Journal of Soils and Sediments

, Volume 15, Issue 11, pp 2265–2275 | Cite as

Evaluation of single extraction procedures for the assessment of heavy metal extractability in citrus agricultural soil of a typical Mediterranean environment (Argolida, Greece)

  • Efstratios Kelepertzis
  • Vasiliki Paraskevopoulou
  • Ariadne Argyraki
  • George Fligos
  • Olga Chalkiadaki
Soils, Sec 3 • Remediation and Management of Contaminated or Degraded Lands • Research Article

Abstract

Purpose

Heavy metals are natural soil constituents; however, the intense use of agrochemicals can increase total contents above background levels as well as the available fractions of the more toxic elements. In this study, the occurrence of some metals was investigated in agricultural soils from an intensely farmed rural area of Greece (Argolida) aiming to evaluate the various available pools and examine their relationship with the reactive and pseudototal soil fraction.

Materials and methods

Thirty soil samples were selected from a large database of a previous geochemical survey in the study area. The pseudototal (aqua regia), reactive (0.43 M HNO3), potentially phytoavailable (0.05 M EDTA), mobilizable (0.43 M HAc), and mobile (0.01 M CaCl2) pools of Cu, Zn, Cd, and Mn were determined. Soil properties were also examined including pH, total organic carbon, calcium carbonate content, and amorphous Al, Mn, and Fe oxides. In order to combine all geochemical information and elucidate the association between available metal pools and soil chemical characteristics, multiple linear regression was employed. The various proportions of available metal pools (%) were expressed as a function of the pseudototal or reactive metal content and general soil properties.

Results and discussion

The mobile pool of trace elements in the studied soils was quite low, while notable amounts of Cu were released by EDTA indicating a greater tendency for complexation. The acetic acid extraction yielded increased percentages of Cd and Mn and for these elements the reactive pools were quite representative of the pseudototal content. Extractable amounts of Zn by all the applied reagents were very low indicating that a considerable part of this metal is of geogenic origin. The empirical regression models showed that prediction of the available pools of Cu, Zn, and Cd from the pseudototal and reactive content is feasible. Although pH is known to be a key factor of at least exchangeable metal pools, its narrow range blurs its influence in the present study.

Conclusions

The relatively low extraction yields of the studied elements show that the potential hazard of metal transfer to plants in the area is minimal despite some elevated pseudototal concentrations. The geochemical reactive and various available pools of Cu, Zn, and Cd in Mediterranean calcareous citrus soils can be determined by a single soil extraction test using dilute nitric acid.

