Abstract
This study characterizes carbonyls (RCHO), polycyclic aromatic hydrocarbons (PAHs), their nitrated (nitro-PAHs) and alkylated (alkyl-PAHs) in particulate matter in the exhaust emissions of a diesel engine. The measurements were made with a standard engine, often found in vans used in Brazil, fueled with pure commercial diesel and mixtures of 10, 20, and 30% biodiesel with 2, 4, and 6% of ethanol. Particulate matter sampling was carried out with a 10-stage cascade impactor. Chemical analyses for PAHs and their derivatives were conducted using gas phase chromatography-mass spectrometry (GC/MS). RCHO were sampled using impingers with 2,4-DNPH and analyzed using HPLC with UV detection. The results showed that emissions of all the PAHs and their derivatives were reduced with the use of biodiesel and ethanol, with the exception of the blend of 30% biodiesel with 4% ethanol. However, all the RCHO emissions increased with biodiesel and ethanol. High correlations were observed between the emissions of PAHs, alkyl-PAHs and nitro-PAHs, which suggests a similarity in the formation mechanisms of these compounds. All PAHs’ emissions have a strong negative correlation with biodiesel content and with RCHO emissions and a medium correlation with ethanol content. In contrast, biodiesel and ethanol with the RCHO emissions lead to a positive correlation coefficient of these compounds which is more pronounced for biodiesel than ethanol.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
Not applicable.
References
ABNT NBR 6601 (2012) Light road vehicles — Determination of hydrocarbon, carbon monoxide, nitrogen oxide, carbon dioxide and particulate material on exhaust gas, Rio de Janeiro, Brazil. https://www.abntcatalogo.com.br/pnm.aspx?Q=ekJqQ1dmUGNmQmY4ZEVSamVNcnhobkFoSVVxNzFNUmJUQWpMQnp1UTFwOD0=
Alves CA, Vicente AMP, Gomes J, Nunes T, Duarte M, Bandowe BAM (2016) Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated-PAHs, nitrated-PAHs and azaarenes) in size-fractionated particles emitted in an urban road tunnel. Atmos Res 180:128–137. https://doi.org/10.1016/j.atmosres.2016.05.013
Arias S, Molina F, Palacio R, López D, Agudelo JR (2022) Assessment of carbonyl and PAH emissions in an automotive diesel engine fueled with butanol and renewable diesel fuel blends. Fuel 316:123290. https://doi.org/10.1016/j.fuel.2022.123290
ASTM, (2019). ASTM D445–19a, Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity). ASTM International. https://doi.org/10.1520/D0445-19A
ASTM, (2017). ASTM D6584 - Standard Test Method for Determination of Total Monoglycerides, Total Diglycerides, Total Triglycerides, and Free and Total Glycerin in B-100 Biodiesel Methyl Esters by Gas Chromatography [WWW Document]. Annual Book of ASTM Standardshttps://doi.org/10.1520/D6584-13E01
ASTM International, (2018). Test Methods for Flash Point By Pensky-Martens Closed Cup Tester. D93–18. https://doi.org/10.1520/D0093-11.
