Environment International 26 (2001) 381 387

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A flow system for the determination of metal speciation in soil by sequential extraction
J. Shiowatanaa,b,*, N. Tantidanaia, S. Nookabkaewa, D. Nacaprichaa,b
b

Department of Chemistry, Faculty of Science, Mahidol University, Rama VI Road, Bangkok 10400, Thailand Institute of Science and Technology for Research and Development, Mahidol University, Rama VI Road, Bangkok 10400, Thailand

Abstract A flow extraction system with on-line and off-line flame atomic absorption spectrometric (FAAS) detection was developed to speed up, facilitate, and improve the accuracy of sequential extraction for metal speciation in solid materials. A flow extraction system with off-line detection was more advantageous than the on-line detection. In the proposed system, extraction was performed in a closed extraction chamber where extractants were flowing through sequentially. The extract from each extraction was collected in 4 10 fractions to obtain a total of approximately 180 ml for subsequent FAAS determination. The system is simple, easy to construct and operate. It has less risk of contamination and human error. A widely used three-step sequential extraction scheme was used to evaluate the novel system by analyzing Ca, Fe, Mn, Cu, and Zn in a certified reference material. The extraction time for three-step sequential extraction of soil sample was 4 h. The analytical results for Ca, Fe, Mn, Cu, and Zn of a soil certified reference material using the proposed system were compared with those of the conventional batch extraction. D 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Atomic absorption; Flow; Metal speciation; Sequential extraction; Soil

1. Introduction Sequential extraction to fractionate metals or other elements in solids materials into several groups of different leachability is widely employed to determine the distribution of metals in different phases. Although procedures used are generally tedious and time-consuming, the results can give detailed information about origin, mode of occurrence, bioavailability, potential mobilizability, and transport of the metals in natural environments. It is therefore widely used as a tool for the study of origin and fate of metals in the environment. Despite the fact that sequential extraction is widely employed for the study of many solid materials such as soil, sludge, sediment and solid waste, uniformity in the procedures used is still lacking (Table 1). In addition, questions are frequently raised about the accuracy and meaningfulness of the sequential extraction methods because of the problem of poor selectivity (Kheboian

* Corresponding author. Tel.: +66-2-2461-360; fax: +66-2-2477-050. E-mail address: scysw@mahidol.ac.th (J. Shiowatana).

and Bauer, 1987; Shan and Chen, 1993), redistribution during extraction processes (Raksasataya et al., 1996; Tu et al., 1994), and results being dependent on operation conditions (Sahuquillo et al., 1999). The most widely used sequential extraction schemes are probably those proposed by Tessier et al. (1979) and the Commission of the European Communities Bureau of Reference (BCR) (Quevauviller, 1998). Being an operationally-defined chemical fractionation, sequential extraction inevitably gives results that are dependent on the extraction parameters such as types, concentration, pH of the reagent, sample/extractant ratio, extraction time and temperature, methods of shaking and phase separation, etc. The effects of extraction conditions, as potential sources of irreproducibility, were investigated (Quevauviller, 1998) using the BCR's three-step sequential extraction procedure to analyze a certified reference material CRM601. The authors found that the pH of the extractant after extraction in the reducible step could differ from its original pH up to 1.5 pH units. The pH change during extraction was dependent on the composition of the sample and can affect the amount of metal leaching considerably. Davidson et al. (1999) indicated

0160-4120/01/$ see front matter D 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 1 6 0 - 4 1 2 0 ( 0 1 ) 0 0 0 1 6 - 2

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Table 1 Variation in extraction procedure by different authors Extractant/ Sample ratio 8 40 8 40 Extraction time (h) 1 16 0.5 16 Extraction temperature (C) 20 25 20 96

Extractant Acid-soluble fraction (or carbonate-bound) 0.11 M CH3COOH, pH 3 1 MCH3COOH/CH3COONa, pH 5 Reducible fraction (or Fe/Mn oxide-bound) 0.04 M NH2OHHCl in CH3COOH, pH 2 0.1 M NH2OHHCl in CH3COOH, pH 2 0.25 M NH2OHHCl in 0.05 M HCl, or in 0.01 M HNO3 0.1 M NH2OHSO4, pH 2 Oxidizable fraction (or organic matter-bound) 8.8 M H2O2 in 0.02 M HNO3, pH 2 Followed by 3.0 3.2 M NH4OAc

