Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
RESEARCH ARTICLE

Ion-exchange technique (IET) for measuring Cu2+, Ni2+ and Zn2+ activities in soils contaminated with metal mixtures

D. M. Schwertfeger A B and W. H. Hendershot A C
+ Author Affiliations
- Author Affiliations

A Department of Natural Resources, McGill University, Macdonald Campus, 21111 Lakeshore Road, Sainte Anne de Bellevue, Quebec, H9X 3V9, Canada.

B Environment and Climate Change Canada, Biological Assessment and Standardisation, 335 River Road, Ottawa ON, K1A 0H3, Canada.

C Corresponding author. Email: william.hendershot@mcgill.ca

Environmental Chemistry 14(1) 55-63 https://doi.org/10.1071/EN16130
Submitted: 22 July 2016  Accepted: 20 September 2016   Published: 19 October 2016

Environmental context. Terrestrial environments receiving trace metal contaminants are often impacted by more than one metal. This study demonstrates the adaptation of an ion-exchange technique to simultaneously obtain Cu2+, Ni2+ and Zn2+ activities in soil extracts. These measurements can be used to better understand and predict the behaviour and bioavailability of soil metals in metal–mixture contamination scenarios.

Abstract. Reliable estimates of metal speciation are critical for predicting metal bioavailability and the toxicological effects of metal mixtures in the soil environment; however, simultaneous measurements of metal free ion activities in complex matrices pose a challenge. Although speciation models maybe useful, the uncertainty of metal binding to natural organic matter requires that such models be validated with empirical data. In this study, an ion-exchange resin technique (IET) was adapted for the analysis of Cu2+, Ni2+ and Zn2+ in soil extracts. The analysis was performed with three different soil types spiked with single and multiple metal additions to obtain a range of metal concentrations and combinations. Method detection limits of 0.006, 0.04 and 0.05 µM for Cu2+, Ni2+ and Zn2+ were achieved. The values obtained by IET were comparable with those estimated by Visual MINTEQ, giving a root mean squared error of 0.21, 0.30 and 0.34 (n = 30) for the Cu, Ni and Zn data. The Cu2+ activities obtained by IET were within an order of magnitude of those obtained by a Cu ion-selective electrode, being on average 6-fold greater, with better agreement occurring in samples having lower organic matter contents. The resulting soil metal speciation data revealed that the partitioning of soil Cu to the potentially bioavailable Cu2+ pool differed in the binary mixture with Ni compared with the single-metal Cu treatments. These data can be used to assess metal bioavailability and aid in the interpretation of ecotoxicological effects observed in soils where multiple metals are a concern.

Additional keywords: free ion activity, ion exchange resin, soil extracts, speciation, trace metals.


References

[1]  D. M. Schwertfeger, W. H. Hendershot, Toxicity and metal bioaccumulation in Hordeum vulgare exposed to leached and nonleached copperamended soils. Environ. Toxicol. Chem. 2013, 32, 1800.
Toxicity and metal bioaccumulation in Hordeum vulgare exposed to leached and nonleached copperamended soils.CrossRef | 1:CAS:528:DC%2BC3sXhtFOjsb3L&md5=a332b6638e99de3181b9745357dbb989CAS | 23606189PubMed | open url image1

[2]  S. Sauvé, M. McBride, W. Hendershot, Soil solution speciation of lead(II): effects of organic matter and pH. Soil Sci. Soc. Am. J. 1998, 62, 618.
Soil solution speciation of lead(II): effects of organic matter and pH.CrossRef | open url image1

[3]  D. R. Parker, J. F. Fedler, Z. A. S. Ahnstrom, M. Resketo, Reevaluating the free-ion activity model of trace metal toxicity toward higher plants: experimental evidence with copper and zinc. Environ. Toxicol. Chem. 2001, 20, 899.
Reevaluating the free-ion activity model of trace metal toxicity toward higher plants: experimental evidence with copper and zinc.CrossRef | 1:CAS:528:DC%2BD3MXjslWisLs%3D&md5=c652e8cab5bb53536b0723d121974580CAS | 11345467PubMed | open url image1

[4]  V. I. Slaveykova, K. Dedieu, N. Parthasarathy, R. Hajdu, Effect of competing ions and complexing organic substances on the cadmium uptake by the soil bacterium Sinorhizobium meliloti. Environ. Toxicol. Chem. 2009, 28, 741.
Effect of competing ions and complexing organic substances on the cadmium uptake by the soil bacterium Sinorhizobium meliloti.CrossRef | 1:CAS:528:DC%2BD1MXjvFaisb0%3D&md5=a9bfb7d331dcc3ff12dbb7317e84c591CAS | 19391692PubMed | open url image1

[5]  P. G. C. Campbell, Interactions between trace metals and aquatic organisms: a critique of the free-ion activity model, in Metal Speciation and Bioavailability in Aquatic Systems (Eds A. Tessier, D. R. Turner) 1995, pp. 44–97 (John Wiley: New York, NY).

