PAHs in water and surface sediments from Douro River estuary and Porto Atlantic coast (Portugal)—impacts on human health

  • Maria João RochaEmail author
  • José Luís Dores-Sousa
  • Catarina Cruzeiro
  • Eduardo Rocha


This study investigated the presence of 16 priority polycyclic aromatic compounds (PAHs) in waters from the Douro River estuary and nearby Atlantic seacoast, which both bath the Porto metropolis. In the area, there is an oil refinery, an important harbour, an intense maritime traffic, small marinas and highly inhabited cities. For the analysis of PAHs, water samples were taken from four sampling sites, at six different times of the year (2011), and extracted by solid-phase extraction (dissolved fraction) and by ultrasound technique (suspended fraction), before their quantification by gas chromatography–mass spectrometry. Results not only proved the ubiquitous distribution of all analysed PAHs in the present habitat, but also that their global amounts (∑16PAHs) were extremely high at all sampling sites. Their average concentrations attained ≈ 55 ng/L and ≈ 52 μg/g dry weight (dw), respectively, in water and surface sediments. Accordingly, the surveyed area was classified as highly polluted by these organics and so, in view of the concentrations, mutagenic/carcinogenic responses in both humans and aquatic animals are possible to occur. The percentages of carcinogenic PAHs for humans (group 1) dissolved in water and in surface sediments were ca. 5 and 6%, respectively. These results are the first reported in the area and can be used as a baseline for future control of the PAHs levels locally while serving the building of global scenarios of PAHs pollution in Europe.

Graphical abstract

Percentage of PAHs, from different categories acordingly to WHO (2016), in both surface sediments and surface waters from Douro River estuary and Porto Atlantic seacoast; group 1 - carcinogenic, group 2A - probably carcinogenic, group 2B - possibly carcinogenic, and group 3 - not classifiable as carcinogenic to humans


GC–MS PAHs Oil refinery Harbour Marina Organic pollution sources 



This research was partially supported by European Regional Development Fund (ERDF) through COMPETE—Operational Competitiveness Programme and POPH—Operational Human Potential Programme and national funds through FCT—Foundation for Science and Technology, under the Strategic Funding UID/Multi/04423/2013, projects PTDC/MAR/70436/2006 (FCOMP-01-0124.FEDER-7382) and PTDC/MAR/105199/2008 (FCOMP-01-0124.FEDER-10620). This work was also implemented in the Framework of the Structured Program of R&D&I INNOVMAR—Innovation and Sustainability in the Management and Exploitation of Marine Resources (NORTE-01-0145-FEDER-000035), within the Research Line ECOSERVICES, supported by the Northern Regional Operational Programme (NORTE2020), through the ERDF.

Supplementary material

10661_2017_6137_MOESM1_ESM.pdf (132 kb)
ESM 1 (PDF 131 kb)


