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Speciation and solubility of copper along a soil contamination gradient

  • Soils, Sec 4 • Ecotoxicology • Research Article
  • Published:
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Abstract

Purpose

The bonding of copper (Cu) in soil is important for bioavailability of Cu and toxicity towards plants and animals. The hypothesis of the present study is that variations in molecular Cu bonding can explain previously reported variations in soil ecotoxicity along a Cu contamination gradient when parent material and mineralogy are similar. The specific aim is to understand molecular bonding at the different levels of bioavailability, and compare this with results from a sequential extraction.

Materials and methods

The studied field samples were retrieved from an anthropogenic contaminated site (Hygum, Denmark) dated to the 1920s. This fallow field shows a steep Cu gradient within a confined area where other soil forming factors are constant. Five surface soil samples (0–15 cm) with Cu levels ranging from background (25 mg Cu kg−1) to strongly contaminated levels (3920 mg Cu kg−1) were analyzed by X-ray absorption spectroscopy [Cu K-edge X-ray absorption near edge structure (XANES)], sequential chemical extractions by a three-step BRC method, particle-size and density fraction, microprobe mapping (2 × 2 μm resolution) and bulk soil chemical analysis.

Results and discussion

Only Cu and the soil organic C contents covaried, and both bulk chemical analyses and microprobe mapping showed strong co-localization of Cu and natural organic matter (NOM). The distribution of Cu between particle-size fractions does not vary significantly, and the clay fraction accounted for 62–75 % of the bulk soil Cu content. The largest Cu fraction (78–81 %) was found in the light density fraction (<1.8 g cm−3). The acid-extractable and the reducible fractions are well explained by a simple linear regression (R 2 = 0.97 and R 2 = 0.99, respectively). Both the oxidizable fraction and the residual fraction level out at the highest contaminations. The molecular environment indicated by XANES was in all the contaminated samples best described by Cu(II) bound to humic acids only. The natural samples’ XANES revealed that a part of the Cu here was mineral bound as Cu(0)/Cu(I).

Conclusions

The microprobe, physical fractionations, and XANES results all supported previous reports that Cu contamination is bound to NOM in soils, and we here show that this is independent of the studied contamination levels when all soil properties except NOM content are constant. Current understanding of sequential chemical extraction protocols does not incorporate this consistently, as the large observed shifts in our extractability of Cu fractions were most likely caused by differences in submicrometer molecular Cu–NOM bonding and not differences in Cu–mineral phase interactions.

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References

  • Boudesocque S, Guillon E, Aplincourt M, Marceau E, Stievano L (2007) Sorption of Cu(II) onto vineyard soils: macroscopic and spectroscopic investigations. J Colloid Interface Sci 307:40–49

    Article  CAS  Google Scholar 

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

  • Christensen BT (1992) Physical fractionation of soils and organic matter in primary particle size and density separates. Adv Soil Sci 20:1–90

    Google Scholar 

  • Evangelou VP, Marsi M (2002) Stability of Ca2+–, Cd2+–, and Cu2+–illite complexes. J Environ Sci Health 37:811–828

    Article  CAS  Google Scholar 

  • Flogeac K, Guillon E, Aplincourt M (2004) Surface complexation of copper (II) on soil particles: EPR and XAFS studies. Environ Sci Technol 38:3098–3103

    Article  CAS  Google Scholar 

  • Fulda B, Voegelin A, Maurer F, Christl I, Kretschmar R (2013) Copper redox transformation and complexation by reduced and oxidized soil humic acid. 1. X-ray absorption spectroscopy study. Envion Sci Technol 47:10903–10911

  • Furnare L, Vailionis A, Strawn DG (2005) Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite. Geochim Cosmochim Acta 69:5219–5231

    Article  CAS  Google Scholar 

  • Gleyzes C, Tellier S, Astruc M (2002) Fractionation studies of trace elements in contaminated soils and sediments: a review of sequential extraction procedures. Trend Anal Chem 21:451–467

    Article  CAS  Google Scholar 

  • Holmstrup MH, Hornum D (2012) Earthworm colonisation of abandoned arable soil polluted by copper. Pedobiologia 55:63–65

    Article  CAS  Google Scholar 

  • Jacobson AR, Dousset S, Andreux F, Baveye PC (2007) Electron microprobe and synchrotron X-ray fluorescence mapping of the heterogeneous distribution of copper in high-copper vineyard soils. Environ Sci Technol 41:6343–6349

