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Analytical Methods
Fast method of elements determination in slim coffees by ICP OES
Anna Szymczycha-Madeja
, Maja Welna, Pawel Pohl
Wroclaw University of Technology, Chemistry Department, Analytical Chemistry Division, Wybrze
_
 ze Wyspian´skiego 27, 50-370 Wroclaw, Poland
a r t i c l e i n f o
 Article history:
Received 8 February 2013Received in revised form 14 August 2013Accepted 8 September 2013Available online 18 September 2013
Keywords:
Slim instant coffeeSample preparationMajor and trace elementsICP OES
a b s t r a c t
Six sample preparation procedures, i.e., the total decomposition in a HNO
3
 and H
2
O
2
 mixture by micro-wave-assisted or hot-plate heating, a partial decomposition by means of solubilisation in
 aqua regia
 ortetramethyl ammonium hydroxide and simple dissolution in diluted HNO
3
 or in H
2
O, for the determina-tion of the total content of Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sr and Zn in slim instant coffees usinginductively coupled plasma optical emission spectrometry were compared. The performance of proce-dures was determined based on the precision and the accuracy of results and limits of detection of ele-ments. It was found that the extraction with
 aqua regia
 provides the best results, i.e., limits of detection of elements within 0.11–108 ng mL 
1
, the precision of 0.6–5% and the accuracy better than 5%. Elements’concentrations agree withthose after thewet digestion in theHNO
3
 and H
2
O
2
 mixture, therefore thispro-cedure is a simple and fast alternative to complete sample decomposition procedures and can be easilyapplied for routine analyses. Six commercial slim coffee products were analysed with the proposedprocedure.
 2013 Elsevier Ltd. All rights reserved.
1. Introduction
Nowadays coffee brewed from ground roasted coffee beans orprepared from soluble (instant) powder is one of the most widelyand habitually consumed non-alcoholic beverage in the world. Itsincreasing popularity is mainly owing to unique flavour, taste, ar-oma as well as recognised health effects (Grembecka, Malinowska,& Szefer, 2007; Oliveira et al., 2012). Additionally, coffee beverageisacknowledgedasa richsourceofelements,includingthosebeingessential to the human health, as well as non-essential and toxicthat the plant may accidentally take up from a polluted soil and/or during industrial operations. Therefore, the determination of to-tal concentrations of elements in coffee enables to assess its nutri-tive quality and also helps to judge its possible ill-effect that maycause to the human health (dos Santos & de Oliveira, 2001; dosSantos, dos Santos, & Conti, 2010). An extended literature reviewdevoted to the subject of the elemental analysis of natural and in-stant coffee has been presented very recently by Pohl, Stelmach,Welna, and Szymczycha-Madej (2012). At present, an interest inthe consumption of specific coffees, e.g., slim coffees, can be ob-served. These particular coffees, being a mixture of instant coffeeand various additional bioactive components, are preferred bythe people, who wish to reduce their weight. So far, however, therehave been no reports at all devoted to the analysis of elements insuch products.The assessment of total concentrations of elements in coffeesamples is primary performed using spectrochemical methodssuch as flame or graphite furnace atomic absorption spectrometry(FAAS or GFAAS) (Ashu & Chandravanshi, 2011; dos Santos, dosSantos, Conti, dos Santos, & de Oliveira, 2009; dos Santos et al.,2010; Filho, Polito, & Neto, 2007; Grembecka et al., 2007; Krivan,Barth, & Morales, 1993; Magalhaes, Lima, Krug, & Arruda, 1999;Oleszczuk et al., 2007; Oliveira et al., 2012; Onianwa, Adetola,Iwegbue, Ojo, & Tella, 1999; Suseela, Bhalke, Vinod Kumar, Tripathi,& Sastry, 2001), inductively coupled plasma optical emissionspectrometry (ICP OES) (Anderson & Smith, 2002; Anthemidis &Pliatsika, 2005; Castro et al., 2009; dos Santos & de Oliveira,2001; dos Santos et al., 2010; Fernandes et al., 2005; Frankova,Drabek, Havlik, Szakova, & Vanek, 2009; Krejcova & Cernohorsky,2003; Martin, Pablos, & Gonzalez, 1998, 1999; Oleszczuk et al.,2007; Rajwanshi et al., 1997; Ribeiro, Moretto, Arruda, & Cadore,2003), inductively coupled plasma mass spectrometry (ICP MS)(Santos, Lauria, & Porto da Silveira, 2004) or instrumental neutronactivationanalysis (INNA) (Krivanet al., 1993;Vega-Carrillo,Iskan-der, & Manzanares-Acuna, 2002; Zaidi, Fatima, Arif, & Qureshi,2006).Unfortunately, for atomic spectrometry measurements have tobe samples of coffee initially prepared, i.e., brought into the solu-tion by appropriate digestion and/or dissolution treatments. Acommon method of the coffee sample preparation is the totaldecomposition by means of the wet oxidative digestion in pressur-ised closed vessel microwave-assisted systems (Asfaw & Wibetoe,2005; Castro et al., 2009; dos Santos & de Oliveira, 2001; Fernandeset al., 2005; Filho et al., 2007; Frankova et al., 2009; Krejcova &
0308-8146/$ - see front matter
 
 2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.foodchem.2013.09.054
Corresponding author. Tel.: +48 71 3203232; fax: +48 71 3202494.