  1. Abdel-Shafy, H. I., & Mansour, M. S. M. (2016). A review on polycyclic aromatic hydrocarbons: source, environmental impact, effect on human health and remediation. Egyptian Journal of Petroleum, 25, 107–123.CrossRefGoogle Scholar
  2. ATSDR (1995). Toxicological profile for polycyclic aromatic hydrocarbons US Department of health and human services—public health service. Atlanta Agency for Toxic Substances and Disease Registry.Google Scholar
  3. ATDSR (2009). Case studies in environmental medicine: Toxicity of polycyclic aromatic hydrocarbons (PAHs). WB 1519, Agency for Toxic Substances and Disease Registry, Atlanta.Google Scholar
  4. Bai, Y., Meng, W., Xu, J., Zhang, Y., Guo, C., Lv, J., & Wan, J. (2014). Occurrence, distribution, environmental risk assessment and source apportionment of polycyclic aromatic hydrocarbons (PAHs) in water and sediments of the Liaohe River Basin, China. Bulletin of Environmental Contamination and Toxicology, 93, 744–751.CrossRefGoogle Scholar
  5. Barakat, A. O., Mostafa, A., Wade, T. L., Sweet, S. T., & El Sayed, N. B. (2011). Distribution and characteristics of PAHs in sediments from the Mediterranean coastal environment of Egypt. Marine Pollution Bulletin, 62, 1969–1978.CrossRefGoogle Scholar
  6. Bastami, K. D., Afkhami, M., Ehsanpour, M., Kazaali, A., Mohammadizadeh, M., Haghparast, S., Soltani, F., Zanjani, S. A., Ghorghani, N. F., & Pourzare, R. (2013). Polycyclic aromatic hydrocarbons in the coastal water, surface sediment and mullet Liza klunzingeri from northern part of Hormuz strait (Persian Gulf). Marine Pollution Bulletin, 76, 411–416.CrossRefGoogle Scholar
  7. Baumard, P., Budzinski, H., Garrigues, P., Sorbe, J. C., Burgeot, T., & Bellocq, J. (1998). Concentrations of PAHs (polycyclic aromatic hydrocarbons) in various marine organisms in relation to those in sediments and to trophic level. Marine Pollution Bulletin, 36, 951–960.CrossRefGoogle Scholar
  8. CCME (1999). Canadian Council of Ministers of the Environment. Canadian Environmental Quality Guidelines. Canadian water quality guidelines for the protection of aquatic life. Polycyclic aromatic hydrocarbons (PAHs).
  9. CCME (2010). Canadian Council of Ministers of the Environment. Canadian Environmental Quality Guidelines. Canadian soil quality guidelines for the protection of environmental and human health: polycyclic aromatic hydrocarbons.
  10. CEC (2011). Commission of the European Communities. Commission regulation (EU) no. 835/2011 of 19 August 2011 amending Regulation (EC) no. 1881/2006 as regards maximum levels for polycyclic aromatic hydrocarbons in foodstuffs. Official Journal of the European Union, 215, 4–8.Google Scholar
  11. Chen, C. H. S., Yuan, T. H., Shie, R. H., Wu, K. Y., & Chan, C. C. (2017). Linking sources to early effects by profiling urine metabolome of residents living near oil refineries and coal-fired power plants. Environment International, 102, 87–96.Google Scholar
  12. Commission, E. (2002). Health and consumer protection directorate-general. SCF/CS/CNTM/PAH/29 ADD1 vol 4 December 2002.Google Scholar
  13. Daniel, T., Sharpley, A., & Lemunyon, J. (1998). Agricultural phosphorus and eutrophication: a symposium overview. Journal of Environmental Quality, 27, 251–257.CrossRefGoogle Scholar
  14. Di Toro, D. M., McGrath, J. A., & Hansen, D. J. (2000). Technical basis for narcotic chemicals and polycyclic aromatic hydrocarbon criteria. I. Water and tissue. Environmental Toxicology and Chemistry, 19, 1951–1970.CrossRefGoogle Scholar
  15. Di Toro, D. M., McGrath, J. A., & Stubblefield, W. A. (2007). Predicting the toxicity of neat and weathered crude oil: toxic potential and the toxicity of saturated mixtures. Environmental Toxicology and Chemistry, 26, 24–36.CrossRefGoogle Scholar
  16. Dudhagara, D. R., Rajpara, R. K., Bhatt, J. K., Gosai, H. B., Sachaniya, B. K., & Dave, B. P. (2016). Distribution, sources and ecological risk assessment of PAHs in historically contaminated surface sediments at Bhavnagar coast, Gujarat. India Environmental Pollution, 213, 338–346.CrossRefGoogle Scholar
  17. EPA (1985). Environmental Protection Agency. Ambient water quality criteria for ammonia. EPA-440/5-85-001. Washington, DC: United States Environmental Protection Agency.Google Scholar
