Spectrochimica Acta Part B 62 (2007) 1051 1064 www.elsevier.

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Sample preparation techniques based on combustion reactions in closed vessels A brief overview and recent applications
rico M.M. Flores a,, Juliano S. Barin a , Mrcia F. Mesko a , Gnter Knapp b
a b

Departamento de Qumica, Universidade Federal de Santa Maria 97105-900, Santa Maria, RS, Brazil Micro- and Radiochemistry, Graz University of Technology, Technikerstrasse 4, A-8010 Graz, Austria Received 27 December 2006; accepted 27 April 2007 Available online 6 May 2007

Abstract In this review, a general discussion of sample preparation techniques based on combustion reactions in closed vessels is presented. Applications for several kinds of samples are described, taking into account the literature data reported in the last 25 years. The operational conditions as well as the main characteristics and drawbacks are discussed for bomb combustion, oxygen flask and microwave-induced combustion (MIC) techniques. Recent applications of MIC techniques are discussed with special concern for samples not well digested by conventional microwave-assisted wet digestion as, for example, coal and also for subsequent determination of halogens. 2007 Elsevier B.V. All rights reserved.
Keywords: Sample preparation; Combustion techniques; Combustion bomb; Oxygen flask; Microwave-induced combustion

Contents Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Wet digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Combustion techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. General aspects of combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Combustion techniques using open vessels and using dynamic systems . . . . . . . . 3.3. Combustion techniques using closed vessels . . . . . . . . . . . . . . . . . . . . . . 3.3.1. Combustion bomb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.2. Oxygen flask . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.3. Absorbing solutions used in combustion bombs and oxygen flask techniques . 3.3.4. Microwave-induced combustion . . . . . . . . . . . . . . . . . . . . . . . . 4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. 2. 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1051 1052 1052 1053 1053 1053 1054 1055 1055 1058 1059 1060 1061 1061

This paper was presented at the 9th Rio Symposium on Atomic Spectrometry, held in Barquisimeto, Venezuela, 510 November 2006, and is published in the special issue of Spectrochimica Acta Part B, dedicated to that conference. Corresponding author. Fax: +55 55 3220 9445. E-mail address: flores@quimica.ufsm.br (.M.M. Flores). 0584-8547/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.sab.2007.04.018

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1. Introduction Currently, with the exception of analytical techniques that permit direct analysis of solids, most available techniques require samples to be prepared as solutions. In this case, dissolved samples may be tolerable but, in general, digestion is strongly recommended and this step has been considered the Achilles' heel for trace analysis [1]. In this respect, as sample preparation techniques are almost always necessary, many procedures have been developed to allow a convenient element determination by instrumental techniques. Digestion techniques have been discussed in books [26] and some reviews [716] that describe applications for many samples and analytes. In spite of all the recent advances in instrumentation, the development of commercial sample digestion systems has been relatively slow, requiring further impetus [1,17]. Despite the spread and successful application to many samples, the use of conventional techniques based on microwave-assisted acid digestion presents some drawbacks for specific applications. In general, the relatively high stability of some organic materials (for example, graphite) impairs an efficient and complete digestion. In this respect, combustion is the most effective, convenient, and perhaps the oldest way used to decompose organic materials. Combustion techniques allow the conversion of carbon and hydrogen to their corresponding oxidation products. Taking into account the high temperature achieved, practically all organic matrices can be decomposed during combustion and less interference may be expected with subsequent analytical determinations. On the other hand, there is a growing interest for the determination of non-metals in many samples (e.g., biological matrices, polymers, etc.) and, unfortunately, conventional techniques based on acid digestion are not completely suitable for this purpose. In general, digestion techniques may be classified into two major groups: wet digestion and combustion techniques [18]. These techniques are summarized in Table 1 and this classification will be followed in this review. Applications using combustion techniques for digestion of organic samples reported from 1982 to 2006 are described. Wet digestion and

open vessel combustion techniques will be briefly discussed for the purpose of comparing some specific features with those using closed vessel combustion, in particular, for microwaveinduced combustion (MIC) techniques. 2. Wet digestion Wet digestion in open vessels is widespread in elemental analysis. In general, nitric acid is used as oxidant alone or in combination with other acids (e.g., sulfuric and hydrochloric acids) or sometimes with hydrogen peroxide, although other reagents can also be used [1921]. In addition, hydrofluoric acid can be used in combination with nitric acid for the total decomposition of silica containing organic matrices [19,22]. Digestion may be performed in open or closed vessels using classical heating blocks or microwave radiation [2325]. In general, open vessel systems are currently more susceptible to systematic errors, especially those related to contamination or analyte losses. However, losses are dependent on the heating source used and kind of evaporation step (if partial or total) [25]. Low digestion temperature with nitric acid at ambient pressure and, therefore, inadequate oxidation capability are the reasons for the use of other acids or acid mixtures in spite of possible interference with subsequent spectrometric techniques [2630]. On the other hand, these techniques allow high throughput using relatively inexpensive equipment and materials, although limitations related to digestion efficiency, blank levels, and acid consumption may remain. Closed vessels have been currently used in order to improve the oxidation efficiency and to reduce the time of digestion. Although digestion using closed vessels may also employ conventional heating, most of the recent applications have been performed using microwave radiation in view of the relatively shorter time involved [3,31] and also to allow specific applications where high purity reagents and matrix removal are necessary [32]. Pressurized wet digestion has been considered as the state-ofthe-art for sample decomposition for trace element determinations [33] and this technique has been successfully used for digestion of a variety of samples [3,31]. Based on the suitability of nitric acid for most instrumental techniques and the high temperature achieved with pressurized systems, this acid could be used alone for the digestion of many organic materials. Sample digestion with nitric acid between 220 and 250 C (commercial microwave equipments are able to fulfill this condition) leads to residual carbon content (RCC) values in the low percentage range. However, some studies have demonstrated that temperatures higher than 300 C are necessary for complete destruction of some organic substances [3338], as for example methylated arsenic compounds [33,37]. Moreover, vessels made with polytetrafluoroethylene (PTFE) or other similar fluorine-containing polymers in general cannot withstand such extreme reaction conditions and, in this case, other materials should be used [4]. Despite this, high pressure systems have been proposed to achieve low RCC using only nitric acid in closed vessels [3944]. However, depending of sample matrix and equipment design, the sample throughput using these special systems may be not suitable for routine analysis. More details