Phase separation technique centrifuge at 2000 10 000 rpm for 10 30 min; membrane filter 0.45 mm; Whatman No. 42

35 10 50

13 0.5 16

25 85

that the difference in extraction pH is an important source of variability in analytical results. Some proposed procedures, which emphasize the need to adjust the pH of extractant during extraction, should therefore not be overlooked. The effect of extractant concentration was studied (Sahuquillo et al., 1999; Maiz et al., 1997) and was found to affect both the extractibility in the exchangeable and acid-soluble metal extraction steps. The sample/extractant ratio used varied from 1:5 to 1:50. Such varying ratios were found to affect extractibility for some metals but not the others (Kennedy et al., 1997; Maiz et al., 1997). The extraction temperature was also found to affect extracting efficiency of some metals (Sahuquillo et al., 1999). The effect of extraction time was found not to be crucial probably owing to the generally very long extraction time employed in most procedures. Maiz et al. (1997) proposed a rapid sequential extraction procedure by reducing the extraction time in their metal bioavailability study of contaminated soils. Perez-Cid et al. (1998) used an ultrasonic probe to reduce the extraction time from 16 h to 7 min. Others recommended the use of minimal extraction time to allow a steady state to be established between sample and extractant but not so long that dissolution of other phases occurs (Kennedy et al., 1997). Moreover, small operational variations such as speed of centrifugation, shaking mode, and solid liquid phase separation procedure were also reported to cause noncomparability (Sahuquillo et al., 1999; Quevauviller et al., 1993). In this work, a novel approach to improve the accuracy and comparability will be presented. Instead of using a conventional batch extraction process, a flow extraction system was developed. Although Hirner (1992) made a suggestion that a dynamic extraction process in a flow cell could help improve the extraction accuracy, no report has been made of any investigation into this approach. A continuous flow extraction system was developed, and the three-step sequential extraction was used to test

the system. Commonly used extraction parameters such as types of reagent, extraction pH, temperature, reagent concentration, and sample/extractant volume ratio were followed and controlled. Flame atomic absorption spectrometry (FAAS) was used for the determination of Ca, Fe, Mn, Cu, and Zn in the extracts. Evaluation of the proposed method was done by analyzing a certified reference material and comparing the summation of concentration of all phases with the certified values. The result of fraction distribution of each metal was compared with that obtained from a conventional batch method. 2. Experimental 2.1. Extraction chamber and setup 2.1.1. An extraction system with an on-line FAAS detection An extraction chamber was designed to contain a weighed sample and to allow extractants to flow sequentially to successively leach metals from the targeted phases of the stirred sample extractant mixture (Fig. 1a). The chamber and its cover were constructed from borosilicate glass to have a capacity of approximately 10 ml. The outlet of the chamber was furnished with a filter (Whatman glass microfiber filter GF/B 1821 with 1-mm particle retention) to allow dissolved matter to flow through. Extractant is pumped through the chamber using a peristaltic pump (Ismatec, MS-CA4/620C) with silicone tubings of 2 mm inner diameter at its highest rate (flow rate when an aqueous solution is pumped through is approximately 10 ml/min). The heating glass coil was approximately 1 m in length and was heated by the winding heating tape (Glas-Col 300-W heating tape). At Steps II and III, extraction was performed at 60 5C and 55 5C, respectively. An electrical voltage of 135 and 120 V was supplied, respectively, to the heating tape to obtain the above temperatures of the extractant.