[6]  X. D. Wang, Y. B. Ma, L. Hua, M. J. McLaughlin, Identification of hydroxyl copper toxicity to barley (Hordeum vulgare) root elongation in solution culture. Environ. Toxicol. Chem. 2009, 28, 662.
Identification of hydroxyl copper toxicity to barley (Hordeum vulgare) root elongation in solution culture.CrossRef | 1:CAS:528:DC%2BD1MXisV2gsb4%3D&md5=9abdeae0875f02935bf508084d742effCAS | open url image1

[7]  F. Degryse, E. Smolders, R. Merckx, Labile Cd complexes increase Cd availability to plants. Environ. Sci. Technol. 2006, 40, 830.
Labile Cd complexes increase Cd availability to plants.CrossRef | 1:CAS:528:DC%2BD2MXhtlarsrfK&md5=cd86a770c906b0380699551230062719CAS | 16509325PubMed | open url image1

[8]  D. M. Di Toro, H. E. Allen, H. L. Bergman, J. S. Meyer, P. R. Paquin, R. C. Santore, Biotic ligand model of the acute toxicity of metals. 1. Technical basis. Environ. Toxicol. Chem. 2001, 20, 2383.
Biotic ligand model of the acute toxicity of metals. 1. Technical basis.CrossRef | 1:CAS:528:DC%2BD38XitlWnuw%3D%3D&md5=6514eabd3c03eaa7197aa29fe555ae53CAS | 11596774PubMed | open url image1

[9]  S. Thakali, H. E. Allen, D. M. Di Toro, A. A. Ponizovsky, C. P. Rooney, F. J. Zhao, J. Zhao, S. P. McGrath, A terrestrial biotic ligand model. 1. Development and application to Cu and Ni toxicities to barley root elongation in soils. Environ. Sci. Technol. 2006, 40, 7085.
A terrestrial biotic ligand model. 1. Development and application to Cu and Ni toxicities to barley root elongation in soils.CrossRef | 1:CAS:528:DC%2BD28XhtV2qs7%2FP&md5=67683ef5f14e64ab77be97dccad5ccd8CAS | 17154020PubMed | open url image1

[10]  S. Lofts, P. Criel, C. R. Janssen, K. Lock, S. P. McGrath, K. Oorts, C. P. Rooney, E. Smolders, D. J. Spurgeon, C. Svendsen, H. Van Eeckhout, F.-Z. Zhao, Modelling the effects of copper on soil organisms and processes using the free ion approach: towards a multi-species toxicity model. Environ. Pollut. 2013, 178, 244.
Modelling the effects of copper on soil organisms and processes using the free ion approach: towards a multi-species toxicity model.CrossRef | 1:CAS:528:DC%2BC3sXotlGju78%3D&md5=8693f9764b46c551c3b40c99eb922861CAS | 23584604PubMed | open url image1

[11]  H. Qiu, M. G. Vijver, C. A. M. van Gestel, E. He, W. J. G. M. Peijnenburg, Modeling cadmium and nickel toxicity to earthworms with the free ion approach. Environ. Toxicol. Chem. 2014, 33, 438.
Modeling cadmium and nickel toxicity to earthworms with the free ion approach.CrossRef | 1:CAS:528:DC%2BC2cXmt1Khug%3D%3D&md5=018258a145b32294aea4d2b875267163CAS | 24424623PubMed | open url image1

[12]  A. L. Nolan, H. Zhang, M. J. McLaughlin, Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques. J. Environ. Qual. 2005, 34, 496.
Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques.CrossRef | 1:CAS:528:DC%2BD2MXislOlt7k%3D&md5=53fe9f1cd968739df01cf08b4cb95775CAS | 15758102PubMed | open url image1

[13]  A. L. Nolan, Y. B. Ma, E. Lombi, M. J. McLaughlin, Speciation and isotopic exchangeability of nickel in soil solution. J. Environ. Qual. 2009, 38, 485.
Speciation and isotopic exchangeability of nickel in soil solution.CrossRef | 1:CAS:528:DC%2BD1MXjt12itb0%3D&md5=3274266e20e093310e21660da4a9ffccCAS | 19202018PubMed | open url image1