Table 1 Classification of digestion procedures for decomposition of organic samples (adapted from Ref. [18]) Combustion Open systems Dry-ashing Low-temperature ashing Wickbold combustion Closed systems Combustion bomb Oxygen flask (Schniger) Microwave-induced combustion Dynamic system Trace-O-Mat Wet digestion Open systems Conventional heating Microwave heating

Closed systems Conventional heating Microwave heating

Flow systems Conventional heating Microwave heating

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about wet digestion techniques may be found in books [15] and literature reviews [716]. 3. Combustion techniques Combustion reactions are based on the decomposition of organic matrices by reaction with oxygen at high temperatures or by oxygen radicals and excited oxygen in plasmas. In these procedures, oxidation (and pyrolysis) processes are present using air or pure oxygen. Therefore, few risks of contamination are expected because commercial oxygen may be considered pure with respect to trace element content. After combustion, analytes can generally be present as non-volatile compounds, or as gaseous or volatilized compounds and combustion products may be dissolved in a suitable solution before the analytical determination. 3.1. General aspects of combustion In combustion, the chemical reaction normally involves two components, a fuel and an oxidant. Combustion of an organic substance is a complex and exothermic reaction that results mainly in CO2 and H2O. Combustion in open systems allows the sample oxidation if oxygen is continuously supplied for the reaction. For closed systems, in general, the resulting pressure and temperatures are dependent of sample mass, oxygen availability (i.e., oxygen pressure), vessel dimensions, and reaction rate between the organic matrix and oxygen. For a compound containing only carbon, hydrogen and oxygen, the reaction may be described as: Ca Hb Oc a 1=4 b 1=2 cO2 Y a CO2 1=2 b H2 O Ignition normally is the starting point for conventional combustion reactions. This process takes place when the oxidation reaction is accelerated and reagents are quickly consumed, being commonly accompanied by light emission [45]. For closed vessels, if the rate of energy released by chemical reaction exceeds the rate at which it can be lost to vessel walls, the temperature increases and, consequently, the reaction rate and hence the rate of energy release also increases quickly [46,47]. Thus, the reaction rate accelerates indefinitely, leading to a quick pressure increase with a fast self-acceleration of the reaction. After ignition takes place, the reaction will continue until the supply of reactants is exhausted. Different procedures have been used for ignition in closed vessel combustion systems, such as electric current, infrared radiation and manual ignition using flames[4]. In combustion bombs, electric current ignition is currently performed. Electric ignition or infrared radiation is used for oxygen flasks technique but this last way is only applicable if the vessel walls are transparent or have minimum absorption of infrared radiation (e.g., glass or quartz). The simplest ignition procedure is by using a manual igniter (as matches) to start the combustion of the sample or the combustible sample reservoir. This procedure has been extensively used for ignition in oxygen flasks in spite of the obvious susceptibility to accidents. On the other hand, MIC

techniques use a new means of sample ignition. In this case, microwave radiation is applied as a heating source for an exothermic reaction between filter paper and ammonium nitrate solution in an oxygen pressurized atmosphere that provides a localized heating of paper, causing ignition. As in the case of infrared radiation ignition, MIC technique avoids direct contact of the sample with metal wires and minimizes possible contamination or analyte losses related to these materials [2]. 3.2. Combustion techniques using open vessels and using dynamic systems Combustion in open vessels has been extensively used to decompose samples containing high levels of carbon. Perhaps the most widely used combustion technique has been dry ashing using a muffle furnace. This system basically consists of a crucible containing the sample that is heated up to temperatures of about 500 C. However, although this procedure is still in use, some problems have arisen mainly due to the risks of analyte loss and contamination [48,49]. Extensive information is available in the literature and more details can be found in Refs. [19] and [50]. In order to minimize common drawbacks using open systems, some special systems have been proposed [51,52]. However, low temperature ashing and Wickbold combustion systems represent an advance in this field in view of specific characteristics [5360]. The Wickbold combustion technique, in particular, is very suitable for processing liquid combustible samples, such as petroleum products, which are hardly digested by other techniques. Similar to both these techniques, a dynamic system (called Trace-O-Mat) has been applied to circumvent analyte losses [6164]. This system uses an effective cooling device to prevent losses of volatile analytes. Despite some advantages, the use of these techniques in routine analytical laboratories has been restricted, mainly due to the relatively low throughput and the necessity of supervision by the analyst.

Fig. 1. Combustion bomb system.

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3.3. Combustion techniques using closed vessels Closed vessel combustion systems are mainly related to two classical techniques, combustion bombs and the oxygen flask. In spite of their advantages for some applications, relatively few papers have been published in recent years. The reason may be attributed to recent improvements in microwave-assisted wet

digestion using high pressure closed vessels that have replaced many applications and provided several benefits when compared to other techniques. In spite of these advantages, wet digestion techniques must still undergo additional development, mainly for use in the subsequent determination of non-metals and for the digestion of some materials such as coal and graphite. Especially for these samples, combustion techniques in closed vessels using

