Spatiotemporal Distribution and Sources of Trace Elements in Ave River (Portugal) Lower Basin: Estuarine Water, Sediments and Indigenous Flora

  • Cristina Maria Cavadas Morais CoutoEmail author
  • Cláudia Ribeiro
  • Ana Rita Ribeiro
  • Alexandra Maia
  • Mariana Santos
  • Maria Elizabeth Tiritan
  • Edgar Pinto
  • Agostinho A. Almeida
Research paper


This study aimed to assess the spatial and seasonal distribution and anthropogenic sources of trace elements (Li, Be, Al, V, Cr, Co, Ni, Cu, Zn, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, and U) by ICP-MS in the Ave River lower basin, Portugal. Mean values (µg L−1) of Al (2384), Zn (55.3), Se (34.6), Cu (24.7), Pb (12.7), Ag (0.75), and Cd (0.66), exceeded the water quality guidelines for the protection of aquatic life. The decreasing order of trace elements concentrations in surface water and sediments was, respectively: Al > Zn > Se > Mo > Li > Ba > V > Cu > Pb > Ni > Cr > U > Be > Co ≈ Sb > Ag ≈ Cd > Tl; and Al > Zn > Li > Ba > Cu > Pb > Cr > V > Ni > Co > U > Be > Se ≈ Mo ≈ Tl ≈ Cd ≈ Sb ≈ Ag. Moreover, the concentrations of nitrate values were higher than 50 mg L−1. To distinguish natural from anthropogenic sources, the geo-accumulation index (Igeo) and the enrichment factor (EF) of sediments were determined. Igeo revealed high contamination by Al, Mn, Ba and Zn, while EF evidenced enrichment for Se, Cd, Zn, Li, Cu, Ag, Pb and U. Bioaccumulation factors (BF) in flora suggested that macroalgae, Medicago marina L. and Plantago lanceolata L., might be accumulators of Se, Mo, Ba and Pb (BF > 1). The highest translocation factor (TF) was found for Mo in leaves (33.6) and flowers (28.1) of P. lanceolata L..

Article Highlights

  • The present work regards a comprehensive study on the occurrence, spatial distribution, possible sources and bioaccumulation of trace elements in this ecosystem, namely in water, sediments and native local flora (plants and macroalgae). In fact, various studies have demonstrated the high anthropogenic pressure of Ave River estuary, the presence of several classes of pollutants and the negative impacts in local aquatic organisms. Nevertheless, there are no studies regarding the monitoring of a large panel of trace elements considering three different matrices (water, sediments and plants) and their possible correlation

  • Pollution indices such as geo-accumulation (Igeo) and enrichment factor (EF) were also determined to investigate sources of these elements. Igeo revealed high contamination by Al, Mn, Ba and Zn, while EF evidenced enrichment for Se, Cd, Zn, Li, Cu, Ag, Pb and U. Bioaccumulation factors (BF) in flora suggested that macroalgae, Medicago marina L. and Plantago lanceolata L. might be accumulators of Se, Mo, Ba and Pb

  • These monitoring data are important to alert local and national authorities to take actions and decisions to protect and improve water quality of Portuguese waterbodies and meet national and European requirements


Waterbodies Plants ICP-MS Heavy metals Zinc 



This work received financial support from the European Union (FEDER funds POCI/01/0145/FEDER/007265) and National Funds (FCT/MEC, Fundação para a Ciência e Tecnologia and Ministério da Educação e Ciência) under the Partnership Agreement PT2020 UID/QUI/50006/2013 and the Project PTDC/SAU-ESA/108871/2008. This work was also supported by CESPU, through Project MYCO-CESPU-2016, ChiralDrugs_CESPU_2017 and BIOENVIROM-CESPU-2018.

Compliance with ethical standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Supplementary material

41742_2019_174_MOESM1_ESM.docx (63 kb)
Supplementary material 1 (DOCX 62 kb)