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2.3. Preparation of standard solutions and glassware Ultrapure water from a Milli-Q water purification unit was used throughout. All glassware used was previously cleaned and soaked in 10% HNO3 and rinsed with pure water. Standard metal solutions (1000 mg/l) were purchased from Merck or prepared in house from pure metals. Working standard solutions were prepared by diluting the stock solution with ultrapure water when needed. 2.4. Extracting reagents A three-step sequential extraction was carried out using the following solutions. Step I: Solution A (0.11 mol/l acetic acid, pH 3) 6.30 ml glacial acetic acid (J.T. Baker analytical grade) was diluted to 1000 ml with ultrapure water. Step II: Solution B (0.04 mol/l hydroxylamine hydrochloride in 25% acetic acid, pH 2) 2.78 g of NH2OHHCl (Merck) was dissolved in ultrapure water and 250 ml of glacial acetic acid was added. The volume was then made up to 1000 ml with ultrapure water. Step III: Solution C (mixture of 30% hydrogen peroxide adjusted to pH 2 and 0.02 MHNO3 at 8:3 volume ratio, pH 2) 30% H2O2 (BDH AnalaR) was adjusted to pH 2 with HNO3 and was mixed with 0.02 M HNO3 at 8:3 volume ratio.
Fig. 1. Diagram of flow extraction setups: (a) with an on-line detection, (b) with an on-line detection and intermittent standard solution introduction, and (c) with an off-line detection.

2.5. Flow sequential extraction procedure A 0.25-g sample was transferred to a clean extraction chamber together with a magnetic bar (1 cm in length). A glass microfiber filter was then laid, followed by a rubber gasket and the cover on top of the chamber. The chamber was securely clamped. Silicone transfer tubings were connected to the extractant reservoir at one end and to the spectrometer or to the collector vial at the other end. The chamber was placed on a magnetic stirrer. The magnetic stirrer and peristaltic pump were switched on to start the extraction. For an on-line detection system, extract from the flow extraction setup was continuously flowing into the nebulizer of a flame atomic absorption spectrometer and the signal was recorded using a strip chart recorder. For an on-line detection with intermittent standard solution introduction, a discrete sampling (Shiowatana, 1995) was introduced. An amount (150 ml) of standard solution was injected via an injection valve to follow the sensitivity change of the detection. When the signal of extract decreased to the baseline level or became steady, the next extractants were passed through accordingly in the same manner. For Steps II and III, extractants are preheated by switching on the heating coil to 135 and 120 V, respectively.

2.1.2. An extraction system with an on-line FAAS detection and intermittent introduction of standard solution to follow the change of detection sensitivity The similar system as in Fig. 1a was used except that an additional standard solution injection valve (150 ml) was inserted between the extraction system and the spectrometer (Fig. 1b). 2.1.3. An extraction system with an off-line FAAS detection The similar system as Fig. 1a was used without connecting the outlet of extraction chamber to the spectrometer. Instead, fractions of extract were collected for subsequent FAAS measurement. 2.2. Flame atomic absorption metal detection A flame atomic absorption spectrometer (Perkin-Elmer Model 3100) equipped with deuterium background corrector was used for the determination of metals. Metal concentrations were obtained by standard addition technique.

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and heated in an oven at 150C for 16 h. After cooling, the digested clear solutions were made up to volume in 50 ml volumetric flasks. 3. Results and discussion 3.1. Effect of pore size of filter on flow rate of extractant Different methods for isolating the extract from solid sample have been used. These included centrifugation with varying speed and time, filtration (Table 1), or the combination of both procedures. Different filters of varying pore size have been used. Sahuquillo et al. (1999) found that filtration after centrifugation did not affect the amount of metals extracted for the acid-soluble and reducible fractions but increased the amount of the oxidizable fraction. Ideally, a 0.45-mm membrane filter should be used to isolate the solution from particulates. However, it was found that with 0.45-mm filter, the peristaltic pump could not pump the solution through. Leakage is hard to control if a more powerful pump is used. The effect of pore size of filter in the flow extraction system on flow rate of extractant was studied. The results in Fig. 2 show that 1mm pore size glass fiber filter (Whatman GF/B 1821) and 2.5-mm pore size cellulose filter (Whatman No. 42) gave acceptable flow rate. It was also found that the extract from 1-mm filter, when refiltered with 0.45-mm filter, did not give any significant difference in metal concentration. Therefore, 1-mm glass fiber filter was used throughout the rest of this work. 3.2. On-line versus off-line detection A typical extraction profile (which will be called extractogram hereafter) of an on-line extraction is presented in Fig. 3. The flow rate of extract to the detector during extraction decreased with time owing to gradual blockage of fine sample particles on the filter. For this reason, the magnitude of signal of the extractogram was not directly related to the concentration of the metal in the extract. Sensitivity change of the detector can be detected by intermittent introduction of 150 ml of standard solution into the extraction line using the setup in Fig. 1b.