Table 2 Combustion bomb digestion of organic materials Sample Automotive shredder Biological samples Butter and plastics Canola oil Coal ash, silicate Coal, animal and plant tissues Coal Element Br, Cl, S S As, Se S B As Be, Cr, Cu, Mn, Ni, Pb, V, Zn Cl Cl, F, N, S F S Te As S Hg Se Br, Cl, F, I, N, P, S Br, Cl, F, P, S Sample size (mg) Digestion conditions 750 1000 600 to 1000 1500 1000 b1500 1000 to 1200 200 ml vessel, 30 atm O2, Na2CO3/NaHCO3 solution containing 1% H2O2, quartz sample cup, cooling in water bath 30 atm O2, 1 g starch as combustion aid, 1 ml H2O 25 atm O2, 1-butanol as combustion aid, 10 ml H2O, glass vessel inserted into the bomb, fused silica combustion cup, 10 min cooling 30 atm O2, 5 ml H2O, 15 min cooling in cold water 2 ml H2O, 10 min cooling 25 atm O2, 10 ml 1.4 mol l 1 HNO3, 10 min cooling in water bath 15 atm O2, quartz liner, 10 ml 10% HNO3, 5 min cooling in water bath 25 to 30 atm O2, 1 g of Eschka mixture (MgO + Na2CO3), 5 ml 10% (NH4)2CO3.H2O, 15 min cooling in water bath 30 atm O2, 5 ml H2O, white oil as combustion aid 20 to 30 atm O2, 5 ml 1 mol l 1 NaOH, 15 min cooling in water bath 20 atm O2, 10 ml H2O, 10 min cooling in water bath 30 atm O2, 0.5 g starch as combustion aid, 3 ml H2O a a 20 atm O2, 10 ml H2O, 5 min shaking 300 ml vessel, 20 atm O2, 10 ml H2O, 5 min shaking 300 ml vessel, 25 atm O2, 0.5 g of kerosene or 1-dodecanol as combustion aid, 10 ml of K2CO3 (25 g l 1) and 5 drops of 30% H2O2, 10 min cooling in water bath 300 ml vessel, 25 atm O2, 0.5 g of kerosene as combustion aid, 10 ml of K2CO3 (25 g l 1) and 5 drops of 30% H2O2 34 bar O2, capsule of acetobutyrate + 0.8 to 1.5 ml paraffin oil as combustion aid, 10 ml 0.5 mol l 1 NaOH + 0.1 ml 30% H2O2, quartz sample cup, 15 min cooling in ice bath and 3 min shaking 340 ml vessel, 25 atm O2, ethanol (0.5 ml) mixed with paraffin pellets (35 to 40 mg) as combustion aid, 5 ml 0.1% HNO3 or 10 ml 10% amine CFA-C solution, 510 min cooling in water bath 30 atm O2, ethylene glycol as combustion aid, 5 ml 1 mol l 1 NaOH, 10 min cooling in water bath 30 atm O2, 5 ml 5% HNO3 + 1% H2O2 30 atm O2, 15 ml (1.8 mmol l 1 Na2CO3 + 1.7 mmol l 1 NaHCO3), quartz sample cup, 10 min cooling on water bath Technique of determination IC Isotopic mass spectrometry HG AAS IC ICP OES GF AAS F AAS Reference [65] [66] [67] [68] [69] [70] [71]

Coal Coal, oil shale Coal, minerals Coal Coal Coal Diesel oil Fish tissue Fish tissue Fuel and waste

1000 1000 200 to 400 500 a a 500 500 500

F AAS (indirect) IC ISE Spectrofluorimetry GF AAS ICP OES ICP OES CV AAS CSV IC

[72] [73] [74] [75] [76] [77] [78] [79] [80] [81]

Fuel and waste

b1000

IC IC

[82] [83]

Incinerator residue Cl, F, S

Milk powder, corn bran, bovine and fish tissues Organic fluorine compounds, air Petroleum Sediment

Ca, Cu, I, K, 250 to 500 Mg, Na, P, S, Zn, F Rare earths elements S 1000 1 ml supernatant (1 g + MgO + toluene + sonication + centrifugation) 1000 300 to 500

ICP OES

[84]

ISE ICP-MS IC

[85] [86] [87]

Solid waste Waste Waste

Cl Cl, S Cl, S

30 atm O2, 5 ml 5% Na2CO3 300 ml vessel, 30 atm O2, 5 ml 1% H2O2, 30 min for cooling 30 atm O2, 25 ml 3% H2O2, cooling in water bath

ISE [88] IC [89] Spectrophotometry [90] and nephelometry

Acronyms: CV AAS: cold vapor atomic absorption spectrometry; CSV: cathodic stripping voltammetry; F AAS: flame atomic absorption spectrometry; GF AAS: graphite furnace atomic absorption spectrometry; HG AAS: hydride generation atomic absorption spectrometry; IC: ion-chromatography; ICP-MS: inductively coupled plasma mass spectrometry; ICP OES: inductively coupled plasma optical emission spectrometry; ISE: ion-selective electrode. a Information not available in English language.

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the combustion bomb, oxygen flask, or MIC provide a convenient way to obtain low RCC digests in a relatively short time. In this regard, although the MIC technique has only been recently proposed, equipment that permits its application is already commercialized and an increasing number of applications could be expected in the future based on previous experience with combustion in closed vessels. 3.3.1. Combustion bomb This technique has been applied for many organic matrices, including automotive shredder, biological samples, butter, polymers, oil, coal, fuels, petroleum, sediment and wastes [6590]. In this system, samples are burned inside a stainless steel bomb in the presence of an excess of oxygen and gaseous products are absorbed into a suitable solution in the same vessel used for combustion. In general, the decomposition of organic matter is effective and may be performed in few minutes. The main parts of a conventional combustion bomb are shown in Fig. 1. Samples are prepared as pellets and positioned in a metallic cup. A platinum wire is placed in close contact with pellet and connected to two electrodes for subsequent ignition. A suitable volume of absorbing solution (typically 5 to 10 ml) is added to the bottom of vessel. After closing, the system is pressurized with oxygen from 20 to 30 atm. Ignition is performed by an electric current that heats the Pt wire and starts the combustion. After cooling, the system is opened and the absorbing solution is removed for subsequent analysis. Sometimes the bomb is immersed in a water bath [65,68,70 72,74,75,81,84,85,87,90] or immersed in ice [83] to accelerate the cooling step. In some cases, the use of combustion aids is necessary to improve the extent of combustion. Some substances that have been used for this purpose include starch [66,76], alcohol and alkanes [67,81,82,84,85], oil [73] and paraffin [83,84]. Using combustion bombs, a relatively high sample mass (in general higher than 0.5 g) can be completely burned and the operation may be completed in less than 30 min taking into account the cooling time. Contamination risks could be associated with the absorbing solutions, although this problem should be more pronounced if trace metals need to be further determined in the digests due to the probable contamination from metallic parts of the vessels. To minimize this risk, special devices have been used to avoid contact between the internal wall of vessels and the absorbing solution. Quartz or fused silica sample cups [65,67,71,83,87] have been used for this purpose. A disadvantage of conventional combustion bombs is related to the efficiency of the washing step that is not automated and sometimes a manual shaking step [79,80,83] must be performed. Despite RCC values being extremely low, only one sample may be processed each time, resulting in relatively low sample throughput. Table 2 summarizes the applications using combustion bombs. As may be seen, many applications are related to the subsequent determination of non-metals, in particular the halogens [65,7274,8185,8890] and S [65,66,68,73,75,78, 8184,87,89,90]. Other elements that have been subsequently determined include As [67,70,77], Se [67,80], P [81,82,84], alkali and alkaline earth elements [84], and transition metals