[14]  C. Parat, J.-Y. Cornu, A. Schneider, L. Authier, V. Sapin-Didier, L. Denaix, M. Potin-Gautier, Comparison of two experimental speciation methods with a theoretical approach to monitor free and labile Cd fractions in soil solutions. Anal. Chim. Acta 2009, 648, 157.
Comparison of two experimental speciation methods with a theoretical approach to monitor free and labile Cd fractions in soil solutions.CrossRef | 1:CAS:528:DC%2BD1MXptleksro%3D&md5=feb0bc697483e4683a31c37906f6be9fCAS | 19646578PubMed | open url image1

[15]  J. Agbenin, G. Welp, Bioavailability of copper, cadmium, zinc, and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes. Environ. Monit. Assess. 2012, 184, 2275.
Bioavailability of copper, cadmium, zinc, and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes.CrossRef | 1:CAS:528:DC%2BC38XjtFOjt78%3D&md5=06f7b26939144a6000b67d37a401840dCAS | 21590301PubMed | open url image1

[16]  J. Rachou, C. Gagnon, S. Sauvé, Use of an ion-selective electrode for free copper measurements in low salinity and low ionic strength matrices. Environ. Chem. 2007, 4, 90.
Use of an ion-selective electrode for free copper measurements in low salinity and low ionic strength matrices.CrossRef | 1:CAS:528:DC%2BD2sXkt1entb8%3D&md5=20f0a1b7ea3513dcb5ac38607f4ac382CAS | open url image1

[17]  S. Sauve, D. R. Parker, Chemical speciation of trace elements in soil solution, in Chemical Processes in Soils (Eds M. A. Tabatabai, D. Sparks) 2005, pp. 655–688 (Soil Science Society of America: Madison, WI).

[18]  I. A. M. Worms, K. J. Wilkinson, Determination of Ni2+ using an equilibrium ion exchange technique: important chemical factors and applicability to environmental samples. Anal. Chim. Acta 2008, 616, 95.
Determination of Ni2+ using an equilibrium ion exchange technique: important chemical factors and applicability to environmental samples.CrossRef | 1:CAS:528:DC%2BD1cXlvVWjur8%3D&md5=7b2e50638b4b506b0641113cf0e5e5aaCAS | open url image1

[19]  C. Fortin, Y. Couillard, B. Vigneault, P. G. C. Campbell, Determination of free Cd, Cu and Zn concentrations in lake waters by in situ diffusion followed by column equilibration ion-exchange. Aquat. Geochem. 2010, 16, 151.
Determination of free Cd, Cu and Zn concentrations in lake waters by in situ diffusion followed by column equilibration ion-exchange.CrossRef | 1:CAS:528:DC%2BD1MXhsFyjt7rN&md5=fd535b1db19208bbff0b480129a57a60CAS | open url image1

[20]  Z. Chen, P. G. C. Campbell, C. Fortin, Silver binding by humic acid as determined by equilibrium ion-exchange and dialysis. J. Phys. Chem. A 2012, 116, 6532.
Silver binding by humic acid as determined by equilibrium ion-exchange and dialysis.CrossRef | 1:CAS:528:DC%2BC38XjtVGhsr0%3D&md5=2825a5ad6a01cd4e236ac43ef4ea8173CAS | 22375620PubMed | open url image1

[21]  A. Crémazy, S. Leclair, K. K. Mueller, B. Vigneault, P. G. C. Campbell, C. Fortin, Development of an in situ ion-exchange technique for the determination of free Cd, Co, Ni, and Zn concentrations in freshwaters. Aquat. Geochem. 2015, 21, 259.
Development of an in situ ion-exchange technique for the determination of free Cd, Co, Ni, and Zn concentrations in freshwaters.CrossRef | open url image1

[22]  Y. Ge, S. Sauvé, W. H. Hendershot, Equilibrium speciation of cadmium, copper, and lead in soil solutions. Commun. Soil Sci. Plant Anal. 2005, 36, 1537.
Equilibrium speciation of cadmium, copper, and lead in soil solutions.CrossRef | 1:CAS:528:DC%2BD2MXmtlWit7w%3D&md5=738019c5cfca1ac6b1910ffa9e80b7b3CAS | open url image1

[23]  A. Schneider, Adaptation of the ion exchange method for the determination of the free ionic fraction of cadmium in solution. J. Environ. Qual. 2006, 35, 394.
Adaptation of the ion exchange method for the determination of the free ionic fraction of cadmium in solution.CrossRef | 1:CAS:528:DC%2BD28XhtFGit7c%3D&md5=2adb965d403cf5bc8f6d456e8faeea73CAS | 16397115PubMed | open url image1