Fig. 2. Effect of type of filter and pore size on extraction flow: (a) glass fiber prefilter, 1.0 mm, (b) Whatman No. 42, 2.5 mm. Sample: sediment; extractant: 0.11 M CH3COOH; sample/chamber volume ratio 0.25 g/10 ml.

For an off-line detection system, extracts were collected in plastic vials at required volume intervals (10 60 ml). When a total volume of 180 ml was collected, the next extractant was passed through and collection of fractions was repeated until all three leaching steps were completed. In between Steps II and III, it is advisable that pure water (ca. 20 ml) was passed through to avoid backflow from vigorous reaction between the two extractants. The extracts were subjected to FAAS measurement after all extraction steps were done. 2.6. Batch sequential extraction procedure A 1.0-g sample was weighed in a 100-ml centrifuge tube and 25 ml of the first extractant (Solution A) was added. The mixture was horizontally shaken for 4 h at ambient temperature. The extract was separated by centrifugation at 3500 rpm for 30 min. The supernatant was decanted and filtered through a Whatman No. 42 filter paper for FAAS measurement. The remaining residue was washed with 10 ml pure water and the washing solution was discarded. The residue was then subjected to Step II extraction. Solution B (25 ml) was added to the residue and the mixture was heated to 96C and shaken for 3 h. The extract was separated and the remaining residue was washed in the same manner as Step I. In Step III, the residue from Step II was quantitatively transferred to an Erlenmeyer flask and 20 ml of Solution C was added. The mixture was heated at 85C for 2 h and then cooled down followed by addition of 20 ml 1 M ammonium acetate pH 2 solution and the heating was continued for 2 h. After cooling, the extract was separated as earlier mentioned. 2.7. Total dissolution of sample and dissolution of residue Closed system digestion vessels from UNISEAL (Israel) of 20 ml capacity were used for acid digestion of soil or sediment samples. Weighed solid samples (0.250 g) or residues were transferred to the vessels together with 5 ml HNO3 and 5 ml HF. The vessels were then tightly sealed

Fig. 3. Extractogram of flow extraction with on-line FAAS detection showing Zn signal for soil sample with 0.11 M CH3COOH extractant.

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3.3. Completeness of extraction in batch extraction and in continuous flow extraction In a batch extraction procedure, extraction is performed until equilibrium is reached for metal ions between the solid sample and the extracting solution. However, Vela et al. (1994) indicated that in some cases, most elements might not achieve equilibrium concentration at the end of the shaking time used. This may be another cause of poor repeatability of the batch extraction. In such system, metal extracted may not reveal the amount extractable. The amount extracted is dependent on the solubility limits that different metal ions can exist in equilibrium with other ions in the extracting solution. The continuous flow extraction is principally an exhaustive extraction process because fresh extractant is continuously passing through the sample until the metal in the target phase is completely leached as seen from the signal being gradually leveling off to baseline level or when no further change in signals was observed. It was found that when 0.25 1.00-g soil sample was subjected to sequential extraction in a 10-ml extraction chamber by the proposed system, approximately 120 180 ml of extractant was adequate to completely leach metals in the target phase. Extraction performed in a continuous flow manner can be more accurate than the batch counterpart for many reasons. First of all, extraction in a flow system can better guarantee complete leaching of the target phase without limitation owing to low solubility of the extractable phase in the solution medium. This is because leaching occurs in a flowing stream of fresh extractant continuously. The completeness of leaching in a batch process depends very much on the solubility of the phase of interest in the extractant at the working conditions. We found better recovery from multiple batch extraction compared to single batch extraction for most soil samples analyzed, which indicated that dissolution of the target phase for most elements was not complete in just one extraction owing to solubility limit (unpublished result).

Fig. 4. Extractogram of flow extraction with on-line FAAS detection and intermittent standard solution introduction showing Zn signal for soil sample with 0.11 M CH3COOH extractant.

