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Washing procedure formixed‐bed ion exchangeresin decontamination forin situ nutrient adsorptionNelson Thiffault a , Robert Jobidon b , CarolDe Blois b & Alison D. Munson aa Ministère des Ressources Naturelles duQuébec , Sainte‐Foyb Centre de Recherche en Biologie Forestière,Faculté de Foresterie et de Géomatique ,Direction de la Recherche ForestièreiversitéLaval , 2700 rue Einstein, Sainte‐Foy,Québecébec, G1K 7P4, Canada , GIF 3W8,CanadaPublished online: 11 Nov 2008.

To cite this article: Nelson Thiffault , Robert Jobidon , Carol De Blois &Alison D. Munson (2000) Washing procedure for mixed‐bed ion exchange resindecontamination for in situ nutrient adsorption, Communications in SoilScience and Plant Analysis, 31:3-4, 543-546, DOI: 10.1080/00103620009370456

To link to this article: http://dx.doi.org/10.1080/00103620009370456

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COMMUN. SOIL SCI. PLANT ANAL., 31(3&4), 543-546 (2000)

Washing Procedure for Mixed-Bed IonExchange Resin Decontamination for InSitu Nutrient Adsorption

Nelson Thiffault,a Robert Jobidon,b Carol De Blois,b andAlison D. Munsona

aCentre de Recherche en Biologie Forestière, Faculté de Foresterie et deGéomatique, Université Laval, Sainte-Foy, Québec G1K 7P4, CanadabMinistère des Ressources Naturelles du Québec, Direction de la RechercheForestière, 2700 rue Einstein, Sainte-Foy, Québec GIF 3W8, Canada

ABSTRACT

Mixed-bed cation + anion exchange resin bags are frequently used to assessin situ nutrient availability in forest soils, and have demonstrated their utilityfor comparing the impacts of different disturbances associated with treatments.They are generally installed in organic or mineral soil horizons for a certaintime period, then recovered and extracted, to inform about nutrient availabilityduring that period. For the method to be effective, the ion exchange sites ofresins must be clear from any contaminants prior to installation in the soil. Awashing procedure to be conducted before in situ burial of mixed-bed resinswas developed and is described. The IONAC NM-60 H+/OH- resins areconsecutively washed with 2 N NaCl, deionized water, and 0.1 N NaOH.Finally, resins are rinsed with deionized water and stored moist and colduntil bag preparation and burial in the soil.

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Copyright © 2000 by Marcel Dekker, Inc. www.dekker.com

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544 THIFFAULTETAL.

INTRODUCTION

Exchange resins have been used to assess soil nutrient availability since the1950s. The first method used resins in free suspension with soil and water (Ameret al., 1955), but subsequently, the resins were placed in nylon-netting (Sibbesen,1977), to avoid the need to separate the resin from the soil. Binkley and Matson(1983) compared the in situ resin bag technique with six other methods forestimating forest soil nitrogen availability; results pointed out that the techniquewas more sensitive to in situ conditions than conventional laboratory methods.This initial investigation led to a widespread use of the technique in fieldexperiments. Researchers used specific anion or cation resins (e.g., Lajtha, 1988;Munson et al., 1993) or mixed-bed cation + anion resins (e.g., Hart et al., 1986;Munson and Timmer, 1995). Repeated washing of cation resins with dilute HC1before burial was introduced by Krause and Ramlal (1987) and is now a commonpractice to remove possible K+ and earthalkaline metals (such as Ca2+)contaminants. However, no such washing technique was shown to be requiredfor mixed-bed cation + anion exchange resins.

In 1997, we used mixed-bed cation + anion exchange resins (J.T. Baker,Phillipsburg, NJ, lot K41638) in mineral soils of a boreal mixed-wood cut-oversite, following the procedure described in Munson and Timmer (1995).Subsequently, at the time of extraction, we found ammonium and sulphurcontamination of blank samples that were not put in the field, taken from thesame lot that was previously used. The presence of these contaminants excludesany interpretation of ammonium availability in the field. The objective of thispaper is to describe a washing method that was elaborated for the mixed-bed type1IONAC NM-60 H7OH" (16-50 mesh) exchange resins, to be conducted prior toinstallation of resin bags. The goal of the procedure is to eliminate anycontaminants and to thereby fully charge exchange sites of the mixed resins.

WASHING PROCEDURE

The general principle of the method is to wash resins with a 2 N NaCl solution,rinse them with deionized water, and finally wash them with a 0.1 NNaOH solutionto eliminate chlorides fixed on the cationic exchange sites during resin washing.The principal chemical reactions involved are as followed: i) cationic resin: R -SO3- Y

+ + C+ - R - SO3" C+ + Y+; ii) anionic resin: R - NH4+ Y- + A" - R - NH4

+ A"+ Y"; where Y+ = H+ or contaminant (NH4

+ or others); Y" = OH" or contaminant(SO3- or others); C+ = Na+; A" = Cl" and OH\

The cationic resin is a strong acid formed by a sulfonated polystyrene chargedwith protons or other cations. In the presence of sodium chloride or sodiumhydroxide, the sulfonated group releases the cation and captures a sodium cation.Sodium has a lower adsorption energy level than hydrogen. So, resins chargedwith it will be more sensitive to the adsorption of cations, once installed in the

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WASHING PROCEDURE FOR ION EXCHANGE RESIN 545

TABLE 1. Sulphur and ammonium content of blank resins used in 1997 and1998, with and without the application of the washing treatment. The 1997 lotwas not submitted to the washing treatment."

