South China. J Geophys Res 122(11):934–11,947Google Scholar
  58. Warneck P (2000) Chemistry of the natural atmosphere. Academic Press, San Diego, 927 ppGoogle Scholar
  59. Wichard T, Poulet SA, Pohnert G (2005) Determination and quantification of a,b,g,d-unsaturated aldehydes as pentafluorobenzyl-oxime derivates in diatom cultures and natural phytoplankton populations: application in marine field studies. J Chromatogr B 814(1):155–161Google Scholar
  60. Williams J, Holzinger R, Gros V, Xu X, Atlas E, Wallace DWR (2004) Measurements of organic species in air and seawater from the tropical Atlantic. Geophys Res Lett 31(23):L23S06 1–5Google Scholar
  61. Wisthaler A, Hansel A, Dickerson RR, Crutzen PJ (2002) Organic trace gas measurements by PTR-MS during INDOEX 1999Google Scholar
  62. Xu Z, Liu J, Zhang Y, Liang P, Mu Y (2010) Ambient levels of atmospheric carbonyls in Beijing during the 2008 Olympic games. J Environ Sci 22:1348–1356Google Scholar
  63. Yamazaki T, Tsugawa W, Sode K (2001) Biodegradation of formaldehyde by a formaldehyde-resistant bacterium isolated from seawater. Appl Biochem Biotechnol 91-3:213–217Google Scholar
  64. Zhou X, Mopper K (1990) Apparent partition coefficients of 15 carbonyl compounds between air and seawater and between air and freshwater; implications for air-sea exchange. Environ Sci Technol 24:1864–1869Google Scholar
  65. Zhou XL, Mopper K (1993) Carbonyl compounds in the lower marine troposphere over the Caribbean Sea and Bahamas. J Geophys Res Oceans 98(C2):2385–2392 99Google Scholar
  66. Zhou XL, Mopper K (1997) Photochemical production of low molecular weight carbonyl compounds in seawater and surface microlayer and their air-sea exchange. Mar ChemMar Chem. 56(3–4):201–213Google Scholar

Web references

  1. http://www.arl.noaa.gov/ready/. Last accessed 23/01/2019

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Authors and Affiliations

  1. 1.National Research Council of ItalyInstitute of Atmospheric Pollution Research (CNR.IIA)MonterotondoItaly

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