E-mail address:
Contents lists available at ScienceDirect
Food Chemistry
 
3
2
O
2
2
SO
4
4
 (Ashu & Chandravanshi, 2011; dos Santoset al., 2009; Rajwanshi et al., 1997), are used for the decompositionof the coffee matrix. The dry ashing at the step of coffee sampledecomposition has also been utilised (Grembecka et al., 2007; Oni-anwa et al., 1999; Santos et al., 2004; Suseela et al., 2001). Amongvarious strategies, closed vessel wet digestions facilitated by themicrowave energy are approved and recommended to be the mosteffective for the mineralisation of coffee samples (Castro et al.,2009; Filho et al., 2007).Dry or wet digestions, although excellent and effective, aretime-consuming and require the use of special tools and equip-ments, large amounts of hazardous reagents or laborious proce-dures. In addition, this methods can lead to the loss of analytesor the contamination of analysed samples. In order to minimisethe use of concentrated reagents, digestion procedures withdiluted solutions of HNO
3
 and employing pressurised closed ves-sels microwave-assisted heating have been proposed for theadvantageous decomposition of ground coffee samples prior toICP OES measurements (Castro et al., 2009; dos Santos et al.,2010).Therefore, the development and the application of alternativesample preparation procedures, which do not require the completesample decomposition, are so important and can arouse a consid-erable interest among analysts and food chemists. Such methodscan considerably diminish the time of the analysis and eliminateall inconveniences of dry and wet ashing treatments. Nevertheless,alternative procedures of the sample preparation of coffee prior tothe determination of concentrations of elements are not very oftendeveloped and used. So far, in case of instant coffee, the alkalinesolubilisation in a solution of TMAH has been proposed by Ribeiroet al. (2003). This procedure appeared to be valid for ICP OES mea-surements of total concentrations of Ca, Cu, Fe, Mg, Mn, Na, P, Se,Sn and Zn. Asfaw and Wibetoe (2005) have tested the dissolutionwith a 0.36 mol L 
1
HNO
3
 solution and the solubilisation in
 aquaregia
 to determine hydride (Se) and non-hydride (Ca, Mg, K, P, S,Zn) forming elements by ICP-OES using a dual-mode sample intro-duction system (MSIS) in various beverages, including instant cof-fee samples as well. In addition, samples of instant coffees wereanalysed for total element contents after the dissolution in hotwater only, followed by appropriate dilution and centrifugation(Oliveira et al., 2012). This procedure was found to be reliable forthe determination of Ca, Mg, K, Na, Fe, Mn, Cr an Ni by high-reso-lution continuum source flame (HR-CS-FAAS) and graphite furnace(HR-CS-GFAAS) atomic absorption spectrometry. Finally, to avoid acomplete digestion step, the direct analysis of coffee samples usingthe slurry sampling (SS) technique has also been proposed. For in-stance, Magalhaes et al. (1999) prepared slurries of soluble coffeesamples in a solution of a diluted HNO
3
 solution (0.2%, v/v) con-taining 10% (v/v) Triton X-100. This method was applied for thedetermination of Al by GFAAS. Anthemidis and Pliatsika (2005)determined Al, Ca, Co, Cr, Cu, Fe, Mg, Mn, Ni and Zn by ICP OESin slurries of coffee powder prepared in a mixture of 0.5% (v/v) Tri-ton X-100 and 1% (v/v) HNO
3
 solutions.The main aim of this work was to develop a precise and accu-rate method of the multi-elemental analysis of instant slim coffeesby ICP OES with the least demanding and simple sample prepara-tion procedure. According to our best knowledge, the present workreports for the first time results of the analysis of such coffee prod-ucts referred to their mineral composition (macro-, micro- andtrace-elements) as well as the comparison of several alternativesample preparation procedures of instant coffee samples, i.e., solu-bilisation in tetramethyl ammonium hydroxide (TMAH),
 aqua re- gia
, diluted HNO
3
 and water, prior to their analysis by ICP OES onthe content of 13 nutritionally important elements, i.e., Ba, Ca,Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sr and Zn. The selected procedure,providing the most precise and accurate results, was applied fortheanalysisofsix differentinstantslim coffeescommerciallyavail-able in Poland.