  1. Allen SE (1989) Chemical analyses of ecological material, 2nd edn. Blackwell Scientific Publications, LondonGoogle Scholar
  2. Alves CM, Boaventura RRAR, Soares HMVM (2009) Evaluation of heavy metals pollution loadings in the sediments of the Ave River Basin (Portugal). Soil Sediment Contam 18(5):603–618CrossRefGoogle Scholar
  3. Alyazichi YM, Jones BG, McLean E (2015) Spatial distribution of sediment particles and trace element pollution within Gunnamatta Bay, Port Hacking, NSW, Australia. Reg Stud Mar Sci 2:124–131CrossRefGoogle Scholar
  4. Alyazichi YM, Jones BG, McLean E, Pease J, Brown H (2017) Geochemical assessment of trace element pollution in surface sediments from the Georges River, Southern Sydney, Australia. Arch Environ Contam Toxicol 72:247–259CrossRefGoogle Scholar
  5. Amare TA, Yimer GT, Workagegn KB (2014) Assessment of metals concentration in water, sediment and macrophyte plant collected from Lake Hawassa, Ethiopia. J Environ Anal Toxicol 4:247Google Scholar
  6. Ansari AA, Gill SS, Gill R, Lanza GR, Newman L (2016) Phytoremediation: management of environmental contaminants, vol 3. Springer, SwitzerlandCrossRefGoogle Scholar
  7. Barbieri M (2016) The importance of enrichment factor (EF) and geoaccumulation index (I geo) to evaluate the soil contamination. J Geol Geophys 5:1CrossRefGoogle Scholar
  8. Basta NT, Ryan JA, Chaney RL (2005) Trace element chemistry in residual-treated soil: key concepts and metal bioavailability. J Environ Qual 34:49–63CrossRefGoogle Scholar
  9. Brautigan DJ, Rengasamy P, Chittleborough DJ (2012) Aluminium speciation and phytotoxicity in alkaline soils. Plant Soil 360:187–196CrossRefGoogle Scholar
  10. CCME-Canadian Council of Ministers of the Environment (2001) Canadian Sediment Quality Guidelines for the Protection of Aquatic Life, Updated. In: Canadian environmental quality guidelines, 1999, Canadian Council of Ministers of the Environment, Winnipeg. Accessed 05 Mar 2018
  11. CCME-Canadian Council of Ministers of the Environment (2017) Water quality guidelines for the protection of aquatic life. Accessed 05 Mar 2018
  12. Chen CW, Kao CM, Chen CF, Dong CD (2007) Distribution and accumulation of heavy metals in the sediments of Kaohsiung Harbor, Taiwan. Chemosphere 66:1431–1440CrossRefGoogle Scholar
  13. Clesceri LS, Greenberg AE, Eaton AD (1998) Standard Methods for the Examination of Water and Wastewater, 20th edn. American Public Health Association, Washington, DCGoogle Scholar
  14. Combs GF, Combs SB (1986) The role of Selenium in nutrition. Academic Press, OrlandoGoogle Scholar
  15. Couto CMCM, Pinto I, Madureira TV, Rocha MJ, Tiritan ME, Lopes JA, Almeida AA (2014) Lower Douro River basin (Portugal) water quality—focus on trace element changes and anthropogenic sources of contamination. Global Nest J 16:251–268Google Scholar
  16. Couto CMCM, Ribeiro C, Maia A, Santos M, Tiritan ME, Ribeiro AR, Pinto E, Almeida A (2018) Assessment of Douro and Ave River (Portugal) lower basin water quality focusing on physicochemical and trace element spatiotemporal changes. J Environ Sci Heal A. Google Scholar
  17. Dan SF, Umoh UU, Osabor VN (2014) Seasonal variation of enrichment and contamination of heavy metals in the surface water of Qua Iboe River Estuary and adjoining creeks, South-South Nigeria. J Oceanogr Mar Sci 5:45–54CrossRefGoogle Scholar
  18. Directive WFD (2000) 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy. Off J Eur Commun 1:72Google Scholar
  19. Doležalová Weissmannová H, Pavlovský J, Chovanec P (2015) Heavy metal contaminations of Urban soils in Ostrava, Czech Republic: assessment of metal pollution and using principal component analysis. Int J Environ Res 9(2):683–696Google Scholar
  20. Ebbs S, Brady D, Norvell W, Kochian L (2001) Uranium speciation, plant uptake, and phytoremediation, practice periodical of hazardous toxic and radioactive. Waste Manag 5:130–135Google Scholar
  21. Feng H, Qian Y, Cochran JK, Zhu Q, Heilbrun C, Li L, Hu W, Yan H, Huang X, Ge M, Nazareski E, Chu YS, Yoo S, Zhang X, Liu CJ (2018) Seasonal differences in trace element concentrations and distribution in Spartina alterniflora root tissue. Chemosphere 204:359–370CrossRefGoogle Scholar
  22. Fitzgerald EJ, Caffrey JM, Nesaratnam ST, McLoughlin P (2003) Copper and lead concentrations in salt mash plants on the Suir Estuary, Ireland. Environ Pollut 123:67–74CrossRefGoogle Scholar
  23. Fonseca AR, Sanches Fernandes LF, Fontainhas-Fernandes A, Monteiro SM, Pacheco FAL (2017) The impact of freshwater metal concentrations on the severity of histopathological changes in fish gills: a statistical perspective. Sci Total Environ 1(599–600):217–226CrossRefGoogle Scholar
  24. Gjorgieva D, Kadifkova-Panovska T, Baceva K, Stafilov T (2011) Assessment of heavy metal pollution in republic of macedonia using a plant assay. Arch Environ Con Tox 60(2):233–240CrossRefGoogle Scholar
  25. Hamilton SJ (2004) Review of selenium toxicity in the aquatic food chain. Sci Total Environ 326:1–31CrossRefGoogle Scholar
  26. Hamzeha M, Ouddanea B, El-dayea M, Halwani J (2013) Profile of trace metals accumulation in core sediment from Seine river estuary (docks basin). Environ Technol 34(9):1107–1116CrossRefGoogle Scholar
  27. Hansel C, Fendorf S, Sutton S, Newville M (2001) Characterization of Fe plaque and associated metals on the roots of mine-waste impacted aquatic plants. Environ Sci Technol 35:3863–3868CrossRefGoogle Scholar