Sulphur (S) Ammonium (N-NH4)n mglOg''resin mglOg"'resin

Without washing1997 resin (lot K41638)1998 resin (lot L41652)

With washing1998 resin (lot L41652)

143

3

1.302.06

± 0.10± 0.02

<0.10

1.100.24

± 0.10± 0.01

<0.05

"Ion extraction was achieved with a 2 NNaCl solution. Washing was done witha 2 N NaCl solution to remove sulfate and ammonium. A dilute NaOH solutionwas used to eliminate chlorides from the resins. Finally, resins are in a Na+/OH'form. Results are reported as MEAN±SD.

soil. The anionic resin is a strong base formed by an alkyl quaternary ammoniumpolystyrene charged with hydroxide groups or other anions. In the presence ofsodium chloride, the alkyl quaternary ammonium group releases an hydroxidegroup and captures a chloride anion. This wash ensures that all the exchange sitesare charged with chlorides, even those that were possibly not occupied by OH'groups. Then, washing with sodium hydroxide replaces all the chlorides byhydroxides because Cl' is less retained on the adsorption sites than OH', whichallows one to quantify the amount of chlorides that are adsorbed in the soil.

Once the reactive solutions are prepared, resins are put in a previously washedplastic container with the 2 N NaCl solution. Gently stirring for one hour willfavor the replacement of 1) protons by sodium cations on cationic resin and 2)hydroxides by chlorides on anionic resin. Thereby, potentially uncharged sulphatedand alkyl quaternary ammonium groups become sodium and chloride saturated,respectively. Resins are then rinsed repeatedly with deionized water. The 0.1 NNaOH solution is added and resins are gently stirred in it for 1 hour, to activatethe replacement of chlorides by hydroxides on anionic resin. Then, resins arerinsed repeatedly with deionized water. Once the resins are rinsed, excess wateris removed and resins are stored moist and cold (4°C) in an hermetically sealedcontainer until bag preparation.

Adsorbed Ions Extraction and Analysis

Adsorbed ions (anions: H2PO/, NO3"; cations: K+, Ca2+, Mg2+, and NH4+) were

extracted in a 2 iV sodium chloride solution. Anions and ammonium were analyzedcolorimetrically by spectrophotometry (FIA-AE, Lachat Instruments, Milwaukee,WI) and cations by plasma atomic emission spectrometry (ICAP-9000, ThermoInstruments, Boston, MA). Table 1 shows the sulphur and ammonium content ofblank resins of two lots used in 1997 and 1998, respectively. The washing treatment

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546 THIFFAULTETAL.

was effective in reducing the sulphur and ammonium contaminants below thelevel of detectability (that is 0.10 and 0.05 mg 10 g1 resin for sulphur andammonium, respectively).

CONCLUSIONS

The use of mixed-bed resins offers great possibilities to assess soil fertility inforestry and agriculture. To be effective, resins must be clear of any ioniccompounds in which researchers are interested. The proposed washing procedurewas effective in eliminating both sulfate and ammonium contaminants fromexchange sites of mixed resins.

ACKNOWLEDGMENTS

Research funding was provided by the Ministere des Ressources Naturelles duQuebec (MRN), Direction de la Recherche Forestiere. The procedure describedwas elaborated in the laboratory facilities of the MRN and we express our gratitudeto staff members of this lab.

REFERENCES

Amer, F., D.R. Bouldin, C.A. Black, and F.R. Duke. 1955. Characterization of soilphosphorus by anion exchange resin adsorption and P32 equilibration. Plant Soil 6:391-408.

Binkley, D. and P. Matson. 1983. Ion exchange resin bag method for assessing forest soilnitrogen availability. Soil Sci. Soc. Am. J. 47:1050-1052.

Hart, S.C., D. Binkley, and R.G. Campbell. 1986. Predicting loblolly pine current growthand growth response to fertilization. Soil Sci. Soc. Am. J. 50:230-233.

Krause, H.H. and D. Ramlal. 1987. In situ nutrient extraction by resin from forestedclear-cut and site prepared soils. Can. J. Soil Sci. 67:943-952.

Lajtha, K. 1988. The use of ion-exchange resin bags for measuring nutrient availability ina arid ecosystem. Plant Soil 105:105-111.

Munson, A.D. and V.R. Timmer. 1995. Soil nitrogen dynamics and nutrition of pinefollowing silvicultural treatments in boreal and Great Lakes-St. Lawrence plantations.For. Ecol. Mgt. 76:169-179.

Munson, A.D., H.A. Margolis, and D.G. Brand. 1993. Intensive silvicultural treatment:Impact on soil fertility and planted conifer response. Soil Sci. Soc. Am. J. 57:246-255.

Sibbesen, E. 1977. A simple ion-exchange resin procedure for extracting plant availableelements from soil. Plant Soil 46:665-669.

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