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Multiple Stirred-Flow Chamber Assembly for Simultaneous Automatic Fractionation of Trace Elements in Fly Ash Samples Using a Multisyringe-Based Flow System Warunya Boonjob,†,‡ Manuel Miro´,*,‡ and Vı´ctor Cerda `‡ Department of Chemistry, Faculty of Science, Mahidol University, Rama VI Road, Bangkok 10400, Thailand, and Department of Chemistry, Faculty of Sciences, University of the Balearic Islands, Carretera de Valldemossa, km. 7.5, E-07122 Palma de Mallorca, Illes Balears, Spain There is a current trend in automation of leaching tests for trace elements in solid matrixes by use of flow injection based column approaches. However, as a result of the downscaled dimensions of the analytical manifold and execution of a single extraction at a time, miniaturized flowthrough column approaches have merely found applications for periodic investigations of trace element mobility in highly homogeneous environmental solids. A novel flow-based configuration capitalized on stirred-flow cell extraction is proposed in this work for simultaneous fractionation of trace elements in three solid wastes with no limitation of sample amount up to 1.0 g. A two-step sequential extraction scheme involving water and acetic acid (or acetic acid/acetate buffer) is utilized for accurate assessment of readily mobilizable fractions of trace elements in fly ash samples. The fully automated extraction system features high tolerance to flow rates (e6 mL min-1) and, as opposed to operationally defined batchwise methods, the solid to liquid ratio is not a critical parameter for determination of overall readily leachable trace elements provided that exhaustive extraction is ensured. Analytical performance of the dynamic extractor is evaluated for fractionation analysis of a real coal fly ash and BCR-176R fly ash certified reference material. No significant differences were found at the 0.05 significance level between summation of leached concentrations in each fraction plus residue and concentration values of BCR176R, thus revealing the accuracy of the automated method. Overall extractable pools of trace metals in three samples are separated in less than 115 min, even for highly contaminated ashes, versus 18-24 h per fraction in equilibrium leaching tests. The multiple stirred-flow cell assembly is thus suitable for routine risk assessment studies of industrial solid byproduct. Fly ash is the finely divided residue that results from combustion of a solid fuel, such as coal1 or municipal solid waste.2 Over the past decade there has been a vast interest in reutilization of * Corresponding author. E-mail:
[email protected]. Telephone: +34 971172746. Fax: +34 971173426. † Mahidol University. ‡ University of the Balearic Islands. 10.1021/ac8009609 CCC: $40.75 2008 American Chemical Society Published on Web 08/23/2008
fly ash in civil engineering works as an inexpensive replacement of Portland cement because of increased life of roads and structures by improving concrete durability.1,3 The elemental and mineralogical compositions and physical properties of fly ashes are a function of original coal and combustion temperature, yet the material is always regarded as a hazardous waste owing to the potentially toxic trace metal content. Batchwise leaching tests are the choice tools for detection of potential hazardous effects resulting from disposal or reuse of solid wastes because relevant knowledge as to mobility, availability, and/or eventual impact of anthropogenic metal ions on ecological systems and biological organisms can be drawn.4,5 A survey of literature revealed the existence of a wealth of extraction protocols currently applied for fractionation of trace elements in fly ash6-10 based on different sequence schemes and carried out under various operationally defined conditions. Common to all fractionation schemes of solid materials is the subjection of a certain amount of collected ash to the action of increasingly aggressive leaching agents aimed at releasing particular metal fractions into the liquid phase under steady-state conditions. Even though batchwise extraction methods are well accepted for environmental risk exposure of trace elements in environmental substrates, the ecotoxicological relevance of the information provided is, in fact, questionable since natural occurring processes are always dynamic, while manual protocols, intended to simulate environmental scenarios, inherently are based upon the establishment of a single equilibrium between solid and liquid phases.11 (1) American Coal Ash Association. Fly Ash Facts for Highway Engineers. U.S. Dept. of Transportation, Federal Highway Administration Report No. FHWA-SA-94-081, 1995. (2) Chandler, A. J.; Eighmy, T. T.; Hartlen, J.; Hjelmar, O.; Kosson, D. S.; Sawell, S. E.; van der Sloot, H. A.; Vehlow, J. Municipal Solid Waste Incinerator Residues; Elsevier: Amsterdam, The Netherlands, 1997. (3) American Society for Testing and Materials (ASTM) on Concrete and Concrete Aggregates and Supplementary Cementitious Materials; Designation: C 61803, Annual Book of ASTM Standards, Vol. 04.02, ASTM International: West Conshohocken, PA, 2003. (4) Filgueiras, A. V.; Lavilla, I.; Bendicho, C. J. Environ. Monit. 2002, 4, 823– 857. (5) Bacon, J. R.; Davidson, C. M. Analyst 2008, 133, 25–46. (6) Smichowski, P.; Polla, G.; Go´mez, D. Anal. Bioanal. Chem. 2005, 381, 302–316. (7) Huang, S. J.; Chang, C. Y.; Mui, D. T.; Chang, F. C.; Lee, M. Y.; Wang, C. F. J. Hazard. Mater. 2007, 149, 180–188.