ASTM:D1298-12b, (2012). Standard Test Method for Density, Relative Density, or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method. ASTM Internationalhttps://doi.org/10.1520/D1298-12B.2
Ballesteros R, Hernández JJ, Guillén-Flores J (2012) Carbonyls speciation in a typical European automotive diesel engine using bioethanol/butanol–diesel blends. Fuel 95:136–145. https://doi.org/10.1016/j.fuel.2011.09.012
Bamford HA, Baker JE (2003) Nitro-polycyclic aromatic hydrocarbon concentrations and sources in urban and suburban atmospheres of the Mid-Atlantic region. Atmos Environhttps://doi.org/10.1016/S1352-2310(03)00102-X
Bório HF, Penteado R, Daemme LC, Godoi R, Errera MR, Corrêa SM (2019) Criteria and aldehyde emissions from a diesel Euro V engine using diesel/biodiesel blends in Brazil. Environmental Science and Pollution Researchhttps://doi.org/10.1007/s11356-019-04345-5
Borrás E, Tortajada-Genaro LA, Vázquez M, Zielinska B (2009) Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions. Atmos Environhttps://doi.org/10.1016/j.atmosenv.2009.08.010
Burtscher H (2005) Physical characterization of particulate emissions from diesel engines: A review. J Aerosol Scihttps://doi.org/10.1016/j.jaerosci.2004.12.001
Casal CS, Arbilla G, Corrêa SM (2014) Alkyl polycyclic aromatic hydrocarbons emissions in diesel/biodiesel exhaust. Atmos Environ 96:107–116. https://doi.org/10.1016/j.atmosenv.2014.07.028
Corrêa SM, Arbilla G (2008) Carbonyl emissions in diesel and biodiesel exhaust. Atmos Environ 42:769–775. https://doi.org/10.1016/j.atmosenv.2007.09.073
Corrêa SM, Arbilla G (2006) Aromatic hydrocarbons emissions in diesel and biodiesel exhaust. Atmos Environ 40:6821–6826. https://doi.org/10.1016/j.atmosenv.2006.05.068
Corrêa SM, Arbilla G, da Silva CM, Martins EM, de Souza SLQ (2021) Determination of size-segregated polycyclic aromatic hydrocarbon and its nitro and alkyl analogs in emissions from diesel-biodiesel blends. Fuel 283:118912. https://doi.org/10.1016/j.fuel.2020.118912
Corrêa SM, Martins EM, Arbilla G (2003) Formaldehyde and acetaldehyde in a high traffic street of Rio de Janeiro, Brazil. Atmos Environ 37:23–29. https://doi.org/10.1016/S1352-2310(02)00805-1
da Silva, D.B.N., Martins, E.M., Corrêa, S.M., (2016). Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro, Brazil. Environ Monit Assess 188. https://doi.org/10.1007/s10661-016-5278-3
De Abrantes R, De Assunção JV, Pesquero CR (2004) Emission of polycyclic aromatic hydrocarbons from light-duty diesel vehicles exhaust. Atmos Environhttps://doi.org/10.1016/j.atmosenv.2003.11.012
Eiguren-Fernandez A, Miguel AH, Froines JR, Thurairatnam S, Avol EL (2004) Seasonal and spatial variation of polycyclic aromatic hydrocarbons in vapor-phase and PM2.5 in Southern California urban and rural communities. Aerosol Sci Technol. https://doi.org/10.1080/02786820490449511
Eiguren-Fernandez A, Miguel AH, Lu R, Purvis K, Grant B, Mayo P, Di Stefano E, Cho AK, Froines J (2008) Atmospheric formation of 9,10-phenanthraquinone in the Los Angeles air basin. Atmos Environhttps://doi.org/10.1016/j.atmosenv.2007.12.029
Finlayson-Pitts BJ, Pitts JN (2000) Global Tropospheric Chemistry and Climate Change, in: Chemistry of the Upper and Lower Atmosphere. https://doi.org/10.1016/b978-012257060-5/50016-2
Guarieiro ALN, Santos JVDS, Eiguren-Fernandez A, Torres EA, da Rocha GO, de Andrade JB (2014) Redox activity and PAH content in size-classified nanoparticles emitted by a diesel engine fuelled with biodiesel and diesel blends. Fuelhttps://doi.org/10.1016/j.fuel.2013.08.029
Guarieiro LLN, de Souza AF, Torres EA, de Andrade JB (2009) Emission profile of 18 carbonyl compounds, CO, CO2, and NO emitted by a diesel engine fuelled with diesel and ternary blends containing diesel, ethanol and biodiesel or vegetable oils. Atmos Environ 43:2754–2761. https://doi.org/10.1016/j.atmosenv.2009.02.036
