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Dohrmann / Applied Clay Science 34 (2006) 3137

further possibility is to re-exchange the index-cation fractions (b 2 m equivalent diameter) problems usually chosen with an appropriate salt and to determin e the do not occur but this changes when samples with amount of the released index-cations by radioactive unfavourable mineralogical components (concerning Applied Clay Science 34 (2006) 31 37 counting, visible spectroscopy or by a measurement CEC methodology) such as carbonates are examined. www.elsevier.com/locate/clay using atomic absorption. When CEC and exchangeable cation values of calcareous Knowledge of CEC and cation distribution of the clayey materials are determined, these minerals become exchanger surfaces can be used as a powerful tool for partially dissolved during the exchange experiments. This the characterisation of clay minerals, clays and soils, is caused by a decrease of the minerals' stability when especially for quantification of the clay minerals, origin they interact with electrolyte-rich solutions. and genesis of soils, clayey sediments and clay deposits, The paper focuses on the development of a model quality control of clay raw material and improvement of that allows the recognition of flawed CEC and exclay mineral properties for industrial use. Exact CEC changeable cation results. It is simple to use and because and exchangeable cation data is often indispensable for of its precision it provides the user with clear inReiner Dohrmann a better understanding of the system under formation about the correctness of exp erimentally deterconsideration. mined data. Landesamt fr Bergbau, Energie und Geologie (LBEG), Bundesanstalt fr Geowissenschaften und Rohstoffe (BGR), The correct determination of the CEC is difficult due Stilleweg 2, D-30655 Hannover, Germany to a number of methodical problems. With the exception 2. Materials Received 3 June 2005; accepted 9 December 2005 of some special conditions such as an acidic pH value of Available online 1 September 2006 Thirty-one German clayey sediments are used in this study. ca. b 5 or in saline and alkaline (electrolyte-rich) clays, The samples were characterised by conventional XRD the correct value of the CEC is more or less independent techniques (Siemens D 500): random powder diffraction, of pressure, temperature, solution/solid ratio, electrolyte Abstract textured air-dried and glycolised clay fractions (5 mg/cm composition and concentration ( Bache, 1976 ). The prepared on glass slides) and quantitative quartz content deterproposed model requires that only samples of this type In this study a model is proposed enabling the detection of incorrect cation exchange capacity (CEC) and exchangeable cation mined with an internal standard. Semi-quantification of the are chosen. High charge smectites, vermiculites, and values. Numerous CEC and exchangeable cation analyses of clayey sediments, soils and bentonites were performed using mineralogical composition was performed considering grain zeolites show a different cation exchange behaviour. triethanolamine-buffered barium chloride, ammonium acetate, silver thiourea and other exchange CEC,chemical techniques. As analyses long as these size distribution, (XRF),inorganic and High charge and vermiculites havelike such a high naturally clayeysmectites materials only contain adsorbents clay minerals, organic substances and a group of mainly detrital minerals organic carbon content. For mineralogical composition see layer charge density the interlayer cations cannot be like quartz, feldspar and that mica, results obtained with most procedures are correct. Dohrmann Problems arise when materials secondary (2006-this issue) contain . phases like soluble Ca-carbonates and -sulphates. During the CEC-experiments, these phases interact with the exchange solution. readily desorbed quantitatively. In the case of vermicuAccording to expectations, results of exchangeable values are incorrect but CEC is also affected [Deller, B., 1981. lites the rate of cation transportation between calcium the 2 : 1 3. Methods Determination of exchangeable acidity, carbonate ions and change of buffer in triethanolamine-buffered solutions percolated layers is slowed down by the high layer charge density through soil samples containing carbonates. Commun. Soil Sci. Plant Analysis 12, 161177.]. Using the proposed Carbonate and 3.1. Cation exchange procedure (Walker, 1959; Graf von Reichenbach, 1966; Malcolm Sulphate Field Model (CSF model) an evaluation of the accuracy of results is possible. and Kennedy, 1969 ). The complete cation exchange 2006 Elsevier B.V. All rights reserved. The method studied is a batch procedure with triethanotherefore is only possible at increased temperature or lamine-buffered BaCl 2 solution (c =0.1 M) followed by a reduring long term experiments. Zeolites on the other hand Keywords: CEC; Exchangeable calcium; Calcareous soils and clays; Gypsiferous soils and clays; CSF model exchange with aqueous MgCl solution (c =0.1 M). All 2 show a pronounced selectivity for certain cations, here analyses were performed in duplicate with additionally at the determination of an overall CEC for unspecified least two different solution/solid ratios. This was done by cations as demanded in the definition is not possible. varying the solid content (2.0 g and 0.5 g, precision= 1. Introduction clear information about the accuracy of experimentally During the last decades, a number of methods for the 0.0005 g) at fixed amounts of solution. To minimise matrix determined data. determination of the CEC have been developed: ameffects AAS and ICP-measurements were performed with diThe idea of this is to provide soil scientists and The cation using exchange capacity is a fundamental prop-5, monium acetate ( study Lewis, 1949 ), triethanolamine buffered luted solutions an exact commercial apparatus (DOSY clay researchers allowing them to decide erty of clay minerals. The that CEC is checked defined by as control a measure Tamm Company, Germany) was barium chloridewith ( a tool Mehlich, 1948; Bascomb, 1964 ), whether experimentally CEC 1970 and exchangeof the ability of a clay or a soil to adsorb cations such 1 33 Ba, Bache, measurements with analytical standards every time itin was used. radioactive tracers ( determined ; 8 5 Sr, Francis able results set of samples are correct. aFor form that they can a be readily desorbed by competing each experiment 250 ml volumetric flask was used andcation Grigal, 1971 of a),given nephelometry ( Adams and Evans, containing 25 ml HNO solution (c =0.5 M) it for The paper focuses on the (development of a model that ), silver ions ( Bache, 1976 ). CEC is reversible and ischemical a sum 1979 ), methylene blue Hang and Brindley, 1970 3 stabilisation. allows the recognition of incorrect results. It is simple to parameter comparable to soil-pH. thiourea ( Chhabra et al., 1975 ), Cu (II) ethylenediamine use and because of its precision it Cu provides the user with In common CEC procedures the negative charge of a (Bergaya and Vayer, 1997 ), (II) triethylenetetramine 3.1.1. Exchange solutions material is balanced with an index-cation. After that the (Meier and Kahr, 1999 ) and several other techniques. The exchange solution (A) is prepared by dissolving 50.0 g CEC is determined by measuring the difference between The ammonium acetate and the barium chloride methods BaCl 2 dihydrate salt in ca. 1 l of de-ionised water. 45.0 ml the initial and the remaining content of the index-cation Fax: 511 6433664. are +49 used widely and they are very time consuming. A triethanolamine is added and after that pH is fixed with HCl at (e.g. silver thiourea method, Chhabra et al., 1975 ). A E-mail address: reiner.dohrmann@lbeg.niedersachsen.de disadvantage of these procedures is that resulting CEC . 8.1. This solution is filled up to exactly 2000 ml. As a second and exchangeable cation values are B.V. often distorted to a solution (B) 25.0 g of BaCl dihydrate salt is dissolved in de0169-1317/$ - see front matter 2006 Elsevier All rights reserved. 2 ionised water and filled up to exactly 1000 ml. For solution large extent ( Kick, 1956; Deller, 1981 ). For pure clay doi: 10.1016/j.clay.2005.12.006

