Skip to main content
Log in

Sorption of Zn(II) and Cu(II) by four Argentinean soils as affected by pH, oxides, organic matter and clay content

  • Original Article
  • Published:
Environmental Earth Sciences Aims and scope Submit manuscript

Abstract

Increasing heavy metal applications to agricultural soils in the form of phosphatic fertilizers and/or atmospheric deposition have led to extensive research on the chemistry of Zn and Cu in soils. Cu(II) and Zn(II) sorption onto different soil fractions of three Mollisols and one Entisol from the southwest of Buenos Aires Province, Argentina, was studied. Different variables affecting the sorption capacity such as pH, cation exchange capacity, specific surface area (SSA), type and amount of clay minerals present, content of Fe-, Al-, and Mn-oxides and oxohydroxides, organic matter and electric charge parameters were investigated. To assess the monometal sorption, batch equilibrium experiments were performed using Cu(II) and Zn(II) metal solutions over a pH range from 4.0 to 7.0. The increase in metal sorption with increasing pH for both metal cations was attributed to an increase in the negative surface charges. At pH 5.0, Cu(II) showed more affinity than Zn(II) for reactive surface soil sites. Removal of organic matter via H2O2 treatment (<2-mm OMR fraction) dramatically decreased the sorption of both cations; however, Cu(II) was sorbed more than Zn(II). The variation in SSA (obtained by water vapor adsorption) in <2-µm (clay fraction) and <2-mm (whole soil fraction) after Zn(II)/Cu(II) sorption at pH 4 and 6 reflected a different interaction between both cations and binding surface sites. Sorption isotherms correlated better with Langmuir than Freundlich equations. Sorption capacities (q max) in <2-µm fraction, ranged from 166 to 111 mmol kg−1 for Cu(II), and from 62 to 31 mmol kg−1 for Zn(II). This study extends the understanding of the sorption mechanisms of Cu(II) and Zn(II) to agricultural soils from the semi-arid Pampean region of Argentina. An understanding of the local soil environment is important in order to reduce or prevent contamination of this valuable resource, especially from fertilizers and other such anthropogenic additions to the soil.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

Explore related subjects

Discover the latest articles, news and stories from top researchers in related subjects.

References

  • Abollino O, Aceto M, Malandrino M, Mentasti E, Sarzanini C, Barberis R (2002) Distribution and mobility of metals in contaminated sites. Chemometric investigation of pollutant profiles. Environ Pollut 119:177–193

    Article  Google Scholar 

  • Abollino O, Aceto M, Malandrino M, Sarzanini C, Mentasti E (2003) Adsorption of heavy metals on Na-montmorillonite. Effect of pH and organic substances. Water Res 37(7):1619–1627

    Article  Google Scholar 

  • Acebal SG, Mijovilovich A, Rueda EH, Aguirre ME, Saragovi C (2000) Iron-oxide mineralogy of a Mollisol from Argentina: a study by selective-dissolution techniques, X-Ray diffraction, and Mössbauer spectroscopy. Clays Clay Miner 48:322–330

    Article  Google Scholar 

  • Agbenin JO, Olojo LA (2004) Competitive adsorption of copper and zinc by a Bt horizon of a savanna alfisol as affected by pH and selective removal of hydrous oxides and organic matter. Geoderma 119:85–95

    Article  Google Scholar 

  • Aguirre ME (1987). Rol de los minerales amorfos en el proceso de cementación a la agregación. MS. Thesis, Universidad Nacional del Sur, Bahía Blanca, Argentina

  • Benton Jones Jr J (1971) Laboratory guide for conducting soil test and plant analysis. The relationship between soil pH and base-saturation percentage for surface and subsoil horizons of selected mollisols, alfisols, and ultisols in Ohio. Ohio J Sci 71:43–55

    Google Scholar 

  • Bradl HB (2004) Adsorption of heavy metal ions on soils and soils constituents. J Colloid Interf Sci 277:1–18

    Article  Google Scholar 

  • Carter DL, Heilman MC, González CL (1965) Ethylene glycol monoethyl ether for determining surface area of silicate minerals. Soil Sci 100:356–360

    Article  Google Scholar 

  • Cerqueira B, Covelo EF, Andrade ML, Vega FA (2011) Retention and mobility of copper and lead in soils as influenced by soil horizon properties. Pedosphere 21(5):603–614

