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Determination of Free Cd, Cu and Zn Concentrations in Lake Waters by In Situ Diffusion Followed by Column Equilibration Ion-exchange

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Abstract

Combining in situ diffusion and column ion-exchange equilibration, we measured free metal ion concentrations (Cd, Cu and Zn) in water samples collected from the epilimnion of 14 lakes in the Rouyn-Noranda area (600 km north-west of Montreal, QC, Canada). Lakes were selected to represent a wide range of physico-chemical characteristics (hardness, pH, dissolved organic matter—DOM, degree of metal contamination), to determine the influence of these parameters on metal speciation. Total dissolved metal concentrations, as determined within the diffusion cells, varied over one to two orders of magnitude: [Cd] 0.19–2.9 nM; [Cu] 36–190 nM; [Zn] 7–2,800 nM. The proportion of total dissolved metal present as free Cd2+ and Zn2+ was relatively constant for the 14 selected lakes, despite the wide pH (4.5–8) and DOM (3–23 mg C/L) ranges, probably reflecting the inverse relationship observed between pH and DOM; this proportion did, however, vary with DOM and pH for Cu. Our experimental free metal ion concentrations were compared with those calculated with the thermodynamic models WHAM (Windermere Humic Aqueous Model VI) and ECOSAT 4.7 (incorporating the NICA-Donnan model). Measured and calculated values were in reasonable agreement for both Cd and Zn although measured values were generally slightly higher, i.e. less than one order of magnitude. For several lakes, measured free Cu concentrations were, however, much higher than the calculated values, suggesting that these models overestimate Cu complexation. The gap between measured and calculated free metal ion concentration becomes more important as the total metal concentration decreases and as pH increases.

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Notes

  1. http://www.ife.ac.uk/Aquatic_Processes/wham/index.html.

  2. http://www.soq.wur.nl/UK/Research/ECOSAT/.

  3. Although we subtracted the mean free metal ion concentration measured using analytical blanks (Cd: 0.030 ± 0.017 nM; Cu: 0.14 ± 0.03 nM; Zn: 6.6 ± 3.1 nM; N = 6), the high variability in Zn contamination, presumably due to sample handling despite all precautions taken, strongly affected some of the low Zn samples.

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Acknowledgments

The authors acknowledge the technical assistance provided by M.G. Bordeleau, F. Beauchamp, R. Néron, M. Guillot and M. Arsenault in the laboratory and R. Rodrigue, J. Orvoine, O. Perceval, I. Louis, A. Giguère, A. Dumoulin, and A. van den Abeele in the field. Comments provided by A. Tessier and K.K. Mueller on earlier versions of the MS were greatly appreciated. Financial support was provided by the Natural Sciences and Engineering Research Council of Canada (NSERC strategic research grant STP 0192937) and by the Fonds québécois de la recherche sur la nature et les technologies (FQRNT team grant). P.G.C. Campbell is supported by the Canada Research Chair Program.

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Authors and Affiliations

  1. INRS-Eau, Terre et Environnement, Université du Québec, 490 de la Couronne, Quebec, QC, G1K 9A9, Canada

    C. Fortin & P. G. C. Campbell

  2. Ecological Assessment Division, Environment Canada, 200 Boulevard Sacré-Coeur, Gatineau, QC, K1A 0H3, Canada

    Y. Couillard

  3. Natural Resources Canada, 601 Booth Street, 2nd Floor, Ottawa, ON, K1A 0E8, Canada

    B. Vigneault

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  1. C. Fortin
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  2. Y. Couillard
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  4. P. G. C. Campbell
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Correspondence to C. Fortin.

Appendix: Ion-exchange technique calibration data

Appendix: Ion-exchange technique calibration data

See Fig. 5 and Table 4.

Fig. 5
figure 5

Distribution coefficients (λ) for Cd, Cu and Zn as a function of pH

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Table 4 Calibration data set for the ion-exchange technique
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Fortin, C., Couillard, Y., Vigneault, B. et al. Determination of Free Cd, Cu and Zn Concentrations in Lake Waters by In Situ Diffusion Followed by Column Equilibration Ion-exchange. Aquat Geochem 16, 151–172 (2010). https://doi.org/10.1007/s10498-009-9074-3

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