2. Materials and methods
 2.1. Samples
Six instant slim coffee products were selected for the analysis.All coffees were purchased from a local pharmacy (Wrocław,Poland). A detailed description of analysed coffee products is pre-sented below:1.
 Slim Coffee Classic 
 (VitaDirect, Poland). Ingredients: instant chic-ory,maltodextrin,guaranaextract,
Garcinacambogia
extractcon-taining hydroxycitric acid, green tea extract, tiramisu aroma.2.
 Slim Coffee Detox
 (VitaDirect, Poland). Ingredients: instant chic-ory, maltodextrin, wheat dextrin Nutriose
, guarana extractcontaining caffeine, fig prickly pear cactus extract CactilNea™,
Bacillus coagulans
 LactoSpore™ culture, ginger.3.
 Slim Coffee Diabetic 
 (VitaDirect, Poland). Ingredients: instantchicory, palatinose (isomaltulose), white mulberry extract, gin-seng extract, cinnamon bark extract, cinnamon.4.
 Slim Coffee
 (VitaDirect, Poland). Ingredients: caffeine, guaranaextract,
 Camelia sinesis
 extract,
 Garcina cambogia
 fruits extractcontaining hydroxycitric acid, instant chicory.5.
 Coffee Slimme
 (Natural Beauty Norge, Norway). Ingredients:instant coffee (coffea arabica), green coffee extract (coffearobusta), chromium chloride.6.
 Green Coffee
 (Bio-Active, Poland). Ingredients: instant coffeesubstitute (roasted barley and rye), fibre (inulin), instant coffee,green coffee extract containing chlorogenic acid,
 
-carnitine,aroma.
 2.2. Reagents
All chemicals were of analytical grade. Concentrated HNO
3
(Merck,Darmstadt,Germany)andHCl(POCh,Gliwice,Poland)solu-tions,inadditiontoa30%(m/v)H
2
O
2
 solution(POCh)andsolid tet-ramethylammoniumhydroxide(TMAH)(Sigma–Aldrich,Germany)were used for the sample preparation. Working standard solutionswere prepared by dilutions of a multi-element (1000
l
g mL 
1
) ICPstandard (Merck). Deionised water (18.3 M
X
cm
1
) was obtainedfromanEASYpurewaterpurificationsystem(Baenstead,Thermo-lyne Corporation, USA). Glassware and plastic bottles were cleanedwitha10%(m/v)HNO
3
solutionandrinsedseveraltimeswithdeion-ised water.
 2.3. Sample preparation procedures
The following sample preparation procedures were tested:
Microwave-assisted digestion (P1)
: 0.5 g of coffee samples wereaccurately weighed into Teflon digestion vessels, and 6 mL of 
 A. Szymczycha-Madeja et al./Food Chemistry 146 (2014) 220–225
 221
 
a concentrated HNO
3
 solution with 1 mL of a 30%, (m/v) H
2
O
2
solution were added. Samples were subjected to the microwaveheating with a maximum power of 600 W for 45 min. Aftercooling, colourless solutions were quantitatively transferredinto 25-mL volumetric flasks and made up to the volume withdeionised water.