The extractogram as seen in Fig. 4 was obtained and the metal concentration in the extract can be calculated. However, an on-line detection system has many other disadvantages when FAAS is used as a detection system such as: a. Extract is totally consumed in the FAAS detection. A replicate measurement or a measurement of more than one element or measurement of other properties of the extracts has to be done by repeating the extraction procedure with a new aliquot of sample. b. The FAAS detection system has to be on operation at all time during extraction process. The long time stability of the spectrometer has to be assured to obtain good accuracy of results. An off-line detection system does not have the above drawbacks and is more favorable. An off-line system was therefore used for further investigation. Fig. 5 presents an extractogram obtained in an off-line system. The amount of metal extracted for each extraction step was obtained by the summation of amounts in all fractions of the corresponding step.

Fig. 5. Extractogram of flow extraction with off-line FAAS detection for a three-step sequential extraction of soil SRM 2710. Sample/chamber volume ratio 0.25 g/10 ml; fraction volume 20 ml.

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Table 2 Comparison of analytical results of batch and flow sequential extraction method for SRM 2710 soil Concentration of metal found (mg/g) (% RSD) Element Ca Fe Mn Cu Zn System batch flow batch flow batch flow batch flow batch flow Step I 1060 70 (6.60) 2020 60 (2.97) 17 2 (11.8) 114 34 (29.8) 1060 110 (10.4) 1830 210 (11.5) 740 70 (9.46) 1560 110 (7.05) 950 75 (7.89) 1590 90 (5.66) Step II 360 16 (4.44) 800 180 (22.6) 6140 210 (3.42) 7660 930 (12.1) 4280 130 (3.04) 3220 610 (19.0) 370 77 (20.8) 1030 100 (9.71) 2250 150 (6.67) 2880 550 (19.1) Step III 156 5 (3.20) n.d.a 1020 40 (3.92) 1950 350 (17.9) 348 8 (2.30) 550 170 (30.9) 1000 80 (8.00) 124 24 (19.3) 394 17 (4.31) 1240 50 (4.03) Residue 10 300 220 (2.13) 8430 700 (8.30) 27 600 1100 (3.98) 24 900 650 (2.61) 2290 110 (4.80) 4730 480 (10.1) 430 40 (9.30) 210 40 (19.0) 1980 10 (0.51) 2250 190 (8.44) Total (mg/g) 11 900 190 (1.56) 11 250 700 (6.22) 34 400 900 (2.62) 34 700 1200 (3.46) 7970 330 (4.14) 10 320 580 (5.63) 2540 90 (3.54) 2910 80 (2.75) 5570 170 (3.05) 7960 460 (5.78) Certified value of total concentration 12 500 300 33 800 1000 10 100 400 2950 130 6952 91 Percent recovery 95.2 90.0 102 103 78.9 102 86 98.6 80.1 114

Batch method: sample 1.00 g, extractant 40 ml. Flow method: sample 0.25 g, chamber volume 10 ml, fraction volume 40 ml. a n.d.: not detected.

3.4. Extraction time In a flow system, extraction was stopped when the target phase is completely leached. A long extraction time to ensure equilibrium being reached was unnecessary. The extraction time for a flow system was found to be very much reduced when compared to the conventional batch method. While a batch sequential extraction usually needs 4 16 h for each step, the flow system can perform the three-step sequential extraction within 4 h. Furthermore, phase separation was done in situ and automatically and no extra time and effort is required for this operation. A batch extraction usually needs more than 30 min for each centrifugal phase separation followed by a manual removal of the liquid phase quantitatively. Washing was usually

required between each step of extraction. A batch extraction not only is much more time consuming but also tedious in operation. 3.5. Comparison of results of flow extraction and batch extraction Table 2 presents the results of metal distribution for Ca, Fe, Mn, Cu, and Zn in a soil sample using a flow system and a conventional batch method. Certified values of total concentration are given to indicate that both methods offered good recovery for all metals studied. The relative standard deviation is also given in parentheses. The repeatability of the flow system is not as good as the batch method especially for results of Steps II and III. This is because the extraction in these two steps needs to be done at elevated temperatures. An accurate control of constant temperature has not been very well achieved. The results presented metal fraction distribution graphically in Fig. 6 show clearly that the total amount for both methods agreed well with certified values. On the other hand, the metal fraction distribution for the two methods differed especially in the case of Cu. It can be seen that carbonate-bound Cu (Step I) is much lower in a batch extraction and higher amount was found in the organic matter-bound fraction (Step III). This may be attributed to readsorption problem, which was seen to be more pronounced for Cu in a batch extraction. Copper is well known for binding strongly with organic ligands in soil (Stumm and Morgan, 1981).