[24]  P. E. Holm, T. H. Christensen, J. C. Tjell, S. P. McGrath, Speciation of cadmium and zinc with application to soil solutions. J. Environ. Qual. 1995, 24, 183.
Speciation of cadmium and zinc with application to soil solutions.CrossRef | 1:CAS:528:DyaK2MXjtVeqtbs%3D&md5=b3c9c41aa7aafe45cee558bee39b8c67CAS | open url image1

[25]  F. F. Cantwell, J. S. Nielsen, S. E. Hrudey, Free nickel ion concentration in sewage by an ion exchange column-equilibration method. Anal. Chem. 1982, 54, 1498.
Free nickel ion concentration in sewage by an ion exchange column-equilibration method.CrossRef | 1:CAS:528:DyaL38XksVeqtLk%3D&md5=ca0cf87e3cc6ddbe69923817c1f1dbcfCAS | open url image1

[26]  C. Fortin, P. G. C. Campbell, An ion-exchange technique for free-metal ion measurements (Cd2+, Zn2+): applications to complex aqueous media. Int. J. Environ. Anal. Chem. 1998, 72, 173.
An ion-exchange technique for free-metal ion measurements (Cd2+, Zn2+): applications to complex aqueous media.CrossRef | 1:CAS:528:DC%2BD3cXis12gtLY%3D&md5=66dafbe88236cf1237a09caa88898125CAS | open url image1

[27]  D. M. Schwertfeger, W. H. Hendershot, Determination of effective cation exchange capacity and exchange acidity by a one-step BaCl2 method. Soil Sci. Soc. Am. J. 2009, 73, 737.
Determination of effective cation exchange capacity and exchange acidity by a one-step BaCl2 method.CrossRef | 1:CAS:528:DC%2BD1MXlsFylsrc%3D&md5=f6d522e1df35ca4902668129994bde62CAS | open url image1

[28]  J. P. Gustafsson, Visual MINTEQ Ver. 3.0 2010 (Royal Institute of Technology, Land and Water Resource Engineering: Stockholm, Sweden).

[29]  D. G. Kinniburgh, C. J. Milne, M. F. Benedetti, J. P. Pinheiro, J. Filius, L. K. Koopal, W. H. Van Riemsdijk, Metal ion binding by humic acid: application of the NICA-Donnan model. Environ. Sci. Technol. 1996, 30, 1687.
Metal ion binding by humic acid: application of the NICA-Donnan model.CrossRef | 1:CAS:528:DyaK28XhvVKgtL4%3D&md5=1d137e3076f5be8bb68b09b28a47f125CAS | open url image1

[30]  Y. Ge, D. MacDonald, S. Sauvé, W. Hendershot, Modeling of Cd and Pb speciation in soil solutions by WinHumicV and NICA-Donnan model. Environ. Model. Softw. 2005, 20, 353.
Modeling of Cd and Pb speciation in soil solutions by WinHumicV and NICA-Donnan model.CrossRef | open url image1

[31]  D. M. Schwertfeger, W. H. Hendershot, Spike/leach procedure to prepare soil samples for trace metal ecotoxicity testing: method development using copper. Commun. Soil Sci. Plant Anal. 2013, 44, 1570.
Spike/leach procedure to prepare soil samples for trace metal ecotoxicity testing: method development using copper.CrossRef | 1:CAS:528:DC%2BC3sXht1Gju78%3D&md5=faae15e299764805efe71fe7452eb66aCAS | open url image1

[32]  J. D. MacDonald, N. Bélanger, W. H. Hendershot, Column leaching using dry soil to estimate solid-solution partitioning observed in zero-tension lysimeters. 1. Method development. Soil Sediment Contam. 2004, 13, 361.
Column leaching using dry soil to estimate solid-solution partitioning observed in zero-tension lysimeters. 1. Method development.CrossRef | 1:CAS:528:DC%2BD2cXls1Olsbc%3D&md5=26f82cc6503d2d4e17bdc813e45b5866CAS | open url image1

[33]  J. A. Sweileh, D. Lucyk, B. Kratochvil, F. F. Cantwell, Specificity of the ion exchange/atomic absorption method for free copper(II) species determination in natural waters. Anal. Chem. 1987, 59, 586.
Specificity of the ion exchange/atomic absorption method for free copper(II) species determination in natural waters.CrossRef | 1:CAS:528:DyaL2sXlsFGisw%3D%3D&md5=ef935b65088ae04b71fd066950e0d207CAS | open url image1



Rent Article (via Deepdyve) Supplementary MaterialSupplementary Material (725 KB) Export Citation Cited By (2)