Cation exchange capacity methodology I: An efficient model for the detection of incorrect cation exchange capacity and exchangeable cation results

R. Dohrmann / Applied Clay Science 34 (2006) 3137

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Fig. 1. Effect of differences in solution capability of exchange solutions on carbonate and sulphate phases and their results on exchangeable calcium values at different solution/solid ratios in CEC determination experiments demonstrated for pure calcite.

supernatant is decanted and filtered into a 250 ml volumetric flask. Step 1) 50 ml of solution (A), 60 min shaking time Step 2) 50 ml of solution (A), 60 min shaking time Step 3) 30 ml of buffer-free solution (B), 30 min shaking time Step 4) 30 ml of de-ionised water, 10 min shaking time Step 5) 30 ml of de-ionised water, 10 min shaking time During the second washing step with de-ionised water (step 5) it cannot be avoided that sometimes the supernatant is cloudy, resulting in a loss of a small portion of the sample followed by a small diminution of the CEC. Repeated centrifugation helps in this case. However, all filtrates are combined and filled up to exactly 250 ml. In this solution the exchangeable cations Na + ,K + ,Mg 2+ and Ca 2 + are analysed. 2+ Re-exchange of adsorbed Ba with Mg 2+ : The adsorbed Ba 2+ is re-exchanged by saturating the clay 5 times with solution C. Shaking time is 20 min at every step with 40 ml of MgCl 2 solution (c =0.1 M). After each step the suspension is centrifuged and the clear supernatant is decanted into a 250 ml volumetric flask. All filtrates are combined. In these solutions Ba 2+ is measured and this represents CEC. Steps 610) 40 ml of solution (C), 20 min shaking time 3.2. Carbonate- and Sulphate Field diagram model
2+