    Article  Google Scholar 

  • Cornell RM, Schwertmann U (2003) The iron oxides. Structure, properties, reactions, occurences and uses. In: Cornell RM, Schwertmann U (eds) Chapter 10, 2nd edn, Wiley. VCH GmbH & Co. KGaA, Weinheim, pp 221-252

  • Covelo EF, Vega FA, Andrade ML (2008) Sorption and desorption of Cd, Cr, Cu, Ni, Pb and Zn by a Fibric Histosol and its organo-mineral fraction. J Hazard Mater 159:342–347

    Article  Google Scholar 

  • Dean JA (1999) Lange’s handbook of chemistry, 15th edn. McGraw-Hill Inc, New York

    Google Scholar 

  • Dohrmann R, Kaufhold S (2010) Determination of exchangeable calcium of calcareous and gypsiferous bentonites. Clays and Clay Miner 58:79–88

    Article  Google Scholar 

  • Egirani E, Baker A, Andrews J (2005) Cu and Zn removal from aqueous solution by mixed mineral systems I. Reactivity and removal kinetics. J Colloid Intef Sci 291:319–325

    Article  Google Scholar 

  • Eren E, Afsin B (2008) An investigation of Cu(II) adsorption by raw and acid-activated bentonite: A combined potentiometric, thermodynamic, XRD, IR, DTA study. J Hazard Mater 151:682–691

    Article  Google Scholar 

  • Fernández Covelo E (2005) Secuencias de selectividad de adsorción y desorción competitiva de metales pesados en suelos. PhD. Thesis, Universidad de Vigo, Vigo, España

  • Gee GW, Bauder JW (1986) Methods of soil analysis. Part 1. In: Klute A. (ed) physical and mineralogical methods. particle-size analysis. American Society of Agronomy and Soil Science Society of America, Madison, pp 399–403

  • Gu X, Evans LJ, Barabash SJ (2010) Modeling the adsorption of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) onto montmorillonite. Geochim et Cosmochim Acta 74:5718–5728

    Article  Google Scholar 

  • Gupta SS, Bhattacharyya KG (2012) Adsorption of heavy metals on kaolinite and montmorillonite: a review. Phys Chem Chem Phys 4:6698–6723

    Article  Google Scholar 

  • Haile-Mariam S, Collins HP, Wright S, Paul EA (2008) Fractionation and long-term laboratory incubation to measure soil organic matter dynamics. Soil Sci Soc Am J 72:370–378

    Article  Google Scholar 

  • Hossner LR (1996) Methods of soil analysis. Part 3. Chemical methods. In: Spark DL (ed) Dissolution for total elemental analysis. Soil Science Society of America and American Society of Agronomy, Madison, pp 49–64

    Google Scholar 

  • Huang B, Li Z, Huang J, Guo L, Nie X, Wang Y, Zhang Y, Zeng G (2014) Adsorption characteristics of Cu and Zn onto various size fractions of aggregates from red paddy soil. J Hazard Mater 264:176–183

    Article  Google Scholar 

  • Kunze GW, Dixon JB (1986) Methods of soil analysis, part I. In: Klute A (ed) Pretreatment for mineralogical analysis. Soil Science Society of America and American Society of Agronomy, Madison, pp 91–99

    Google Scholar 

  • Lafont D, Soulages OE, Acebal SG, Bonorino AG (2013) Sorption and desorption of mercury(II) in saline and alkaline soils of Bahía Blanca, Argentina. Environ Earth Sci 70:1379–1387

    Article  Google Scholar 

  • Lavado RS, Rodríguez MB, Scheiner JD, Taboada MA, Rubio G, Alvarez R, Alconada M, Zubillaga (1998) Heavy metals in soils of Argentina: Comparison between urban and agricultural soils. Commun Soil Sci Plant Anal 29(11–14):1913–1917

    Article  Google Scholar 

  • Li T, Jiang H, Yang X (2013) Competitive sorption and desorption of Cd and Pb in paddy soils of eastern China. Environ Earth Sci 68:1599–1607

    Article  Google Scholar 

  • Lombardi B, Baschini M, Torres Sánchez RM (2002) Characterization of montmorillonites from bentonite deposits of North Patagonia, Argentina: physicochemical and structural parameter correlation. J Arg Chem Soc 90(4):87–91

    Google Scholar 

  • Lu SG, Xu QF (2008) Competitive adsorption of Cd, Cu, Pb and Zn by different soils of Eastern China. Environ Geology 57:685–693