Fig. 2. Oxygen flask system.

[71,84]. Even an application for subsequent determination of rare earths elements by inductively coupled plasma mass spectrometry (ICP-MS) was recently reported [86]. In general, S and the halogens are determined by ion-chromatography (IC) [65,68,73,8183,87,89] and atomic spectrometric techniques have been used for determination of As, B, Be, Ca, Cr, Cu, Hg, I, K, Mg, Mn, Na, Ni, P, Pb, Se, Te, V and Zn [67,69 72,76,79,84,86]. In view of difficulties using other techniques, combustion bombs have been applied especially for coal digestion [7077]. Other important matrices could be also cited, such as fish tissues [79,80,84], fuel [79,81,82], and wastes [81,82,8890]. Although the combustion bomb may be considered an old technique, it is still in use and some recent applications (since 2000) have been described in the literature [65,70,76,80,8387,89] showing its suitability, especially for subsequent determination of S and the halogens. 3.3.2. Oxygen flask Based on the pioneering work of Berthelot, Hempel [91] proposed a combustion procedure using closed glass vessels (10 l). A convenient absorbing solution was dispensed in the bottom of vessel that was further filled with oxygen at atmospheric pressure (Fig. 2). However, only after Schniger's work in 1955 [92], which reduced the whole method to a micro-scale procedure, was this procedure accepted for more general applications (this system is sometimes called Schniger flask or Schniger system) [93]. This technique has been applied to many samples, including biological materials, coal, drugs, organic compounds, fuel, fossils, polymers, etc. [94144]. In this technique, the sample is wrapped with paper (low-ash content filter paper is generally used) and positioned in a platinum holder. The combustion vessel is filled with oxygen at atmospheric pressure and the platinum holder containing the wrapped sample is inserted into the vessel (usually an Erlenmeyer-type glass vessel). In general, sample

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Table 3 Digestion of organic materials by combustion using the oxygen flask Sample Biological samples Biological samples Element I F Sample size (mg) 20 to 25 100 to 200 Digestion conditions 500 ml flask, 5 ml 0.5% TMAH, standing for 1 h 1000 ml flask, 15 ml 0.01 mol l 1 Al(NO3)3 + Sr(NO3)2 (GF MAS) or 510 ml of citrate buffer (ISE), shaking for 30 min 2% acidified sodium formate 500 ml flask, 10 ml 12 mol l 1 HCl 300 ml flask, 5 ml H2O, standing for 1 h, shaking 2000 ml flask 500 ml flask, 5 ml 0.1 mol l 1 NaOH, standing for 1 h 3% H2O2 500 ml flask, 5 ml H2O, catalyst (10 mg WO3 + 5 mg Sn), shaking for 2 min and standing for 1 h 500 ml flask, 6% H2O2 (S), 0.01 mol l 1 KMnO4 + 3% H2SO4 (Hg), shaking for 2 min, standing for 20 min 500 ml flask, 10 ml 0.7% HNO3 H2O2 500 ml flask, filter paper with adhesive paper as combustion aid, 15 ml TISAB solution 1000 ml flask, 10 ml 3% HNO3, standing for 20 min 200 ml flask, 10 ml 0.06 mol l 1 KOH, standing for 1 h 1000 ml flask, 1 ml 0.5 mol l 1 NaOH + 5 ml 5% H2O2, standing for 30 min 300 ml flask, 5 to 10 mg benzoic acid as combustion aid, 5 ml 1 mol l 1 HNO3, standing for 30 min 300 ml modified flask, 2.5 ml 8 mol l 1 HNO3, standing for 30 min, leaching of Pt holder for 3 min in the absorbing solution 10 ml H2O + 0.7 ml 30% H2O2, standing for 30 min 6% H2O2 in 0.18 mol l 1 NaOH or 2% hydrazine sulphate 10 ml H2O + 0.8 ml 30% H2O2 500 ml flask, 1 ml 0.5 mol l 1 NaOH + 3 ml 5% H2O2 + 20 ml H2O, standing for 40 min 500 ml flask, silica basket, 10 ml 6 mol l 1 HCl, shaking for 10 min 250 ml flask, 10 ml H2O + 0.5 ml 30% H2O2 + 3 ml 0.03 mol l 1 NaHCO3, shaking, standing for 30 min 250 ml flask, 10 ml H2O + 0.5 ml 30% H2O2 + 3 ml 0.03 mol l 1 NaHCO3, shaking for 5 min 10 ml of saturated bromine water or 20 ml 10% KH2PO4 + 4 ml 0.4 mol l 1 NaClO + 2 ml 2 mol l 1 NaOH, shaking for 5 min 300 ml modified flask, 5 ml 0.2 mol l 1 NaOH + 0.5 ml 3% hydrazine sulphate, standing for 30 min 5 ml H2O + 15 ml 0.005 mol l 1 Ce(NO3)3 + 5 ml of 10% glycerol solution, standing for 10 min and shake vigorously 500 ml flask, 4 ml H2O, 2 drops of acetone or dichloromethane as combustion aid 2000 ml flask, 20 ml H2O 5 ml 0.05 mol l 1 DBH (1,3-dibromo-5,5-dimethylhydantoin) in 0.5 mol l 1 NaOH 20 ml 2 mmol l 1 NaHCO3 + 100 mg l 1 NH2NH2 Technique of determination ICP-MS GF MAS, ISE Reference [94] [95]