(C) 20.0 g of MgCl hexahydrate is dissolved in de-ionised 2 water and filled up to exactly 1000 ml. 3.1.2. Exchange of originally adsorbed cations with Ba Using 5 single steps (steps 15) with different shaking times and exchange solutions the originally adsorbed cations are desorbed. Therefore the exchange solutions are added to oven-dried clayey samples (b2 mm, dried at max. 60 C) that are weighed in sealable 85 ml centrifuge tubes. Suspensions are shaken in an end over end shaker. Subsequently suspensions are centrifuged at 4000 rpm for 5 min and the clear

The proposed model was developed for soil scientists and clay researchers who want to be sure about the accuracy of their analysis. Incorrect values are easy to detect using this model. There are only minor exceptions. 3.2.1. Principle The principle of the Carbonate- and Sulphate Field Model (CSF model) is based on the differences in the capability of exchange solutions towards dissolution of carbonate and

Fig. 2. Examplesfor incorrect and correct exchangeable Ca

2+

values. The

Fig. 3. Application of the Carbonate- and Sulphate Field graph for a series of natural samples. Evaluation of the incorrectness of exchangeable calcium data of calcareous clays is possible by a visible control: Data points that are located within the Carbonate and Sulphate Field are incorrect. Those of non-calcareous clays are placed on the line and are correct.

data point of the calcareous Opalinuston (filled square) is placed within the Carbonate and Sulphate Field and exchangeable calcium values are therefore detected to be false. The point for the carbonate and sulphate free sample (filled circle, Reuverton) is located on the y=x-line and represents correct values.

34 R. Dohrmann / Applied Clay Science 34 (2006) 3137

Fig. 4. Application of the Carbonate- and Sulphate Field model for different exchangeable cations and the CEC. Exchangeable sodium (A) and potassium (B) values are correct. For exchangeable magnesium (C) 2 dolomite-bearing samples are marked indicating slightly incorrect values. Dependent on carbonate content, CEC (D) values are strongly affected. All analyses were performed using barium chloride method.

sulphate minerals dependent on solution/solid ratio. In Fig. 1 this process is outlined for pure calcite. The example shows the typical situation in an exchange experiment where two different amounts of solid are used and all other parameters are fixed. As calcite is the only mineral present and the CEC of calcite is below detection limit (b0.1 meq/100 g) the calcium cations extracted represent soluble calcium. For the system A on the left ( Fig. 1 ) with the smaller amount of solid (0.5 g) absolutely a smaller amount of calcium (195.5 ppm) is measurable after the experiment is finished compared to the system B with 2 g of solid (346.6 ppm). For the calculation of exchangeable calcium values solution concentration has to be multiplied by several factors, one of those is solution/solid ratio. The goal of this issue is now that although the absolute calcium concentration of the solution in system A is lower compared to that of system B, calculated exchangeable calcium values are higher in system A. The chemical principle of

this is that an exchange solution has a relatively higher solution capability for smaller than for larger portions of solid when dissolution is only partial and not complete. 3.2.2. Introduction of the Carbonate- and Sulphate Field Model Generally CEC and exchangeable cation values of non-acidic samples studied do not necessarily have to change to a large degree dependent on solution/solid ratio. However, due to unwanted chemical reactions incorrect values are common when soluble Caphases are present. To achieve a reliable control for the accuracy of the experimentally obtained data a new type of diagram is proposed called the Carbonate- and Sulphate Field Model. Averages of measurements of CEC or single exchangeable cation values at different solution/solid ratios (0.5 g and 2.0 g) give a pair of values resulting in a point in the Carbonate and Sulphate Field Diagram.