Keywords

Calcareous soil Chemical extractions Heavy metals Mobility Soil contamination 

References

  1. Behera SK, Singh MV, Singh KN, Todwal S (2011) Distribution variability of total and extractable zinc in cultivated acid soils of India and their relationship with some selected soil properties. Geoderma 162:242–250CrossRefGoogle Scholar
  2. Bouman OT, Curtin D, Campbell CA, Biederbeck VO, Ukrainetz H (1995) Soil acidification from long-term use of anhydrous ammonia and urea. Soil Sci Soc Am J 59:1488–1494CrossRefGoogle Scholar
  3. Brun LA, Maillet J, Hinsinger P, Pépin M (2001) Evaluation of copper availability to plants in copper-contaminated vineyard soils. Environ Pollut 111:293–302CrossRefGoogle Scholar
  4. CEC (1986) Council Directive 12 June 1986 on the protection of the environment, and in particular the soil when sewage sludge is used in agriculture. Official Journal of the European Community. No L.181 (86/278/CEC). Brussels: Commission of the European Communities; pp 6–12Google Scholar
  5. Chaignon V, Sanchez-Neira I, Herrmann P, Jaillard B, Hinsinger P (2003) Copper bioavailability and extractability as related to chemical properties of contaminated soils from a vine-growing area. Environ Pollut 123:229–238CrossRefGoogle Scholar
  6. de Santiago-Martín A, Van Oort F, González C, Quintana J, Lafuente A, Lamy I (2015) Improving the relationship between soil characteristics and metal bioavailability by using reactive fractions of soil parameters in calcareous soils. Environ Toxicol Chem 34:37–44CrossRefGoogle Scholar
  7. Dudka S, Miller WP (1999) Accumulation of potentially toxic elements in plants and their transfer to human food chain. J Environ Sci Health B 34:681–708CrossRefGoogle Scholar
  8. Duplay J, Semhi K, Errais E, Imfeld G, Babcsanyi I, Perrone T (2014) Copper, zinc, lead and cadmium bioavailability and retention in vineyard soils (Rouffach, France): the impact of cultural practices. Geoderma 230–231:318–328CrossRefGoogle Scholar
  9. Fan J, He Z, Ma LQ, Stoffella PJ (2011) Accumulation and availability of copper in citrus grove soils as affected by fungicide application. J Soils Sediments 11:639–648CrossRefGoogle Scholar
  10. Fernández-Calviño D, Rodríguez-Suárez JA, López-Periago E, Arias-Estévez M, Simal-Gándara J (2008) Copper content of soils and river sediments in a winegrowing area, and its distribution among soil or sediment components. Geoderma 145:91–97CrossRefGoogle Scholar
  11. Gaudette HE, Flight WR, Toner L, Folger DW (1974) An inexpensive titration method for the determination of organic carbon in recent sediments. J Sediment Res 44:249–253Google Scholar
  12. Gupta SK, Vollmer MK, Krebs R (1996) The importance of mobile, mobilisable and pseudo total heavy metal fractions in soil for three-level risk assessment and risk management. Sci Total Environ 178:11–20CrossRefGoogle Scholar
  13. ISO 10390 (1994) Soil quality—determination of pHGoogle Scholar
  14. Jiao W, Ouyang W, Hao F, Wang F, Liu B (2014) Long-term cultivation impact on the heavy metals behavior in a reclaimed wetland, Northeast China. J Soils Sediments 14:567–576CrossRefGoogle Scholar
  15. Kabata-Pendias A, Pendias H (2001) Trace elements in soils and plants, 3rd edn. CRC Press LLC, Boca RatonGoogle Scholar
  16. Kelepertzis E (2014) Accumulation of heavy metals in agricultural soils of Mediterranean: insights from Argolida basin, Peloponnese, Greece. Geoderma 221–222:82–90CrossRefGoogle Scholar
  17. Kelepertzis E, Argyraki A (2015) Geochemical associations for evaluating the availability of potentially harmful elements in urban soils: lessons learnt from Athens, Greece. Appl Geochem 59:63–73CrossRefGoogle Scholar
  18. Kelepertzis E, Stathopoulou E (2013) Availability of geogenic heavy metals in soils of Thiva town (central Greece). Environ Monit Assess 185:9603–9618CrossRefGoogle Scholar
  19. Komárek M, Száková J, Rohošková M, Javorská H, Chrastný V, Balík J (2008) Copper contamination of vineyard soils from small wine producers: a case study from the Czech Republic. Geoderma 147:16–22CrossRefGoogle Scholar
  20. Li Y, Zhang M-K (2013) A comparison of physiologically based extraction test (PBET) and single-extraction methods for release of Cu, Zn, and Pb from mildly acidic and alkali soils. Environ Sci Pollut Res 20:3140–3148CrossRefGoogle Scholar
  21. Li L, Wu H, van Gestel CAM, Peijnenburg WJGM, Allen HE (2014) Soil acidification increases metal extractability and bioavailability in old orchard soils of Northeast Jiaodong Peninsula in China. Environ Pollut 188:144–152CrossRefGoogle Scholar
  22. Loring DH, Rantala RTT (1992) Manual for the geochemical analyses of marine sediments and suspended particulate matter. Earth Sci Rev 32:235–283CrossRefGoogle Scholar
  23. Luo X-S, Yu S, Li X-D (2012) The mobility, bioavailability, and human bioaccessibility of trace metals in urban soils of Hong Kong. Appl Geochem 27:995–1004CrossRefGoogle Scholar
  24. Lv J, Liu Y, Zhang Z, Dai J, Dai B, Zhu Y (2015) Identifying the origins and spatial distributions of heavy metals in soils of Ju country (Eastern China) using multivariate and geostatistical approach. J Soils Sediments 15:163–178CrossRefGoogle Scholar
  25. Meers E, Laing GD, Unamuno V, Ruttens A, Vangronsveld J, Tack FMG, Verloo MG (2007) Comparison of cadmium extractability from soils by commonly used single extraction protocols. Geoderma 141:247–259CrossRefGoogle Scholar
  26. Menzies NW, Donn MJ, Kopittke PM (2007) Evaluation of extractants for estimation of the phytoavailable trace metals in soils. Environ Pollut 145:121–130CrossRefGoogle Scholar