    Article  CAS  Google Scholar 

  • Karlsson T, Persson P, Skyllberg U (2006) Complexation of copper(II) in organic soils and in dissolved organic matter–EXAFS evidence for chelate ring structures. Environ Sci Technol 40:2623–2628

    Article  CAS  Google Scholar 

  • Khan M, Bolan N, MacKay A (2005) Adsorption and desorption of copper in pasture soils. Commun Soil Sci Plant Anal 36:2461–2487

    Article  CAS  Google Scholar 

  • Kumpiene J, Mench M., Bes CM, Fitts JP (2011) Assessment of aided phytostabilization of copper-contaminated soil by X-ray absorption spectroscopy and chemical extractions. Environ Poll 159:1536–1542

  • Lair GJ, Gerzabek MH, Haberhauer G, Jakusch M, Kirchmann H (2006) Response of the sorption behavior of Cu, Cd, and Zn to different soil management. J Plant Nutr Soil Sci 169:60–68

  • Lehmann J, Solomon D, Kinyangi J, Dathe L, Wirick S, Jacobsen C (2008) Spatial complexity of soil organic matter forms at nanometre scales. Nat Geosci 1:238–242

  • Li Y, Kawashima N, Li J, Chandra AP, Gerson AR (2013) A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite. Adv Colloid Interf Sci 197:1–32

    Google Scholar 

  • Lützow VM, Kögel-Knabner I, Ekschmidt K, Marschner B, Flessa H (2006) Stabilization of organic matter in temperate soils: mechanisms and their relevance under different soil conditions - a review. Eur J Soil Sci 57:426–445

    Article  Google Scholar 

  • Ma Y, Lombi E, Oliver IW, Nolan AL, McLaughlin MJ (2006) Long-term aging of copper added to soils. Environ Sci Technol 40:6310–6317

    Article  CAS  Google Scholar 

  • Manceau A, Matynia A (2010) The nature of Cu bonding to natural organic matter. Geochim Cosmochim Acta 74:2556–2580

    Article  CAS  Google Scholar 

  • Matera V, Le Hécho I, Laboudigue A, Thomas P, Tellier S, Astruc M (2003) A methodological approach for the identification of arsenic bearing phases in polluted soils. Environ Pollut 126:51–64

    Article  CAS  Google Scholar 

  • Nyamangara J (1998) Use of sequential extraction to evaluate zinc and copper in a soil amended with sewage sludge and inorganic metal salts. Agric Ecosyst Environ 69:135–141

    Article  CAS  Google Scholar 

  • Oorts K (2010) Copper. In: Alloway B (ed) Heavy metals in soils, 3rd edn. Springer, Dordrecht, pp 367–394

  • Quenea K, Lamy I, Winterton P, Bermond A (2009) Interactions between metals and soil organic matter in various particle size fractions of soil contaminated with waste water. Geoderma 149:217–223

    Article  CAS  Google Scholar 

  • Rauret G, López-Sánchez J-F, Sahuquillo A, Barahona E, Lachica M, Ure A et al (2000) Application of a modified BCR sequential extraction (three-step) procedure for the determination of extractable trace metal contents in a sewage sludge amended soil reference material (CRM 483), complemented by a three-year stability study of acetic acid. J Environ Monit 2:228–233

    Article  CAS  Google Scholar 

  • Rauret G, López-Sánchez JF, Sahuquillo A, Rubio R, Davidson C, Ure A et al (1999) Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials. J Environ Monit 1:57–61

    Article  CAS  Google Scholar 

  • Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Radiat 12:537–541

    Article  CAS  Google Scholar 

  • Scott-Fordsmand JJ, Krogh PH, Weeks JM (2000a) Responses of Folsomia fimetaria (Collembola: Isotomidae) to copper under different soil copper contamination histories in relation to risk assessment. Environ Toxicol Chem 19:1297–1303

    Article  CAS  Google Scholar 

  • Scott-Fordsmand JJ, Weeks JM, Hopkin SP (2000b) Importance of contamination history for understanding toxicity of copper to earthworm Eisenia fetica (Oligochaeta: Annelida), using neutral-red retention assay. Environ Toxicol Chem 19:1774–1780

    Article  CAS  Google Scholar 

  • Sen Gupta S, Bhattacharyya KG (2011) Kinetics of adsorption of metal ions on inorganic materials: a review. Adv Colloid Interf Sci 162:39–58