Biological samples and food Biological samples Biological sample Biological samples Biological samples Biomass fuel Coal Coal Drugs Gas oil Hair Human plasma, hair Milk Organic compounds Organic compounds Organic compounds Organic compounds Organic compounds Organic compounds Organic arsenic compounds Organic bismuth compounds Organic bromine compounds Organic bromine or chlorine compounds Organic bromine or chlorine compounds Organic bromine or chlorine compounds Organic fluorine compounds Organic fluorine compounds Organic fluorine compounds Organic iodine compounds Organic iodine compounds Organic halogenated compounds

I As Cl As, Cu, Mn, Sb, Zn I Cl F Hg, S Se S F Se

40 250 to 500 20 to 25 2 to 6 30 50 to 250 50 Equivalent to 0.2 to 1% of S 40 to 50 Hair 200 mg plasma 1 ml dried at 60 C 500 to 600 20 to 25 3 Equivalent to 0.6 to 1 mg of Cu 10 to 15 30 to 50 2 to 10 10 3 to 5 1 to 4 5 to 7 (mixed with 23 mg of benzoic acid) 3 to 6 5 to 7 5 to 10 5 to 10 Equivalent to 7 mg of F 2.2 to 5.3

CSV GF AAS GC RNAA ICP-MS Titration ISE CV AFS, ICP OES IC Titration ISE

[96] [97] [98] [99] [100] [101] [102] [103] [104] [105] [106]

Fluorospectrophotometry [107]

I S Cd Cu Cl, P Br, Cl, S Br, Cl, P As Bi Br Br, Cl

Spectrophotometry Potentiometric titration Potentiometric titration Potentiometric titration Potentiometric titration IC IC Potentiometric titration Spectrophotometry RP-HPLC Spectrophotometry

[108] [109] [110] [111] [112] [113] [114] [115] [116] [117] [118]

Br, I Br, Cl F F F I I Br, Cl, I

Titration Potentiometric titration Titration Potentiometric titration Potentiometric titration Titration IP-HPLC Potentiometric titration

[119] [120] [121] [122] [123] [124] [125] [126]

2 to 11 (mixed with 500 ml flask, 10 ml H2O + hydrazine hydrate solution, shaking 3040 mg of for 15 min and standing for 15 min cellulose powder)

.M.M. Flores et al. / Spectrochimica Acta Part B 62 (2007) 10511064 Table 3 (continued ) Sample Organic phosphorus compounds Organic phosphorus compounds Organic tungsten compounds Organometallic compounds Petroleum Pharmaceutical product Phosphines Plants Plants Plants Plants Plants Polymers Polymers flameretarded Poultry feedstuff Sugar Urine (lyophilized) Water Element P P W S S Se P F S Se F S Cl Br, Cl Sample size (mg) 2 to 10 Equivalent to 1 mg of P Equivalent to 1.5 to 2.5 mg of W 2.9 to 7.6 Digestion conditions 300 to 500 ml flask, 10 ml 10% HNO3, shaking for 20 min 12 ml H2O + 0.8 ml 30% H2O2, shaking for 30 min Modified oxygen flask with detachable U-shape Pt basket, 3 ml 1 mol l 1 NaOH, shaking, standing for 30 min 3 ml H2O Technique of determination ICP OES Potentiometric titration Potentiometric titration Titration Potentiometric titration IC Titration ISE Spectrophotometry Atom-trapping F AAS ISE ICP OES Titration GC after derivatization GC-ECD ASV RNAA Spectrophotometry

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Reference [127] [128] [129] [130] [131] [132] [133] [134] [135] [136] [137] [138] [139] [140] [141] [142] [143] [144]

0.1 ml (paper 1000 ml flask, 20 ml H2O + 0.010 to 0.015 g NaNO2, on gelatin capsules) shaking, standing for 30 to 45 min 40 500 ml flask, 10 ml H2O 5 to 10 30 to 50 100 1000 (as pellet) 30 to 50 5 to 10 10 to 200 500 ml flask, silica fused hook 500 ml flask, 2.5 ml citrate buffer, shaking, standing for 30 min 5 ml 5% H2O2, standing for 30 min 5000 ml flask, 10 ml 2.5 mol l 1 H3CCOOH 500 ml fused silica flask, 2.5 ml citrate buffer, shaking, standing for 30 min 500 ml flask, absorbing solution into a test tube, standing for 10 to 15 min 1000 ml flask, 10 ml H2O 2000 ml flask, 25 ml 0.1 mol l 1 HCl, stirring for 25 min 10,000 ml flask, modified sample holder with borosilicate glass cup, 5 ml 1 mol l 1 HNO3, standing for 30 min, shaking 2000 ml flask, 25 ml 0.05 mol l 1 H2SO4 250 ml flask, 5 ml 5% H2SO4

Se 200 to 300 Cd, Cu, Pb, 1500 Zn I 50 to 100 P 500 l

Acronyms: ASV: anodic stripping voltammetry; CSV: cathodic stripping voltammetry; CV AFS: cold vapor atomic fluorescence spectrometry; F AAS: flame atomic absorption spectrometry; GC: gas chromatography; GC-ECD: gas chromatography with electron capture detector; GF AAS: graphite furnace atomic absorption spectrometry; GF MAS: graphite furnace molecular absorption spectrometry; IC: ion-chromatography; ICP-MS: inductively coupled plasma mass spectrometry; ICP OES: inductively coupled plasma optical emission spectrometry; IP-HPLC: ion-pair high performance liquid chromatography; ISE: ion-selective electrode; RP-HPLC: reversed phase high performance liquid chromatography; RNAA: radiochemical neutron activation analysis.