  28. Kabata-Pendias A, Pendias H (1992) Trace elements in soils and plants, 2nd edn. CRC Press, Boca RatonGoogle Scholar
  29. Magesh NS, Chandrasekar N, Elango L (2017) Trace element concentrations in the groundwater of the Tamiraparani river basin, South India: insights from human health risk and multivariate statistical techniques. Chemosphere 185:468–479CrossRefGoogle Scholar
  30. Malmström ME, Rolli V, Cui Q, Brandt N (2009) Sources and fates of heavy metals in complex, urban aquatic systems: modelling study based on Stockholm, Sweden, WIT transactions on ecology and the environment, vol 122. WIT Press, New York (ISSN 1743-3541 (on-line)) Google Scholar
  31. Mendiguchía C, Moreno C, García-Vargas M (2007) Evaluation of natural and anthropogenic influences on the Guadalquivir River (Spain) by dissolved heavy metals and nutrients. Chemosphere 69(10):1509–1517CrossRefGoogle Scholar
  32. Muller G (1969) Index of geo-accumulation in sediments of the Rhine River. Geo J 2:108–118Google Scholar
  33. Oliveira RES, Lima MMCL and Vieira JMP (2005) An indicator system for surface water quality in river basins. The fourth inter-celtic colloquium on hydrology and management of water resources. Accessed 26 May 2017
  34. Parques e Vida Selvagem (2006), accessed 25/01/2018
  35. Petrova S, Velcheva I, Yurukova L, Berova M (2014) Plantago lanceolata L. as a biomonitor of trace elements in an urban area. Bulg J Agric Sci 20(2):325–329Google Scholar
  36. Prasad MNV, Freitas HMO (2003) Metal hyperaccumulation in plants—biodiversity prospecting for phytoremediation technology. Electron J Biotechn 6(3):276–312Google Scholar
  37. Prasad MNV, Sajwan KS, Naidu R (2006) Trace elements in the environment: biogeochemistry, biotechnology, and bioremediation. Taylor and Francis, CRC Press, Boca RatonGoogle Scholar
  38. Raskin I, Ensley BD (2000) Phytoremediation of toxic metals using plants to clean up the environment. Wiley, New YorkGoogle Scholar
  39. Renjan S, Rao VP, Kessarkar PM (2017) Major and trace metals in suspended and bottom sediments of the Mandovi and Zuari estuaries, western India: distribution, source, and pollution. Environ Sci Pollut Res 24:27409–27429CrossRefGoogle Scholar
  40. Ribeiro CMR, Maia AS, Ribeiro AR, Couto C, Almeida AA, Santos M, Tiritan ME (2016) Anthropogenic pressure in a Portuguese river: endocrine-disrupting compounds, trace elements and nutrients. J Environ Sci Health A 51(12):1043–1052CrossRefGoogle Scholar
  41. Ribeiro C, Couto C, Ribeiro AR, Maia AS, Santos M, Tiritan ME, Pinto E, Almeida AA (2018) Distribution and environmental assessment of trace elements contamination of water, sediments and flora from Douro River estuary, Portugal. Sci Total Environ 639:1381–1393CrossRefGoogle Scholar
  42. Roy S, Labelle S, Mehta P et al (2005) Phytoremediation of heavy metal and PAH-contaminated brownfield sites. Plant Soil 272(1–2):277–290CrossRefGoogle Scholar
  43. Savitha P (2014) Role of selenium. J Pharm Sci Res 6(1):56–59Google Scholar
  44. Soares HMVM, Boaventura RAR, Machado AASC, Esteves da Silva JCG (1999) Sediments as monitors of heavy metal contamination in the Ave river basin (Portugal): multivariate analysis of data. Environ Pollut 105(3):311–323CrossRefGoogle Scholar
  45. Summer K, Reichelt-Brushett A (2018) Trace element contaminant uptake in phytocap vegetation and implications for koala habitat, Lismore, Australia. Environ Sci Pollut Res 25:24281–24292CrossRefGoogle Scholar
  46. Sutherland RA, Tolosa CA, Tack FMG, Verloo MG (2000) Characterization of selected element concentrations and enrichment ratios in background and anthropogenically impacted roadside areas. Arch Environ Contam Toxicol 38:428–438CrossRefGoogle Scholar
  47. Tangahu BV, Sheikh Abdullah SR, Basri H, Idris M, Anuar N, Mukhlisin M (2011) A review on heavy metals (As, Pb, and Hg) uptake by plants through phytoremediation. Int J Chem Eng. Google Scholar
  48. U. S. Department of Energy (1994) Mechanisms of plant uptake, translocation, and storage of toxic elements. Summary Report of a workshop on phytoremediation research needs.;jsessionid=D72C8DD9003DCF51984EE254A6ED8BCB?purl=/10109412-BckU4U/webviewable/. Accessed 16 May 2018
  49. USEPA (2007) Method 3051A microwave assisted acid digestion of sediments, sludges, soils, and oils. USEPA, Washington, DCGoogle Scholar
  50. Wedepohl KH (1995) The composition of the continental crust. Geochim Cosmochim Ac 59(7):1217–1232CrossRefGoogle Scholar
  51. Windham L, Weis JS, Weis P (2003) Uptake and distribution of metals in two dominant saltmarsh macrophytes, Spartina alterniflora (cordgrass) and Phragmites australis (common reed). Estuar Coast Shelf S 56:63–72CrossRefGoogle Scholar
  52. Woitke P, Wellmitz J, Helm D, Kube P, Lepom P, Litheraty P (2003) Analysis and assessment of heavy metal pollution in suspended solids and sediments of the river Danube. Chemosphere 51:633–642CrossRefGoogle Scholar
  53. Yang J-L, Zhang G-L (2015) Formation, characteristics and ecoenvironmental implications of urban soils—a review. Soil Sci Plant Nutr 61(sup1):30–46CrossRefGoogle Scholar
  54. Yin S, Yuehan W, Wei X, Yangyang L, Zhenyao S, Chenghong F (2016) Contribution of the upper river, the estuarine region, and the adjacent sea to the heavy metal pollution in the Yangtze estuary. Chemosphere 155:564–572CrossRefGoogle Scholar