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Two additional major problems have been also recognized,5,12,13 that is, the lack of selectivity of leaching agents for releasing metals associated with a discrete geological phase which is to be influenced by the extractant exposure time and redistribution of target species among phases during extraction, that is, trace elements released by one extractant could associate with other undissolved solid components or freshly exposed surfaces within the time-scale of the extraction step. In order to alleviate the above drawbacks and gain full knowledge on the kinetics of the metal leaching processes, recent trends have been focused on the development of flow-through dynamic (nonequilibrium) partitioning methods to better simulate the percolation of rainwater through environmental solid profiles.11 The fundamental principles of these novel extraction strategies, mostly based on the various generations of flow injection analysis, are critically discussed in a recent review article.14 Most of these approaches integrate a microcolumn packed with a given amount of solid sample at the low milligram level (typically 5-50 mg)15–19 within the flow network through which defined volumes of extractants are pumped either in a continuous-flow or flowprogramming fashion.15-22 The most severe limitations are the small inner capacity of microcartridges and backpressure increase when using sample weights above 100 mg, whereby the technique is merely suitable for fractionation of highly homogeneous samples, otherwise sample representativeness might not be assured. One attempt to expand the scope of dynamic extraction was to design semiautomatic stirred-flow cell extractions where large amounts of sample (>250 mg) could be handled.23 However, this concept was proven unsuitable for fractionation schemes because of the lack of steady leachant flow rate throughout the extraction protocol.23 Regular recalibration of the peristaltic pump used for delivery of extractants or frequent renewal of flexible Tygon pump tubing was actually imperative.23,24 Despite the fact that flow-through methods are reported to greatly accelerate leaching tests,15–22 as opposed to batchwise end-over-end
method, samples are processed one at a time. This is indeed the major shortcoming of flow-through extractors coupled in-line to atomic absorption or atomic emission spectrometers.15–17,19–21 To make dynamic extractions/fractionations practical for routine analysis, there is a need for development of novel instrumentation capable of performing sequential extractions in a parallel fashion. To this end, a fully automated flow-through extraction assembly capitalized on coupling multisyringe pumping with stirred-flow chambers is proposed in this work for reliable and simultaneous execution of multiple extractions. To the best of our knowledge, no analytical setup for parallel dynamic fractionation of environmental samples has been reported so far. By replacing peristaltic pumps with rugged liquid drivers (namely, syringe pumps), the hyphenated extractor is capable of enduring the flow backpressure caused by fine particle clogging of membrane filters of sample containers. The devised system was exploited for expeditious investigation of the leaching behavior of trace elements in fly ash using a two-step sequential extraction protocol. This is the first application of fully automated flow-through extraction for evaluation of potentially mobilizable pools of trace elements in fly ash. Distilled water as endorsed in the European standard EN 1245725 and the German DIN 38414-S426 tests was used as the first leaching solution for ascertainment of the most ecotoxicological relevant fraction, that is, the water soluble elements. Acetic acid or acetic acid/acetate buffer is utilized as the second extractant following the guidelines of the toxicity characteristic leaching procedure (TCLP)27 for ascertainment of increased release of metals by natural or anthropogenic acidification processes, such as acid spill or acid rainfall. The analytical performance of the parallel flow-through extractor is explored for dynamic fractionation of Cu, Cd, Ni, Pb, and Zn in coal fly ash. Method validation is accomplished through the use of mass balance and analysis of a certified municipal solid waste incineration (MSWI) fly ash material (BCR-176R).