  18. EPA (2000). Environmental Protection Agency. Deposition of air pollutants to the great waters: third report to congress. Office of air quality planning and standards EPA-453/R-00-0005.Google Scholar
  19. EPA (2012). Environmental Protection Agency. Classification of polycyclic aromatic hydrocarbons.
  20. FEE (2014). Blue flag beach criteria and explanatory notes. Foundation for Environmental Education.
  21. Feng, C., Xia, X., Shen, Z., & Zhou, Z. (2007). Distribution and sources of polycyclic aromatic hydrocarbons in Wuhan section of the Yangtze River, China. Environmental Monitoring and Assessment, 133, 447–458.CrossRefGoogle Scholar
  22. Feo, M. L., Sprovieri, M., Gherardi, S., Sammartino, S., & Marsella, E. (2011). Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in the harbour of Naples (Southern Italy): time and spatial distribution patterns. Environmental Monitoring and Assessment, 174, 445–459.CrossRefGoogle Scholar
  23. Hijosa-Valsero, M., Bécares, E., Fernández-Aláez, C., Fernández-Aláez, M., Mayo, R., & Jiménez, J. J. (2016). Chemical pollution in inland shallow lakes in the Mediterranean region (NW Spain): PAHs, insecticides and herbicides in water and sediments. Science of the Total Environment, 544, 797–810.CrossRefGoogle Scholar
  24. Horii, Y., Ohura, T., Yamashita, N., & Kannan, K. (2009). Chlorinated polycyclic aromatic hydrocarbons in sediments from industrial areas in Japan and the United States. Archives of Environmental Contamination and Toxicology, 57, 651–660.CrossRefGoogle Scholar
  25. Kim, A., Vane, C. (2007). Simultaneous determination of PAHs and PCBs by GC-MS analysis. British Geological Survey Internal Report IR/07/045. pp. 9.Google Scholar
  26. Li, W.-H., Tian, Y.-Z., Shi, G.-L., Guo, C.-S., Li, X., & Feng, Y.-C. (2012). Concentrations and sources of PAHs in surface sediments of the Fenhe reservoir and watershed, China. Ecotoxicology and Environmental Safety, 75, 198–206.CrossRefGoogle Scholar
  27. Li, P., Cao, J., Diao, X., Wang, B., Zhou, H., Han, Q., Zheng, P., & Li, Y. (2015). Spatial distribution, sources and ecological risk assessment of polycyclic aromatic hydrocarbons in surface seawater from Yangpu Bay, China. Marine Pollution Bulletin, 93, 53–60.CrossRefGoogle Scholar
  28. Lim, L., Wurl, O., Karuppiah, S., & Obbard, J. P. (2007). Atmospheric wet deposition of PAHs to the sea-surface microlayer. Marine Pollution Bulletin, 54, 1212–1219.CrossRefGoogle Scholar
  29. Madureira, T. V., Velhote, S., Santos, C., Cruzeiro, C., Rocha, E., & Rocha, M. J. (2014). A step forward using QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) based extraction and gas chromatography-tandem mass spectrometry-levels of priority polycyclic aromatic hydrocarbons in wild and commercial mussels. Environmental Science and Pollution Research, 21, 6089–6098.CrossRefGoogle Scholar
  30. Magi, E., Bianco, R., Ianni, C., & Di Carro, M. (2002). Distribution of polycyclic aromatic hydrocarbons in the sediments of the Adriatic sea. Environmental Pollution, 119, 91–98.CrossRefGoogle Scholar
  31. Malik, A., Verma, P., Singh, A. K., & Singh, K. P. (2011). Distribution of polycyclic aromatic hydrocarbons in water and bed sediments of the Gomti River, India. Environmental Monitoring and Assessment, 172, 529–545.CrossRefGoogle Scholar
  32. Neff, M. (1979). Polycyclic aromatic hydrocarbons in the aquatic environment: sources, fates and biological effects. London: Applied Science Publishers.Google Scholar
  33. Nekhavhambe, T. J., Van Ree, T., & Fatoki, O. S. (2014). Determination and distribution of polycyclic aromatic hydrocarbons in rivers, surface runoff, and sediments in and around Thohoyandou, Limpopo Province, South Africa. Water SA, 40, 415–424.CrossRefGoogle Scholar
  34. Olivella, M., Ribalta, T., Defebrer, A., Mollet, J., & Delasheras, F. (2006). Distribution of polycyclic aromatic hydrocarbons in riverine waters after Mediterranean forest fires. Science of the Total Environment, 355, 156–166.CrossRefGoogle Scholar
  35. Patrolecco, L., Ademollo, N., Capri, S., Pagnotta, R., & Polesello, S. (2010). Occurrence of priority hazardous PAHs in water, suspended particulate matter, sediment and common eels (Anguilla anguilla) in the urban stretch of the River Tiber (Italy). Chemosphere, 81, 1386–1392.CrossRefGoogle Scholar