Guarieiro LLN, de Pereira PA, P., Torres, E.A., da Rocha, G.O., de Andrade, J.B., (2008) Carbonyl compounds emitted by a diesel engine fuelled with diesel and biodiesel–diesel blends: Sampling optimization and emissions profile. Atmos Environ 42:8211–8218. https://doi.org/10.1016/j.atmosenv.2008.07.053
He C, Ge Y, Tan J, You K, Han X, Wang J (2010) Characteristics of polycyclic aromatic hydrocarbons emissions of diesel engine fueled with biodiesel and diesel. Fuelhttps://doi.org/10.1016/j.fuel.2010.03.014
Hu S, Herner JD, Robertson W, Kobayashi R, Chang MCO, Huang S. Mei, Zielinska B, Kado N, Collins JF, Rieger P, Huai T, Ayala A (2013) Emissions of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs from heavy-duty diesel vehicles with DPF and SCR. J Air Waste Manage Assochttps://doi.org/10.1080/10962247.2013.795202
Kang H-J, Lee S-Y, Kwon J-H (2016) Physico-chemical properties and toxicity of alkylated polycyclic aromatic hydrocarbons. J Hazard Mater 312:200–207. https://doi.org/10.1016/j.jhazmat.2016.03.051
Karavalakis G, Boutsika V, Stournas S, Bakeas E (2011) Biodiesel emissions profile in modern diesel vehicles. Part 2: Effect of biodiesel origin on carbonyl, PAH, nitro-PAH and oxy-PAH emissions. Sci Total Environ 409:738–747. https://doi.org/10.1016/j.scitotenv.2010.11.010
Keyte IJ, Albinet A, Harrison RM (2016) On-road traffic emissions of polycyclic aromatic hydrocarbons and their oxy- and nitro- derivative compounds measured in road tunnel environments. Sci Total Environ 566–567:1131–1142. https://doi.org/10.1016/j.scitotenv.2016.05.152
Khalili NR, Scheff PA, Holsen TM (1995) PAH source fingerprints for coke ovens, diesel and gasoline engines, highway tunnels, and wood combustion emissions. Atmos Environ 29:533–542. https://doi.org/10.1016/1352-2310(94)00275-P
Li J, Xu H, Song D, Wang Z, Zhang B, Feng R, Gu Y, Jiang Z, Ji X, Liu S, Ho SSH, Qu L, Sun F (2022) Emission characteristics and assessment of potential health risks on PM2.5-bound organics from incense burning. Atmos Pollut Res 13, 101326. https://doi.org/10.1016/j.apr.2022.101326
Li R, Wang Z, Xu G (2017) Study on Carbonyl Emissions of Diesel Engine Fueled with Biodiesel. Int J Chem Eng 2017:1–12. https://doi.org/10.1155/2017/1409495
Marr LC, Kirchstetter TW, Harley RA, Miguel AH, Hering SV, Hammond SK (1999) Characterization of polycyclic aromatic hydrocarbons in motor vehicle fuels and exhaust emissions. Environ Sci Technolhttps://doi.org/10.1021/es981227l
Martins EM, Arbilla G, Bauerfeldt GF, de Paula M (2007) Atmospheric levels of aldehydes and BTEX and their relationship with vehicular fleet changes in Rio de Janeiro urban area. Chemosphere 67:2096–2103. https://doi.org/10.1016/j.chemosphere.2006.09.088
Martins LD, Da Silva Júnior CR, Solci MC, Pinto JP, Souza DZ, Vasconcellos P, Guarieiro ALN, Guarieiro LLN, Sousa ET, De Andrade JB (2012) Particle emission from heavy-duty engine fuelled with blended diesel and biodiesel. Environ Monit Assesshttps://doi.org/10.1007/s10661-011-2142-3
Pang X, Mu Y, Yuan J, He H (2008) Carbonyls emission from ethanol-blended gasoline and biodiesel-ethanol-diesel used in engines. Atmos Environ 42:1349–1358. https://doi.org/10.1016/j.atmosenv.2007.10.075
Pies C, Hoffmann B, Petrowsky J, Yang Y, Ternes TA, Hofmann T (2008) Characterization and source identification of polycyclic aromatic hydrocarbons (PAHs) in river bank soils. Chemosphere 72:1594–1601. https://doi.org/10.1016/j.chemosphere.2008.04.021
R Development Core Team, (2017). R: A language and environment for statistical computing. Vienna, Austria. R Foundation for Statistical Computing, Vienna, Austria. ISBN 3–900051–07–0, URL http://www.R-project.org.