4. Conclusions A novel approach using continuous flow extraction for sequential extraction was proposed. The advantages of the continuous flow extraction can be summarized as follows: 1. Simple and easy to perform.

Fig. 6. Fraction distribution for Ca, Fe, Mn, Cu, and Zn of SRM 2710 soil sample by batch and flow sequential extraction. Total certified concentrations are included.

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2. Tedious procedures such as solid liquid phase separation by centrifugation and manual filtration is not required. 3. Less risk of contamination from experimental environment and personal procedural errors. 4. Rapid because no equilibrium is to be established between the solid liquid phases. A three-step extraction can be done within 4 5 h compared to 2 3 days for a batch method. 5. No washing step is required. If necessary, washing between steps can be simply done by flowing pure water between extraction steps. Extraction in a continuous flow system has still many areas to be investigated. The problem of readsorption in this system should be much less than the batch process because extraction time is greatly reduced thereby allow minimum opportunity for readsorption to occur. Acknowledgments This work is sponsored by the Thailand Research Fund. Chulabhorn Foundation's Royal Golden Jubilee Scholarship to one of the authors is gratefully acknowledged. References
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Kennedy VH, Sanchez AL, Oughton DH, Rowland AP. Use of single and sequential chemical extractants to assess radionuclide and heavy metals availability from soils for root uptake. Analyst 1997;122:89R 100R. Kheboian C, Bauer CF. Accuracy of selective extraction procedures for metal speciation in model aquatic sediments. Anal Chem 1987;59: 1417 23. Maiz I, Esnaola MV, Millan E. Evaluation of heavy metals availability in contaminated soils by a short sequential extraction procedure. Sci Total Environ 1997;206:107 15. Perez-Cid B, Lavilla I, Bendicho C. Speeding up of a 3-stage sequential extraction method for metal speciation using focused ultrasound. Anal Chim Acta 1998;360:35 41. Quevauviller Ph. Operationally defined extraction procedures for soil and sediment analysis: I. Standardization. Trends Anal Chem 1998;17: 289 98. Quevauviller Ph, Rauret G, Griepink B. Conclusions of the workshop. Single and sequential extraction in sediments and soils. Int J Environ Anal Chem 1993;51:231 5. Raksasataya M, Langdom AG, Kim ND. Assessment of the extent of Pb redistribution during sequential extraction by two different methods. Anal Chim Acta 1996;332:1 14. Sahuquillo A, Lopez-Sanchez JF, Rubio R, Rauret G, Thomas RP, Davidson CM, Ure AM. Use of a certified reference material for extractable trace metals to assess sources of uncertainty in the BCR three-stage sequential extraction procedure. Anal Chim Acta 1999;382:317 27. Shan XQ, Chen B. Evaluation of sequential extraction for speciation of trace metals in model soil containing natural minerals and humic acid. Anal Chem 1993;65:802 7. Shiowatana J. Flame AAS determination of Fe in serum with discrete sampling. J Sci Soc Thailand 1995;24:197 206. Stumm W, Morgan JJ. Aquatic chemistry. An introduction emphasizing chemical equilibria in natural waters. 2nd ed. New York: Wiley, 1981. Tessier A, Campbell PGC, Bisson M. Sequential extraction procedure for the speciation of particulate trace metals. Anal Chem 1979;51:844 51. Tu Q, Shan XQ, Qian J, Ni ZM. Trace metal redistribution during extraction of model soils by acetic acid/sodium acetate. Anal Chem 1994;66: 3562 98. Vela LD, Jervis RE, Krishnan SS. Physical and chemical phenomena affecting the leachability of elements in solid wastes. J Radioanal Nucl Chem 1994;150:45 8.