  27. Michaud AM, Bravin MN, Galleguillos M, Hinsinger P (2007) Copper uptake and phytotoxicity as assessed in situ for durum wheat (Triticum turgidum durum L.) cultivated in Cu-contaminated, former vineyard soils. Plant Soil 298:99–111CrossRefGoogle Scholar
  28. Mirlean N, Roisenberg A, Chies JO (2007) Metal contamination of vineyard soils in wet subtropics (southern Brazil). Environ Pollut 149:10–17CrossRefGoogle Scholar
  29. Novozamsky I, Lexmond TM, Houba VJG (1993) A single extraction procedure of soil for evaluation of uptake of some metals by plants. Int J Environ An Ch 51:47–58CrossRefGoogle Scholar
  30. Peijnenburg WJGM, Zablotskaja M, Vijver MG (2007) Monitoring metals in terrestrial environments within a bioavailability framework and a focus on soil extraction. Ecotoxicol Environ Saf 67:163–179CrossRefGoogle Scholar
  31. Qasim B, Motelica-Heino M, Joussein E, Soubrand M, Gauthier A (2015) Potentially toxic element phytoavailability assessment in Technosols from former smelting and mining areas. Environ Sci Pollut Res 22:5961–5974CrossRefGoogle Scholar
  32. Quevauviller P, Rauret G, Rubio R, López-Sánchez J-F, Ure A, Bacon J, Muntau H (1997) Certified reference materials for the quality control of EDTA- and acetic acid-extractable contents of trace elements in sewage sludge amended soils (CRMs 483 and 484). Fresen J Anal Chem 357:611–618CrossRefGoogle Scholar
  33. Rajkumar M, Sandhya S, Prasad MNV, Freitas H (2012) Perspectives of plant-associated microbes in heavy metal phytoremediation. Biotechnol Adv 30:1562–1574CrossRefGoogle Scholar
  34. Reimann C, Filzmoser P, Garrett R, Dutter R (2008) Statistical data analysis explained: applied environmental statistics with R. Wiley-Blackwell, ChichesterCrossRefGoogle Scholar
  35. Rodrigues SM, Henriques B, Ferreira da Silva E, Pereira ME, Duarte AC, Römkens PFAM (2010) Evaluation of an approach for the characterization of reactive and available pools of twenty potentially toxic elements in soils: part I—the role of key soil properties in the variation of contaminants’ reactivity. Chemosphere 81:1549–1559CrossRefGoogle Scholar
  36. Rodrigues SM, Cruz N, Coelho C, Henriques B, Carvalho L, Duarte AC, Pereira E, Römkens PFAM (2013) Risk assessment for Cd, Cu, Pb, and Zn in urban soils: chemical availability as the central concept. Environ Pollut 183:234–242CrossRefGoogle Scholar
  37. Rodríguez Martín JA, Ramos-Miras JJ, Boluda R, Gil C (2013) Spatial relations of heavy metals in arable and greenhouse soils of a Mediterranean environment region (Spain). Geoderma 200–201:180–188CrossRefGoogle Scholar
  38. Rodríguez Martín JA, De Arana E, Ramos-Miras JJ, Gil C, Boluda R (2015) Impact of 70 years urban growth associated with heavy metal pollution. Environ Pollut 196:156–163CrossRefGoogle Scholar
  39. Römkens P, Guo H-Y, Chu C-L, Liu T-S, Chiang C-F, Koopmans G (2009) Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning. J Soils Sediments 9:216–228CrossRefGoogle Scholar
  40. Sahuquillo A, Rigol A, Rauret G (2002) Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments. J Environ Monit 4:1003–1009CrossRefGoogle Scholar
  41. Sahuquillo A, Rigol A, Rauret G (2003) Overview of the use of leaching/extraction tests for risk assessment of trace metals in contaminated soils and sediments. Trends Anal Chem 22:152–159CrossRefGoogle Scholar
  42. Schramel O, Michalke B, Kettrup A (2000) Study of the copper distribution in contaminated soils of hop fields by single and sequential extraction procedures. Sci Total Environ 263:11–22CrossRefGoogle Scholar
  43. Schwertmann U (1964) Differenzierung der Eisenoxide des Bodens durch photochemische Extraktion mit saurer Ammoniumoxalat-Lösung. Z Pflanzenernaehr Bodenkd 105:194–202CrossRefGoogle Scholar
  44. Shan Y, Tysklind M, Hao F, Ouyang W, Chen S, Lin C (2013) Identification of sources of heavy metals in agricultural soils using multivariate analysis and GIS. J Soils Sediments 13:720–729CrossRefGoogle Scholar
  45. Sungur A, Soylak M, Ozcan H (2014) Investigation of heavy metal mobility and availability by the BCR sequential extraction procedure: relationship between soil properties and heavy metals availability. Chem Speciat Bioavailab 26:219–230CrossRefGoogle Scholar
  46. Sungur A, Soylak M, Yilmaz E, Yilmaz S, Ozcan H (2015) Characterization of heavy metal fractions in agricultural soils by sequential extraction procedures: the relationship between soil properties and heavy metal fractions. Soil Sediment Contam 24:1–15CrossRefGoogle Scholar
  47. Ure AM, Quevauviller P, Muntau H, Griepink B (1993) Speciation of heavy metals in soils and sediments. An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the Commission of the European Communities. Int J Environ An Ch 51:135–151CrossRefGoogle Scholar
  48. Walkley A, Black IA (1934) An examination of the Degtjareff method for determining soil organic matter and a proposed modification of the chromic acid titration method. Soil Sci 37:29–37CrossRefGoogle Scholar
  49. Wu C, Luo Y, Zhang L (2010) Variability of copper availability in paddy fields in relation to selected soil properties in Southeast China. Geoderma 156:200–206CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Efstratios Kelepertzis
    • 1
  • Vasiliki Paraskevopoulou
    • 2
  • Ariadne Argyraki
    • 1
  • George Fligos
    • 1
  • Olga Chalkiadaki
    • 2
  1. 1.Faculty of Geology and GeoenvironmentUniversity of AthensAthensGreece
  2. 2.Faculty of Chemistry, Laboratory of Environmental ChemistryUniversity of AthensAthensGreece

Personalised recommendations