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If the data point ( Fig. 2 ; filled circle) has a position on a line with a slope of 1 (y =x) the exchangeable cation or CEC values are highly likely to be correct. The average of the results of 2 different solution/solid ratios (n= 4) then represents the result. If the data point deviates form the proposed y =x-line more than the permitted laboratory error, calculated from results at a number of clayey samples, ( Fig. 2 ; filled square) the values determined can be regarded as being incorrect. Then both values for different solution/solid ratios are wrong. Unless there are serious analytical error deviations, it is not possible that the results of exchangeable cations or CEC are lower for 0.5 g of sample mass than for 2 g. Therefore data points cannot fall into the field below the y =x-line (not realised area, Fig. 3 ). The two following examples demonstrate the principle of the proposed model: Example 1: Exchangeable calcium measurement of a noncalcareous clay (Reuverton, Germany): 21.6 meq/ 100 g and 21.6 meq/100 g are values for the duplicates using 2.0 g and 21.4 meq/100g and 21.7 meq/100 g are values for the duplicates using 0.5 g. The data point in the Carbonate and Sulphate Field Diagram ( Fig. 2 ) is (21.6 meq/ 100 g |21.6 meq/100 g) for (2 g| 0.5 g). This point is located directly on the line (y =x) with a slope of one and data represented is presumed to be correct. The direct indication for this assumption is given by checking the difference between the sum of exchangeable cations and CEC. For exchangeable magnesium, potassium and sodium values of 5.6, 0.8 and 0.3 meq/100 g were measured. Therefore the sum of exchangeable cations is 28.3 meq/100 g which correlates well with the mineralogical composition and the CEC at 2 g (29.1 meq/100 g) as well as at 0.5 g (30.2 meq/100 g). Example 2: Ca-measurement of a calcareous clayey sediment (Opalinuston, Germany, 3.1 wt.% calcite): 19.3 meq/100 g respectively 19.2 meq/100 g for 2.0 g and 42.5 meq/100 g respectively 43.8 meq/ 100 g for 0.5 g. The data point ( Fig. 2 ) in the Carbonate- and Sulphate Field Diagram is (19.3 meq/100 g | 43.2 meq/100 g) for (2 g| 0.5 g). This point is located within the field above the y =x-line and represents an incorrect result. The explanation for this inaccuracy is that carbonate minerals like calcite or dolomite become partially dissolved by exchange solutions used in CEC-determination procedures. The extent of dissolution depends on solution/solid ratio, reaction time and concentration, and type of electrolyte used. Keeping the amount and composition of solutions fixed, more carbonate minerals

are dissolved using higher solution/solid ratios (Fig. 1 ). This is the case in example 2. For 2 g there is a smaller exchangeable Ca 2+ value compared to the analysis using the 0.5 g sample. Both values are incorrect.

4. Results 4.1. Application of the CSF model In Fig. 3 the Carbonate- and Sulphate Field principle is applied to a series of calcareous and non-calcareous clays. Reg arding the results it is obvious that using this simple graph it is possible to evaluate the accuracy of exchangeable calcium data. The model can also be used for exchangeable sodium, potassium and magnesium, as well as for CEC (Fig. 4 ). For exchangeable sodium ( Fig. 4 A) and potassium values ( Fig. 4 B) no deviation of data points from the y= x-line is observed. Therefore results are assumed to be correct following example 1. In the case of exchangeable magnesium ( Fig. 4 C) there is a small influence of dolomite for 2 samples representing partial dolomite dissolution. Reg arding Fig. 4 D it is evident that CEC data is strongly affected by carbonates. The reason for this inaccuracy is that as witherite (BaCO ) 3 precipitates during the first 5 exchange steps this barium carbonate is partially dissolved during the 5 re-exchange steps with magnesium chloride solution.

Fig. 5. Exchangeable Ca

2+

values of a natural clay with addition of

0.5 wt.% calcite (filled square) and without addition of calcite (filled circle). Due to complete dissolution of the carbonate fraction for the data pair of the calcareous clay, a position on the y =x-line is invented. Here only the difference between the sum of exchangeable cations and CEC reveals the correctness of the data points. This assumption is based on the fact that Ca-sulphate is not present.

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5. Discussion 5.1. Limits of the CSF model The limit of the application of this model is attained when soluble min erals or substances are dissolved completely during the exchange experiment. Usually dissolution is only partial but this is not always the case. It occurs when the concentration of the soluble mineral is very low or when the dissolution capability of an exchange solution for a certain component is very high. This limitation of the model is demonstrated in Fig. 5 . Here a natural clay was analysed for CEC and exchangeable cations with silver thiourea method ( Chhabra et al., 1975 ) and a sample mass of 1 g and 0.5 g. Subsequently, this clay was used for another experiment where a small portion of calcite (Merck, 63200 m fraction) was added to give a carbonate content of 0.5 wt.%. After the experiment was finished exchangeable calcium data shows that there is no quantifiable difference between the experiments with 1 g and 0.5 g. This indicates that the whole calcite portion was dissolved during the exchange experiment. To evaluate the accuracy of the exchangeable calcium data the difference between the sum of exchangeable cations (39.8 meq/100 g) and the CEC (31.1 meq/ 100 g) must be considered. By that an excess of 8.7 meq/ 100 g suggests that exchangeable cation or CEC data are incorrect. When additionally a calcite XRD reflection indicates the presence of this mineral it is possible to predict that exchangeable calcium values should be wrong. In the case of Na 2 CO 3 -activated bentonites or high alkaline clays/soils the whole cation fraction (sum of exchangeable cations and cations in pore water solution) is extracted during cation exchange procedure. By that the base saturation is N100% (=excess of exchangeable cations). Consequently, for these materials evaluation of the correctness of the results using the proposed model is not straightforward. 6. Conclusions The Carbonate- and Sulphate-Field diagram is a useful tool for a fast evaluation of the accuracy of experimental CEC data. It provides the user with helpful information and is easy to use. The limit of the model is reached when soluble phases are only minor constituents or when the exchange solution has a high dissolution capability with respect to the soluble phase. Another restriction is that the correctness of exchangeable cation data of samples with a high electrolyte con-