masses smaller than 100 mg can be combusted using glass vessels up to 1000 ml. Other materials have been used to fit the sample in the Pt holder, including polyethylene, methylcellulose and gelatin capsules [93]. Ignition may be carried out using an electrical current or focused infrared lamps but, for most systems, a piece of paper can be manually ignited before introduction of the Pt holder into the vessel. After combustion, the vessel can be manually shaken to facilitate the washing of the internal surfaces. This technique is commonly applied to digest one sample each time. Contrary to combustion bombs, the low sample mass that can be burned using the oxygen flask is a limitation for subsequent analysis at very low concentration. In addition, the procedure needs continuous attention by the analyst during combustion and some contamination sources may be present, mainly related to the material used to wrap or encapsulate the sample [98]. On the other hand, this system requires the use of very simple and relatively inexpensive glassware. Nowadays, oxygen flask systems are still commercialized. Procedures using this technique have been applied to different samples and applications described in the literature in the last 25 years are presented in Table 3. As can be seen, most applications are related to the subsequent determination of nonmetals, in particular, for subsequent determination of halogens. Fluorine has been further determined in biological samples

[95,106], coal [102], organic fluorine compounds [121123], and plants [134,137]. Applications for Br have been performed in organic compounds [113,114,117120,126] and polymers [140]. Chlorine has been determined in digests of biological samples [98], biomass [101], organic compounds [112114,118,120,126], and polymers [139,140]. Combustion of biological samples [94,96,100,108], organic compounds [119124,125,126,], and lyophilized urine [143] has been used for further determination of I. Sulphur [103,105,109,113,130,131,135,138], P [112,114,127,128,133,134], and Se [104,107,132,136,141] are other important elements determined in organic matrices using this technique for sample preparation. Other applications include As [97,99,115], Bi [116] and transition metals [99,110,111,129, 142]. Despite the use for subsequent determination of Hg in the past [93], only one application was found for this element since 1982 [103]. On the other hand, recent applications (since 2000) represent only 12% of total references covered in the reviewed period. Most applications use vessels with volumes between 200 to 1000 ml, although higher volumes are also used, including 2 [99,123,141,143], 5 [136], and also 10 l [142]. In addition to filter paper, other combustion aids have been used, such as benzoic acid [109] and organic solvents [122]. After combustion, a standing time varying from 10 to 60 min is recommended

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Fig. 3. Characteristics of the MIC technique related to microwave-assisted and combustion digestion procedures (performed in closed vessels).

for some analytes. Moreover, vessels can be manually shaken to obtain better analyte recoveries [102,116,118,119,127,128]. Usually, techniques normally applied for subsequent determination involve potentiometric or normal titrations. Other techniques include atomic spectrometry [94,97,100,103,127,136,38], electroanalytical techniques [95,96,102,106,134,137,142], and chromatography [98,104,113,114,117,125,132,140,141]. Among the main applications of the oxygen flask are included digestion of biological samples [94100,106108,143], organic compounds [109114], plants [134138], and halogenated compounds [117,118,119,120,121,122,123,124,125,126]. In contrast to combustion bombs, only two applications were found for coal using this technique [102,103]. 3.3.3. Absorbing solutions used in combustion bombs and oxygen flask techniques An important aspect of combustion techniques is related to absorbing solutions. After combustion, the analytes must be quantitatively retained in the solution prior to the determination step. Unfortunately, there is no universal absorbing solution and its selection depends mainly on the kind of analyte and its suitability for the determination technique. As can be seen in Tables 2 and 3, the major applications of combustion bombs and oxygen flasks are for non-metals determination, especially for halogens, phosphorus and sulfur. Different absorbing solutions have been used for fluorine. Water or carbonate solution [73,81,82,102,122,123] is the most used absorbing media, although alkaline solutions have been also used, probably due to their suitability for further determination of F (IC, ion selective electrode, titration). Total ionic strength adjustment buffer [106] or citrate buffer [95,134,137] may be used when ISE is the determination technique. For chlorine, the absorbing solutions are very similar to those used for sulfur, as hydrogen peroxide diluted in water [89,90,101,112,114] or sodium/potassium carbonatebicarbonate solution [65,81,82,88]. A combination of these solutions has also been used [118]. Hydrazine sulfate was proposed in some studies [113,120,126] however, good results have been obtained using only water [73,98,140]. For bromine, the solutions were similar to the absorbing solutions used for chlorine and sulfur, based mainly on carbonate or alkaline solutions [65,81,82,113, 114,118,120,126,140]. To avoid losses of iodine, alkaline solutions have been used for both combustion techniques. Solutions of sodium hydroxide, sodium formate and sodium/potassium carbonatebicarbonate have been successfully applied [81,96,100,108,125,126]. On the other hand, the use of dilute H2SO4 was reported in one study for analysis of lyophilized urine [143]. Optionally, solutions of tetramethylammonium hydroxide or tertiary amines, can be used

as absorbing solutions. These solutions, in particular CFA-C, allow the stabilization of the dissolved iodine in the liquid phase and low relative standard deviations are obtained in comparison with NaOH solutions [62]. An alkaline solution of 1,3-dibromo5,5-dimethylhydantoin reagent was also proposed to improve iodine recoveries [124]. During combustion, sulfur trioxide and sulfur dioxide can be formed from organic sulfur compounds in the sample. In this case, sulfur oxides should be absorbed using oxidizing solutions to assure that all organic sulfur are present as sulfate before the determination step. In general, hydrogen peroxide diluted in water is used alone [66,68,89,90,103,105,135] or together sodium/potassium carbonatebicarbonate [65,81,82], or sodium hydroxide [83,109,113] solutions. However, some studies report good results for sulfur using only water as the absorbing solution [66,73,75,130]. For phosphorus, when organic samples are burned, different species of phosphorus oxides can be formed and an oxidant solution containing HNO3 [127] or H2O2 [81,112,114,128] could be used to convert these species to orthophosphate before the determination step. Combustion techniques have been not currently used for subsequent determination of metals. However, some studies reported good results using dilute inorganic acids, as HNO3 [71,84,110,

Fig. 4. Vessel and sample holder for the MIC technique.