Copyright information

© University of Tehran 2019

Authors and Affiliations

  • Cristina Maria Cavadas Morais Couto
    • 1
    • 2
    Email author
  • Cláudia Ribeiro
    • 1
    • 3
  • Ana Rita Ribeiro
    • 1
    • 4
  • Alexandra Maia
    • 1
  • Mariana Santos
    • 1
  • Maria Elizabeth Tiritan
    • 1
    • 3
    • 5
  • Edgar Pinto
    • 2
  • Agostinho A. Almeida
    • 2
  1. 1.CESPU, Instituto de Investigação e Formação Avançada em Ciências e Tecnologias da Saúde, Rua Central de GandraGandra PRDPortugal
  2. 2.LAQV/REQUIMTE, Departamento de Ciências Químicas, Laboratório de Química AplicadaFaculdade de Farmácia, Universidade do PortoPortoPortugal
  3. 3.Centro Interdisciplinar de Investigação Marinha e Ambiental (CIIMAR/CIMAR), Universidade do Porto, Edifício do Terminal de Cruzeiros do Porto de LeixõesMatosinhosPortugal
  4. 4.Laboratory of Separation and Reaction Engineering, Laboratory of Catalysis and Materials (LSRE-LCM)Faculdade de Engenharia, Universidade do PortoPortoPortugal
  5. 5.Laboratório de Química Orgânica e FarmacêuticaDepartamento de Ciências Químicas, Faculdade de Farmácia, Universidade do PortoPortoPortugal

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