centration like high alkaline clays or soils cannot be proven. However, when natural clays, soils or bentonites are examined the proposed CSF model usually offers a reliable answer to the question regard ing whether or not the experimentally determined CEC and exchangeable cation values are correct. Acknowledgements The author would like to acknowledge the financial support generously provided by Stipendiatenamt of Aachen Technical University, Germany as well as the Deutsche Forschungsgemeinschaft, project II C 6-Ec 72/3, and Prof. Dr. Wolfram Echle for critical discussions. References
Adams, J.M., Evans, S., 1979. Determination of the cation-exchange capacity (layer charge) of small quantities of clay minerals by nephelometry. Clays and Clay Minerals 27, 137139. Bache, B.W., 1970. Barium isotope method for measuring cationexchange capacity of soils and clays. Journal of the Science of Food and Agriculture 21, 169171. Bache, B.W., 1976. The measurement of cation exchange capacity of soils. Journal of the Science of Food and Agriculture 27, 273280. Bascomb, C.L., 1964. Rapid method for the determination of the cation exchange capacity of calcareous and non-calcareous soils. Journal of the Science of Food and Agriculture 15, 821823. Bergaya, F., Vayer, M., 1997. CEC of clays; measurement by adsorption of a copper ethylenediamine complex. Applied Clay Science 12, 275280. Chhabra, R., Pleysier, J., Cremers, A., 1975. The measurement of the cation exchange capacity and exchangeable cations in soils: a new method. Proc. Int. Clay Conf. , pp. 439449. Wilmette, Illinois, USA. Deller, B., 1981. Determination of exchangeable acidity, carbonate ions and change of buffer in triethanolamine-buffered solutions percolated through soil samples containing carbonates. Communications in Soil Science and Plant Analysis 12, 161177. Dohrmann, R., 2006-this issue. Cation Exchange Capacity Methodology III: Correct exchangeable calcium determination of calcareous clays using a new silver-thiourea method. Applied Clay Science. 34, 4757. Francis, C.W., Grigal, D.F., 1971. A rapid and simple procedure using
8 5 Sr

for determining cation exchange capacities of soils and clays.

Soil Science 112, 1721. Graf von Reichenbach, H., 1966. Anomalien des Kationenaustausches beiVermiculiten. ZeitschriftfurPflanzenernahrung und Bodenkunde 113, 203. Hang, P.T., Brindley, G.W., 1970. Methylene blue adsorption by clay minerals. Determination of surface areas and cation exchange capacities. Clays and Clay Minerals 10, 203212. Kick, H., 1956. Bemerkungen zur T- und S-Wert-Bestimmung nach Mehlich in Bden mit hheren Gehalten an CaCO Pflanzenernahrung, Dungung und Bodenkunde 75, 6769. Lewis, D.R., 1949. Analytical data on reference clay materials. Sect. 3, Base-exchange data. 1950, American Petroleum Institute Project 49 Clay Mineral Standards, Preliminary Report # 7, pp. 91.
3

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Malcolm, R.L., Kennedy, V.C., 1969. Rate of cation exchange on clay minerals as determined by specific ion electrode techniques. Soil Science Society of America Proceedings 34, 247253. Mehlich, A., 1948. Determination of cation- and anion-exchange properties of soils. Soil Science 66, 429445. Meier, L.P., Kahr, G., 1999. Determination of the cation exchange capacity (CEC) of clay minerals using the complexesof copper (II)

ion with triethylenetetramine and tetraethylenepentamine. Clays and Clay Minerals 47, 386388. Walker, G.F., 1959. Diffusion of exchangeable cations in vermiculite. Nature 184, 13921393.