    Article  CAS  Google Scholar 

  • Smolders E, Oorts K, van Sprang P, Schoeters I, Janssen CR, McGrath SP, McLaughlin MJ (2009) Toxicity of trace metals in soils as affected by soil type and aging after contamination: using calibrated bioavailability models to set ecological soil standards. Environ Toxicol Chem 28:1633–1642

    Article  CAS  Google Scholar 

  • Solomon D, Lehmann J, Harden J, Wang J, Kinyangi J, Heymann K et al (2012) Micro- and nano-environments of carbon sequestration: multi-element STXM–NEXAFS spectromicroscopy assessment of microbial carbon and mineral associations. Chem Geol 329:53–73

    Article  CAS  Google Scholar 

  • Strandberg B, Axelsen JA, Pedersen MB, Jensen J, Attrill MJ (2006) Effect of a copper gradient on plant community structure. Environ Toxicol Chem 25:743–753

    Article  CAS  Google Scholar 

  • Strawn DG, Baker LL (2008) Speciation of Cu in a contaminated agricultural soil measured by XAFS, micro-XAFS, and micro-XRF. Environ Sci Technol 42:37–42

  • Strawn DG, Baker LL (2009) Molecular characterization of copper in soils using X-ray absorption spectroscopy. Environ Pollut 157:2813–2821

    Article  CAS  Google Scholar 

  • Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Anal Chem 51:844–851

    Article  CAS  Google Scholar 

  • Tongamp W, Takasaki Y, Shibayama A (2009) Arsenic removal from copper ores and concentrates through alkaline leaching in NaHS media. Hydrometallurgy 98:213–218

    Article  CAS  Google Scholar 

  • Ulery AL, Drees LR (2008) Methods of soil analysis—part 5—mineralogical methods. Soil Sci Soc America; 521 p

  • van Reeuwijk L (ed) (2002) Procedures for soil analysis, 6th edn. ISRIC, Wageningen

    Google Scholar 

  • Wang F, Pan G, Li L (2009) Effects of free iron oxyhydrates and soil organic matter on copper sorption–desorption behavior by size fractions of aggregates from two paddy soils. J Environ Sci 21:618–624

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  • Xia K, Bleam W, Helmke PA (1997) Studies of the nature of Cu2+ and Pb2+ binding sites in soil humic substances using X-ray absorption spectroscopy. Geochim Cosmochim Aacta 61:2211–2221

  • Young SD (2010) Chemistry of heavy metals and metalloids in soils. In: Alloway B (ed) Heavy metals in soils, trace metals and metalloids in soils and their bioavailability, 3rd edn. Springer, Dordrecht, pp 51–95

  • Zimmerman AJ, Weindorf DC (2010) Heavy metal and trace metal analysis in soil by sequential extraction: a review of procedures. Int J Anal Chem 387803:1–7

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by a grant from the Aarhus University Research Foundation. Parts of this research were carried out at Beamline X1 of the DORIS light source at DESY. DESY is a member of the Helmholtz Association (HGF). The authors thank Birte Eriksen, Bente Rasmussen and Anne Thoisen for laboratory assistance, and Thomas Ulrich for help with carrying out the electron microprobe mapping.

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Authors and Affiliations

  1. Department of Geoscience, Aarhus University, Høegh-Guldbergs Gade 2, 8000, Aarhus C, Denmark

    Margrethe T. Nielsen & Søren M. Kristiansen

  2. Department of Bioscience, Aarhus University, Vejlsøvej, 8600, Silkeborg, Denmark

    Janeck J. Scott-Fordsmand

  3. HASYLAB, DESY, Notkestraße 85, 22607, Hamburg, Germany

    Michael W. Murphy

Authors
  1. Margrethe T. Nielsen
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  2. Janeck J. Scott-Fordsmand
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  3. Michael W. Murphy
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  4. Søren M. Kristiansen
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Corresponding author

Correspondence to Søren M. Kristiansen.

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Responsible editor: Kirk T. Semple

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Nielsen, M.T., Scott-Fordsmand, J.J., Murphy, M.W. et al. Speciation and solubility of copper along a soil contamination gradient. J Soils Sediments 15, 1558–1570 (2015). https://doi.org/10.1007/s11368-015-1109-3

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  • DOI: https://doi.org/10.1007/s11368-015-1109-3

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