.M.M. Flores et al. / Spectrochimica Acta Part B 62 (2007) 10511064 Table 4 Typical maximum combustion temperatures and RCC for some materials (initial oxygen pressure of 20 atm and sample mass ranging from 250 to 400 mg, HNO3 reflux for 5 min) Sample Activated coal Biological materials Botanical leaves Carbamazepine Graphite Low-ash coal Polyethylene Polyvinylchloride
a

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Temperature,C a 1500 1400 1380 1410 1250 1420 1570 1300

RCC, % a b0.6 b0.5 b0.4 b0.4 b1.2 b0.8 b0.6 b1.0

Data presented during the 9th Rio Symposium on Atomic Spectrometry (Book of abstracts, p. 87, IL-18, 2006).

111,142] as absorbing solutions. However, in the case of combustion bombs, if a higher concentration of HNO3 is necessary (e.g., 1.4 mol l 1), internal glass or quartz liners should be used in order to minimize contamination by metallic parts of the bomb [71]. 3.3.4. Microwave-induced combustion Based on its individual characteristics, the MIC technique allows the combination of some advantages of combustion bombs and pressurized wet digestion in a single system. Fig. 3 shows the combination of characteristics for both of these techniques. In particular, the possibility of using inert materials and relatively high sample masses is important aspects for routine trace analysis. In addition, this technique should be especially suitable for further determination of metals and non-metals in organic materials. In a general way, MIC involves the combustion of organic samples in closed quartz vessels pressurized with oxygen with the ignition step being performed by microwave radiation. After combustion, gases are absorbed in a suitable solution and a reflux step, if necessary, may be applied in order to assure analyte recovery. This technique has been adapted to a commercial microwave oven originally developed for conventional closed vessel wet digestion [145]. In this case, quartz vessels and a pressure control system may be used without change to their original design. A quartz device is inserted into a quartz vessel and it acts both as a sample holder and for the protection of a PTFE cap. Details are presented in Fig. 4. The same valve used to release the pressure after conventional wet digestion is also used to pressurize the system with O2. Combustion gases and residual oxygen are subsequently released using this valve. Similar to their use in combustion bombs, samples are pressed as pellets. Each pellet is weighed and positioned on a small piece of low-ash filter paper that is previously placed on the quartz holder. About 50 l of 6 mol l 1 ammonium nitrate solution is then added as igniter and the system is closed and pressurized with oxygen (15 to 25 atm). A rotor with up to eight vessels is placed into the microwave cavity and the microwave radiation is applied at maximum power (1400 W) to start the combustion. In general, ignition occurs within 3 to 10 s (in this period the absorbing solution is slightly warmed). During combustion, the microwave power is turned off and a white and bright light is emitted that indicates the high temperature attained, frequently above 1300 C (similar to combustion bombs). At this temperature most organic matrices

Fig. 5. Typical pressure profile for microwave-induced combustion.

are completely destroyed and converted to their corresponding oxidation products. In Table 4, results from our laboratory are presented showing the achieved temperatures during the combustion of organic matrices. Typical RCC values are also presented. In general, the temperature varies from 1250 (for graphite) to 1570 C and the highest temperatures are obtained with coal and non-chlorinated polymer samples. Depending on the analyte, in some cases the time necessary for absorption may be only 5 to 10 min. However, for some elements, e.g., fluorine, a longer time for absorption, typically more than 20 min, is necessary. This relatively long time presents a drawback, particularly for combustion bombs where manual shaking to accelerate the absorption process is very difficult. However, a special advantage of MIC is the possibility to apply a reflux step just after the combustion by continuing the microwave irradiation (e.g., 5 to 10 min at maximum power). When reflux is possible, an effective washing of the sample holder and internal parts of vessel occurs. In addition, this step could be compared with a vapor phase digestion technique in closed vessels where biological matrix decomposition is achieved using HNO3 vapor [146,147]. Moreover, dilute nitric acid may be suitable with the MIC technique as an absorbing solution for many analytes [148]. This aspect should be emphasized because analytes can be retained in a more suitable solution for most instrumental analytical techniques, notably for those based on atomic
Table 5 Residual carbon content (%) for selected organic samples using wet digestion systems with concentrated HNO3 and the MIC technique Sample Activated coal Carbamazepine Coke Graphite HPA-1 a Solid residue Solid residue HPA-2 a 0.6 0.4 Solid residue Multiwave 3000 Solid residue Solid residue Solid residue Solid residue Ethos 1 Solid residue Solid residue Solid residue Solid residue MIC 0.5 0.3 0.3 0.8

HPA (high pressure asher, maximum temperature of 320 C) and Multiwave 3000 (maximum temperature of 280 C) systems, Anton Paar GmbH; Ethos 1 Advanced Microwave Digestion System, Milestone S.r.l. a Courtesy of Dr. Peter Fecher (Baverisches Landesamt fr Gesundheit und Lebensmittelsicherheit, Zentrallabor Chemie, Erlangen, Germany).