    Article  Google Scholar 

  • Ma YB, Uren NC (1998) Dehydration, diffusion and entrapment of zinc in bentonite. Clays Clay Miner 46:132–138

    Article  Google Scholar 

  • McKeague JA, Day JH (1966) Dithionite- and oxalate-extractable Fe and Al as aids in differentiating various classes of soils. Can J Soil Sci 46:13–22

    Article  Google Scholar 

  • Mehra OP, Jackson ML (1960) Iron oxide removal from soils and clays by a dithionite-citrate system buffered with sodium bicarbonate. Clays Clay Miner 7:317–327

    Article  Google Scholar 

  • Mesquita M, Vieira e Silva J (2002) Preliminary study of pH effect in the application of Langmuir and Freundlich isotherms to Cu and Zn competitive adsorption. Geoderma 106:219–234

    Article  Google Scholar 

  • Mikutta R, Kleber M, Kaiser K, Jahn R (2005) Review: organic matter removal from soils using hydrogen peroxide, sodium hypochlorite and disodium peroxodisulfate. Soil Sci Soc Am J 69:120–135

    Article  Google Scholar 

  • Ming-Kuí Z, Zhen-Li H, Calvert DV, Stoffella PJ (2006) Extractability and mobility of copper and zinc accumulated in sandy soils. Pedosphere 16(1):43–49

    Article  Google Scholar 

  • Nabulo G, Oryem Origa H, Nasinyama W, Cole D (2008) Assessment of Zn, Cu, Pb and Ni contamination in wetland soils and plants in the Lake Victoria basin. Int J Environ Sci Tech 5(1):65–74

    Article  Google Scholar 

  • Pérez-Novo C, Pateiro-Moure M, Osorio F, Novoa-Muñoz JC, López-Periago E, Arias-Estévez M (2008) Influence of organic matter removal on competitive and noncompetitive adsorption of copper and zinc in acid soils. J Colloid Interf Sci 322:33–40

    Article  Google Scholar 

  • Ponizowsky A, Tsadillas C (2003) Lead (II) retention by alfisol and clinoptilolite cation balance and pH effect. Geoderma 115:303–312

    Article  Google Scholar 

  • Regazzoni AE (1984) Ph.D. Thesis, Universidad Nacional de Tucumán, Argentina

  • Rietveld HM (1969) A profile refinement method for nuclear and magnetic structures. J Appl Crystallogr 2:65–71

    Article  Google Scholar 

  • Rodríguez-Caravajal J (1990) Fullprof, a program for Rietveld refinements and pattern matching analysis. Abstracts XV of Congress of the IUCr, Toulouse, p 127

  • Rueda EH, Ballesteros MC, Grassi RL, Blesa MA (1992) Dithionite as a dissolving reagent for goethite in the presence of EDTA and citrate. Application to soil analysis. Clays Clay Miner 40:575–585

    Article  Google Scholar 

  • Sarfrazi M, Mehdi SM, Hassan G, Abbas ST (2007) Metal contamination in Nullah Dek water and accumulation in rice. Pedosphere 17(1):130–136

    Article  Google Scholar 

  • Schwertmann U, Taylor RM (1989) Iron oxides. In: Dixon JB, Weed SB (eds) Minerals in soil environment, 2nd edn, SSSA Book Ser. 1. SSSA, Madison, pp 379–438

  • Selim H (1992) Modeling the transport and retention of organics nonlinear equilibrium or kinetic reactivity of SO =4 in soils. Adv Agron 47:331–384

    Article  Google Scholar 

  • Smolén S, Sady W (2007) The effect of nitrogen fertilizer form and foliar application on Cd, Cu and Zn concentrations in carrots. Folia Hort Ann 19(1):87–96

    Google Scholar 

  • Srinivasarao Ch, Gayatri SR, Venkateswarlu B, Jakkula VS, Wani SP, Kundu S, Sahrawat KL, Rajasekha Rao BK, Marimuthu S, Gopala Krishna G (2014) Heavy metals concentration in soils under rainfed agro-ecosystems and their relationship with soil properties and management practices. Int J Environ Sci Technol 11(7):1959–1972

    Article  Google Scholar 

  • StatSoft Inc (1995) Statistica for Windows. StatSoft, Inc., Tulsa

  • Sumner ME, Miller WP (1996) Methods of Soil Analysis. Part 3. Chemical methods. In: Spark DL (ed) Cation exchange capacity, and exchange coefficients. Soil Science Society of America and American Society of Agronomy, Madison, pp 65–94