  36. Pérez-Fernández, B., Viñas, L., Franco, M. Á., & Bargiela, J. (2015). PAHs in the Ría de Arousa (NW Spain): a consideration of PAHs sources and abundance. Marine Pollution Bulletin, 95, 155–165.CrossRefGoogle Scholar
  37. Phillips, D. H. (1999). Polycyclic aromatic hydrocarbons in the diet. Mutatation Research—Genetic Toxicology and Environmental Mutagenesis, 443, 139–147.CrossRefGoogle Scholar
  38. Rengarajan, H. I., & Mansour, M. S. M. (2016). A review on polycyclic aromatic hydrocarbons: source, environmental impact, effect on human health and remediation. Egyptian Journal of Petroleum, 25, 107–123.CrossRefGoogle Scholar
  39. Rengarajan, T., Rajendran, P., Nandakumar, N., Lokeshkumar, B., Rajendran, P., & Nishigaki, I. (2015). Exposure to polycyclic aromatic hydrocarbons with special focus on cancer. Asian Pacific Journal of Tropical Biomedicine, 5, 182–189.CrossRefGoogle Scholar
  40. Rocha, M. J., Cruzeiro, C., Ferreira, C., & Rocha, E. (2012a). Occurrence of endocrine disruptor compounds in the estuary of the Iberian Douro River and nearby Porto Coast (NW Portugal). Toxicological and Environmental Chemistry, 94, 252–261.CrossRefGoogle Scholar
  41. Rocha, M. J., Ferreira, P. C., Reis, P. A., Cruzeiro, C., & Rocha, E. (2011). Determination of polycyclic aromatic hydrocarbons in coastal sediments from the Porto region (Portugal) by microwave-assisted extraction, followed by SPME and GC-MS. Journal of Chromatographic Science, 49, 695–701.CrossRefGoogle Scholar
  42. Rocha, M. J., Ribeiro, M., Ribeiro, C., Couto, C., Cruzeiro, C., & Rocha, E. (2012c). Endocrine disruptors in the Leça River and nearby Porto Coast (NW Portugal): presence of estrogenic compounds and hypoxic conditions. Toxicological and Environmental Chemistry, 94, 262–274.CrossRefGoogle Scholar
  43. Rocha, M. J., Ribeiro, M. F. T., Cruzeiro, C., Figueiredo, F., & Rocha, E. (2012b). Development and validation of a GC-MS method for determination of 39 common pesticides in estuarine water—targeting hazardous amounts in the Douro River estuary. International Journal of Environmental Analytical Chemistry, 92, 1587–1608.CrossRefGoogle Scholar
  44. Srogi, K. (2007). Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review. Environmental Chemistry Letters, 5, 169–195.CrossRefGoogle Scholar
  45. Viguri, J., Verde, J., & Irabien, A. (2002). Environmental assessment of polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Santander Bay, Northern Spain. Chemosphere, 48, 157–165.CrossRefGoogle Scholar
  46. Vila-Escalé, M., Vegas-Vilarrúbia, T., & Prat, N. (2007). Release of polycyclic aromatic compounds into a Mediterranean creek (Catalonia, NE Spain) after a forest fire. Water Research, 41, 2171–2179.CrossRefGoogle Scholar
  47. Wang, J.-Z., Nie, Y.-F., Luo, X.-L., & Zeng, E. Y. (2008). Occurrence and phase distribution of polycyclic aromatic hydrocarbons in riverine runoff of the Pearl River Delta. China. Marine Pollution Bulletin, 57, 767–774.CrossRefGoogle Scholar
  48. WHO (2011). World Health Organization. Guidelines for drinking-water quality—nitrate and nitrite in drinking-water.Google Scholar
  49. WHO (2016). International Agency for Research in Cancer (IARC). IARC monographs on the evaluation of carcinogenic risks to humans (
  50. Zhang, S., Zhang, Q., Darisaw, S., Ehie, O., & Wang, G. (2007). Simultaneous quantification of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) in Mississippi river water, in New Orleans, Louisiana, USA. Chemosphere, 66, 1057–1069.CrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  • Maria João Rocha
    • 1
    • 2
    Email author
  • José Luís Dores-Sousa
    • 1
  • Catarina Cruzeiro
    • 1
    • 2
  • Eduardo Rocha
    • 1
    • 2
  1. 1.Histomorphology, Physiopathology, and Applied Toxicology Group, Interdisciplinary Centre of Marine and Environmental Research (CIIMAR)University of Porto (UPorto)PortoPortugal
  2. 2.Laboratory of Histology and Embryology, Department of Microscopy, Institute of Biomedical Sciences Abel Salazar (ICBAS)UPortoPortoPortugal

Personalised recommendations