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Table 6 General comparison of digestion procedures based on combustion techniques using closed vessels Parameter O2 pressure (atm) Sample mass (g) Reflux step Main application Sample throughput Contamination/losses and vessels Ignition type Pressure and temperature control Combustion bomb Up to 30 0.5 to 1.5 Not allowed Non-metals One sample each run Contamination by metallic parts Electrical Not allowed Oxygen flask Atmospheric pressure 0.05 to 0.1 Not allowed Non-metals One sample each run Analyte adsorption on Pt holder Electrical, infrared and manual Not allowed MIC Up to 25 Up to 0.5 Allowed Metals and non-metals Up to eight samples each run High purity quartz pieces Microwave radiation Pressure and temperature measurement

spectrometry [149]. On the other hand, if halogens are determined by liquid chromatography an alkaline buffer may be used as the absorbing/reflux solution. For combustion bombs, the use of corrosive acid solutions must be avoided to prevent damage to the vessel walls and this aspect may be considered a limitation for this technique. However, for MIC techniques, even concentrated nitric acid can be used as an absorbing/refluxing solution without damage to the vessels. Residual carbon content allows a quantitative and convenient way to evaluate the efficiency of sample oxidation [150]. This parameter is frequently used to compare the performance of digestion techniques and can be critical for some analytical techniques (e.g., hydride generation atomic absorption spectrometry or polarography). As can be seen in Table 4, a high efficiency of matrix oxidation is achieved using MIC techniques, with RCC values typically below 1%. Combustion time will depend on the oxygen pressure, sample type and sample mass. Some substances (e.g., aliphatic compounds) burn more easily than others (e.g., aromatic compounds). Obviously, as the sample mass increases, the reaction time is longer. On the other hand, at higher oxygen pressure the combustion reaction proceeds more quickly. For biological samples (350 mg with 20 bar O2), the combustion time is typically less than 50 s. As expected, the maximum pressure attained during combustion depends on the sample mass. Fig. 5 shows the typical change in pressure during combustion using the MIC technique. In general, the maximum pressure during combustion is below 60 bar (500 mg of sample). However, this pressure remains for only few seconds, returning quickly to lower values. This pressure is 20 bar below the maximum operating pressure for the microwave oven and about 50% of its maximum safety pressure (120 bar). This aspect is important in view of assuring safe operation. During the reflux step, the microwave radiation is applied and pressure is increased up to the correspondent maximum selected parameter (in Fig. 5, 80 bar) and pressure is only due to the heating of the absorbing solution. 3.3.4.1. Applications of the MIC technique. Most procedures for the digestion of coal, coke and graphite requiring further analysis by atomic spectrometric techniques involve dry ashing or combustion techniques and such samples are difficult to bring into solution by conventional wet digestion procedures even using highly oxidizing agents [151]. In addition, a number of pure substances used in the pharmaceutical industry (e.g., carbamazepine) may be converted to stable aromatic compounds

during nitric acid wet digestion, resulting in a high amount of solid residue in the digests. In order to compare the efficiency of high performance wet digestion systems with the MIC technique, samples of activated coal, carbamazepine, coke and graphite were digested using a High Pressure Asher (HPA), a Multiwave 3000 system (Anton Paar GmbH) and an Ethos-1 (TFM vessels, Milestone Srl) system. Results are shown in Table 5. Digestions were performed using 190 mg of sample and concentrated HNO3. Heating was applied as follows: 280 C for 2 h (HPA-1) and 250 C for 1 h (Multiwave 3000 and Ethos-1). In addition, 90 mg of sample was digested under hard conditions using an HPA system (320 C for 3 h, HPA-2). For the MIC, digestion conditions were: 400 mg of sample and reflux with HNO3 for only 5 min. As can be observed in Table 5, procedures using the Multiwave, Ethos-1 and HPA-1 systems were not effective for the selected samples. Only using low sample mass and extreme conditions (HPA-2 procedure) it was possible to obtain digests with low RCC. However, even with a digestion time of 3 h, graphite was not digested. Using the MIC technique, low RCC values were obtained for all samples within only 5 min (or 25 min if cooling time is considered). As the MIC technique is relatively new, information for other samples (coal and pharmaceutical products for further F and Pb determination) is available up to now in only three papers [145,148,152] and in a recently published book [153]. In these publications, Cd and Cu [145] and Cu and Zn [148] were determined in many biological samples by atomic absorption spectrometric techniques with good results relative to RCC values and accuracy. Similar results were found for carbon black-containing elastomers and further determination of Al, Fe, Mn, Sr and Zn by inductively coupled plasma optical emission spectrometry [152]. 4. Conclusion In view of their advantages, the combustion bomb and oxygen flask techniques have been recommended for sample preparation by such official bodies as the International Organization for Standardization ISO and ASTM. These institutions have validated methods where combustion techniques are recommended for digestion of coal and further determination of Cl [154,155], F [156], and Hg [157]. Other applications include the determination of Br [158,159], Cl [159], and S [160162] after combustion of rubber, and also the digestion of plastics and carbonaceous materials for subsequent determination of S [163].

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In summary, combustion bombs and the oxygen flask are still in use, but their applications have been limited for the decomposition of samples that are difficult to be processed using wet digestion techniques. Currently, both techniques are wellestablished for these applications; however, no relevant improvements have been proposed in the last few years taking into account the increased requirements related to trace and ultra trace analysis. In this regard, MIC technique seem to present some characteristics that could be useful for these purposes. Table 6 summarizes the main characteristics of closed vessel combustion techniques. Some special features of the MIC technique may be stressed: i) combustion up to 500 mg of sample is possible in a relatively low volume vessel, ii) ignition is carried out using microwave radiation, avoiding additional devices such as metallic electrodes or infrared lamps, iii) conventional wet digestion vessels are the same for the MIC technique and no changes in the vessel, rotor parts or pressure control device are necessary, iv) up to eight samples can be simultaneously processed, v) blanks are low, and vi) contrary to other combustion techniques, MIC allows a reflux step that minimizes potential losses due to analyte adsorption. Among the expected limitations, these are similar to those observed for the Trace-O-Mat technique, and include possible analyte adsorption in the quartz holder, the necessity to press the solid samples, and unsuitability to use HF. Acknowledgements The authors are grateful to CNPq, CAPES and Fapergs for supporting this study and thanks to Dr. Peter Fecher (Bayerisches Landesamt fr Gesundheit und Lebensmittelsicherheit, GDCh), Dr. Joo A. Medeiros (UFRJ) and Dr. Francisco J. Krug (CENA-USP) for comments and discussions. References
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