  • Taubaso C, Dos Santos Afonso M, Torres Sánchez RM (2004) Modeling soil surface charge density using mineral composition. Geoderma 121:123–133

    Article  Google Scholar 

  • Torres Sánchez RM, Okumura M, Mercader RM (2001) Charge properties of red Argentine soils as an indicator of iron oxide/clay associations. Aust J Soil Res 29:1–12

    Google Scholar 

  • Torres Sánchez RM, Falasca S (1997) Specific surface and surface charges of some Argentinean soils. Z Pflanz Bodenkunde 160:223–226

    Article  Google Scholar 

  • Tschapek M, Torres Sánchez RM, Wasowski C (1989) Handy methods for determining the isoelectric point of soils. Z Pflanz Bodenkunde 152:73–76

    Article  Google Scholar 

  • Urbano Terrón P, Rojo Hernández C (1992) Condiciones del suelo y desarrollo de las plantas según Russell. Cap. 18, In: Urbano Terrón P, Rojo Hernández C (eds) Mundi-Prensa, Madrid

  • USDA (United States Department of Agriculture) (1999) Soil taxonomy: a basic system for classifying soil. Agriculture Handbook, 436. Washington, D.C., USA, p 863

  • Usman ARA (2008) The relative adsorption selectivities of Pb, Cu, Zn, Cd and Ni by soils developed on shale in New Valley, Egypt. Geoderma 144:334–343

    Article  Google Scholar 

  • Vega FA, Covelo EF, Andrade ML (2008) A versatile parameter for comparing the capacities of soils for sorption and retention of heavy metals dumped individually or together: Results for cadmium, copper and lead in twenty soil horizons. J Colloid Interf Sci 327:275–286

    Article  Google Scholar 

  • Vega FA, Andrade ML, Covelo EF (2010) Influence of soil properties on the sorption and retention of cadmium, copper and lead, separately and together, by 20 soil horizons: comparison of linear regression and tree regression. J Hazard Mater 174:522–533

    Article  Google Scholar 

  • Waterlot C, Bidar G, Pelfrêne A, Roussel H, Fourrier H, Douay F (2013) Contamination, fractionation and availability of metals in urban soils in the vicinity of former lead and zinc smelters. Pedosphere 23(2):143–159

    Article  Google Scholar 

  • Wong JW, Li KL, Zhou LX, Selvam A (2007) The sorption of Cd and Zn by different soils in the presence of dissolved organic matter from sludge. Geoderma 137:310–317

    Article  Google Scholar 

  • Wu J, Laird DA, Thompson MI (1999) Sorption and desorption of Cu on soil clay components. J Environ Qual 28:334–338

    Article  Google Scholar 

  • Yanagisawa H, Sato M, Nodera M, Wada O (2004) Excessive zinc intake elevates systemic blood pressure levels in normotensive rats-potential role of superoxide-induced oxidative stress. J Hypertens 22:543–550

    Article  Google Scholar 

  • Zhou SW, Xu MG, Ma YB, Chen SB, Wei DP (2008) Aging mechanism of copper added to bentonite. Geoderma 147:86–92

    Article  Google Scholar 

  • Zhuang P, Li ZA, Zou B, Xia HP, Wang G (2013) Heavy metal contamination in soil and soybean near the Dabaoshan mine, South China. Pedosphere 23(3):298–304

    Article  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the financial support of the Universidad Nacional del Sur, Bahía Blanca, Argentina. R.M.T.S. is member of CONICET and M.A.F. acknowledges a CONICET fellowship. Special thanks are given to anonymous reviewer for useful and clarifying comments. Financial support from FONCyT (Fondo para la Investigación Científica y Tecnológica), Argentina Project No PICT-1250 and FONARSEC (Fondo Argentino Sectorial) Project FSNano-008 are gratefully acknowledged.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Rosa M. Torres Sánchez.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 171 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Fernández, M.A., Soulages, O.E., Acebal, S.G. et al. Sorption of Zn(II) and Cu(II) by four Argentinean soils as affected by pH, oxides, organic matter and clay content. Environ Earth Sci 74, 4201–4214 (2015). https://doi.org/10.1007/s12665-015-4518-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12665-015-4518-0

Keywords

Navigation