(8) Smichowski, P.; Polla, G.; Gomez, D.; Espinosa, A. J. F.; Lopez, A. C. Fuel 2008, 87, 1249–1258. (9) Brunori, C.; Balzamo, S.; Morabito, R. Fresenius J. Anal. Chem. 2001, 371, 843–848. (10) Smeda, A.; Zyrnicki, W. Microchem. J. 2002, 72, 9–16. (11) Fedotov, P. S.; Miro´, M. Fractionation and Mobility of Trace Elements in Soils and Sediments; John Wiley and Sons: New York, 2008; Chapter 12, pp 467-520. (12) Bermond, A. Anal. Chim. Acta 2001, 445, 79–88. (13) Hlavay, J.; Prohaska, T.; Weisz, M.; Wenzel, W. W.; Stingeder, G. J. Pure Appl. Chem. 2004, 76, 415–442. (14) Dong, L.-M.; Yan, X. P. Talanta 2005, 65, 627–631. (15) Beauchemin, D.; Kyser, K.; Chipley, D. Anal. Chem. 2002, 74, 3924–3928. (16) Beeston, M. P.; Glass, H. J.; van Elteren, J. T.; Slejkovec, Z. Anal. Chim. Acta 2007, 599, 264–270. (17) Jimoh, M.; Frenzel, W.; Mu ¨ ller, V.; Stephanowitz, H.; Hoffmann, E. Anal. Chem. 2004, 76, 1197–1203. (18) Buanuam, J.; Miro´, M.; Hansen, E. H.; Shiowatana, J. Anal. Chim. Acta 2006, 570, 224–231. (19) Silva, M.; Kyser, K.; Beauchemin, D. Anal. Chim. Acta 2007, 584, 447– 454. (20) Fedotov, P. S.; Savonina, E. Yu.; Wennrich, R.; Spivakov, B. Ya. Analyst 2006, 131, 509–515. (21) Schreiber, M.; Otto, M.; Fedotov, P. S.; Wennrich, R. Chemosphere 2005, 61, 107–115. (22) Fedotov, P. S.; Zavarzina, A. G.; Spivakov, B. Y.; Wennrich, R.; Mattusch, J.; Titze, K de P.C.; Demin, V. V. J. Environ. Monit. 2002, 4, 318–324. (23) Shiowatana, J.; Tantidanai, N.; Nookabkaew, S.; Nacapricha, D. J. Environ. Qual. 2001, 30, 1195–1205. (24) Shiowatana, J.; Tantidanai, N.; Nookabkaew, S.; Nacapricha, D. Environ. Int. 2001, 26, 381–387.
EXPERIMENTAL SECTION Reagents and Solutions. All reagents were of analytical grade and Milli-Q water (Milllipore Synthesis A10, France) was used throughout. The acetic acid extractant (pH 2.88) was prepared by dilution of 5.7 mL of glacial acetic acid (Scharlau Chemie, Spain) with water to a volume of 1 L. Acetic acid/sodium acetate buffer solution (pH 4.93) was prepared by adding 5.7 mL of glacial acetic acid and 64.3 mL of 1.0 mol L-1 NaOH to 500 mL of water and diluting to a volume of 1 L. Ortho-phosphoric acid (Scharlau Chemie), nitric acid (Merck, Germany), and fluoroboric acid (Probus, Spain) were used for microwave digestion. ICP-multielement standard solution XI (AccuTrace Reference Standard, AccuStandard, CT) was employed for external calibration. A matrix matched procedure was used for analyses of water, acetic acid, and acetic acid/acetate buffer leachates.
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(25) EN 12457-4, Characterization of Waste. Leaching. Compliance Test for Leaching of Granular Waste Materials and Sludges. Part 1-4 (September 2002), CEN/TC 292: Characterization of Waste, 2002. (26) DIN 38414-S4, German Standard Methods for the Examination of Water, Wastewater and Sludge. Sludge and Sediment Group (Group S). Determination of Leachability by Water. VCH-Verlag: Weinheim, Germany, 1984. (27) United States Environmental Protection Agency, Office of Solid Waste, Economic, Methods, and Risk Analysis Division. Toxicity Characteristic Leaching Procedure (TCLP), Method 1311 within Test Methods for Evaluating Solid Waste (SW-846). 1996.
Figure 1. Multisyringe stirred-flow cell setup for three simultaneous flow-through leaching tests.
Polyethylene containers were cleansed in a 10% (v/v) HNO3 bath overnight and then washed successively with deionized water prior to use. Multisyringe Stirred Flow Cell Extractor. The miniaturized device for dynamic fractionation of multiple solid samples is composed of two multisyringe pump modules (BU 4S, Crison Instruments, Allela, Spain) hyphenated to three stirred-flow extraction chambers and one or two 45-position rack autosamplers (Micro Sampler, Crison Instruments). The piston pumps are furnished with 10-mL glass syringes of 10 mL each which are connected in block to a single stepper motor, whereby three extractant solutions might be simultaneously delivered to the extraction chambers at will. Each syringe is equipped with a two-way solenoid commutation valve, which allows connection with the sample container or reagent reservoir regardless of piston displacement. The extraction chambers were designed to contain a weighed sample (