Rajput N, Lakhani A (2009) PAHs and their Carcinogenic Potencies in Diesel Fuel and Diesel Generator Exhaust. Human Ecol Risk Assesshttps://doi.org/10.1080/10807030802615980
Ravindra K, Sokhi R, Vangrieken R (2008) Atmospheric polycyclic aromatic hydrocarbons: Source attribution, emission factors and regulation. Atmos Environ 42:2895–2921. https://doi.org/10.1016/j.atmosenv.2007.12.010
Soclo HH, Garrigues P, Ewald M (2000) Origin of Polycyclic Aromatic Hydrocarbons (PAHs) in Coastal Marine Sediments: Case Studies in Cotonou (Benin) and Aquitaine (France) Areas. Mar Pollut Bull 40:387–396. https://doi.org/10.1016/S0025-326X(99)00200-3
Song C, Zhao Z, Lv G, Song J, Liu L, Zhao R (2010) Carbonyl compound emissions from a heavy-duty diesel engine fueled with diesel fuel and ethanol–diesel blend. Chemosphere 79:1033–1039. https://doi.org/10.1016/j.chemosphere.2010.03.061
Souza CV, Corrêa SM (2016) Polycyclic aromatic hydrocarbons in diesel emission, diesel fuel and lubricant oil. Fuel 185:925–931. https://doi.org/10.1016/j.fuel.2016.08.054
Souza CV, Corrêa SM (2015) Polycyclic aromatic hydrocarbon emissions in diesel exhaust using gas chromatography-mass spectrometry with programmed temperature vaporization and large volume injection. Atmos Environ 103:222–230. https://doi.org/10.1016/j.atmosenv.2014.12.047
Standard Test Method for Determination of Water in Petroleum Products , Lubricating Oils , and Additives by Coulometric Karl Fischer Titration ASTM D6304-16. Annual Book of ASTM Standardshttps://doi.org/10.1520/D6304-16.2
Tsai JH, Chen SJ, Huang KL, Lin YC, Lee WJ, Lin CC, Lin WY (2010) PM, carbon, and PAH emissions from a diesel generator fuelled with soy-biodiesel blends. J Hazard Mater. https://doi.org/10.1016/j.jhazmat.2010.02.085
Wang L, Atkinson R, Arey J (2007) Formation of 9,10-phenanthrenequinone by atmospheric gas-phase reactions of phenanthrene. Atmos Environhttps://doi.org/10.1016/j.atmosenv.2006.11.008
WHO-IARC (2006) IARC Monographs on the Evaluation of carcinogenic Risks to Humans. WHO, Lyon
Yang P-M, Lin Y-C, Lin KC, Jhang S-R, Chen S-C, Wang C-C, Lin Y-C (2015) Comparison of carbonyl compound emissions from a diesel engine generator fueled with blends of n-butanol, biodiesel and diesel. Energy 90:266–273. https://doi.org/10.1016/j.energy.2015.06.070
Zhang J, Cai L, Yuan D, Chen M (2004) Distribution and sources of polynuclear aromatic hydrocarbons in Mangrove surficial sediments of Deep Bay, China. Mar Pollut Bull 49:479–486. https://doi.org/10.1016/j.marpolbul.2004.02.030
Zhang Y, Shen Z, Sun J, Zhang L, Zhang B, Zhang T, Wang J, Xu H, Liu P, Zhang N, Cao J (2020) Parent, alkylated, oxygenated and nitro polycyclic aromatic hydrocarbons from raw coal chunks and clean coal combustion: Emission factors, source profiles, and health risks. Sci Total Environ 721:137696. https://doi.org/10.1016/j.scitotenv.2020.137696
Zhao J, Zhang Y, Wang T, Sun L, Yang Z, Lin Y, Chen Y, Mao H (2019) Characterization of PM2.5-bound polycyclic aromatic hydrocarbons and their derivatives (nitro-and oxy-PAHs) emissions from two ship engines under different operating conditions. Chemosphere 225:43–52. https://doi.org/10.1016/j.chemosphere.2019.03.022
Acknowledgements
The authors would like to thank FAPERJ, FUNADESP and CNPq for its continuous support in funding our research.
Author information
Authors and Affiliations
Contributions
Sergio Machado Corrêa: Conceptualization, Methodology, Software, Formal analysis, Investigation, Resources, Writing—original draft, Supervision. Graciela Arbilla: Validation, Data curation, Writing—review & editing, Visualization. Cleyton Martins Silva: Validation, Data curation, Writing—review & editing, Visualization. Eduardo Monteiro Martins: Validation, Writing—review & editing, Visualization. Simone Lorena Quitério Souza: Validation, Writing—review & editing, Visualization.
Corresponding author
Ethics declarations
Ethical approval
Not applicable.
Consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Gerhard Lammel
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Corrêa, S.M., Arbilla, G., da Silva, C.M. et al. Determination of carbonyls and size-segregated polycyclic aromatic hydrocarbons, and their nitro and alkyl analogs in emissions from diesel–biodiesel-ethanol blends. Environ Sci Pollut Res 30, 62470–62480 (2023). https://doi.org/10.1007/s11356-023-26547-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-023-26547-8