Hot plate heating digestion (P2)
: 0.5 g of coffee samples wereplaced into 150-mL Pyrex beakers and 10 mL of a concentratedHNO
3
 solution was added. Solutions were heated on a hot plateat 85
C for about 3 h. Then they were cooled and 5 mL of a 30%(m/v) H
2
O
2
 solution was added. The heating was continueduntil clear solutions were obtained and their volumes werereduced to about 2 mL. Resulting aliquots were quantitativelytransferred into 25-mL volumetric flasks and made up to thevolume with deionised water.
Solubilisation in aqua regia (P3)
: 0.5 g of coffee samples wereweighed into 30-mL polypropylene (PP) centrifuge tubes and2 mL of 
 aqua regia
 was added. Resulting mixtures were soni-cated in an ultrasonic bath for 15 min, then made up to 25 mL with deionised water and finally centrifuged for 10 min at12,000 rpm.
SolubilisationinTMAH(P4)
:0.5 gofcoffeesampleswereweighedinto 30-mL PP centrifuge tubes and 0.5 mL of a 25% (m/v) TMAHaqueous solution was added. Tubes were shaken at 80
C for30 min,cooled,madeupto25 mLwithdeionisedwaterandthencentrifuged for 10 min at 12,000 rpm.
Dissolution in HNO
 3
 (P5)
: 1.0 g of coffee samples were weightedinto 30-mL PP centrifuge tubes and dissolved in 10mL of a 2.0%(m/v)HNO
3
solutionadded.Resultingsamplesolutionswerecen-trifugedfor10 min at12,000 rpm toremoveany solid particles.
Dissolution in H 
 2
O (P6)
: 1.0 g of coffee samples were weightedinto 30-mL PP centrifuge tubes and dissolved in 10 mL of H
2
Oadded. Resulting sample solutions were centrifuged for10 min at 12,000 rpm to remove any solid particles.Until the analysis, sample solutions were kept at 4
C. The sam-ple of each instant slim coffee brand was analysed in triplicate(
n
 = 3).
 Slim Coffee Classic 
 was used for the comparison of differentsample preparation procedures. With each set of sample solutions,blank sample solutions were prepared and subjected to all sampletreatments to correct final results. The chosen sample preparationprocedure was applied then to other coffee products prior to thedetermination of 13 elements in these samples by ICP OES againstthe external calibration with simple standard solutions.
 2.4. Apparatus
An inductively coupled plasma sequential spectrometer JY38S(Jobin Yvon, France) was used to measure total concentrations of Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sr, Zn in all solutions. Oper-ating parameters were as follows: 1.2 kW of a RF power,15 L min
1
of a plasma flow rate, 0.2 L min
1
of a sheath-gas flowrate and 0.38 L min
1
of a carrier-gas flow rate. Sample solutionswere introduced into the plasma using a V-groove nebuliser anda Scott type spray chamber at a flow rate of 1.1 mL min
1
. Analyt-ical lines of Ba II 233.53 nm, Ca I 317.93 nm, Cd II 228.80 nm, Cr II267.72 nm, Cu I 324.75 nm, Fe II 259.94 nm, Mg I 285.21 nm, Mn II259.37 nm, Ni II 221.65 nm, P I 214.65 nm, Pb II 220.35 nm, Sr II407.77 nm and Zn I 213.86 nm were measured.A Milestone (Italy) high-pressure microwave digestion system(MLS-1200 MEGA), equipped with a rotor MDR 300/10, was usedfor the microwave-assisted sample decomposition. An Elpin (Po-land) thermostatic water bath shaker (type 357) and a JP Selecta(Spain) ultrasonic cleaning bath with heating (UltrasonsH) wereused for experiments with
 aqua regia
 and TMAH based samplesolubilisations.AMPW-350centrifuge(MPWMed.Instruments,Po-land)wasusedtoacceleratetheseparationofliquidphasesfromso-lid particles.
 2.5. Statistical methods
Statistical analysis of the obtained results was performedaccording to
 t 
-test at the 95% significance level. The degree of therelationship between concentration of elements in analysed slimcoffees was evaluated by calculating Pearson’s
 r 
 correlation coeffi-cients (Ellison, Barwick, & Farrank, 2009).
3. Results and discussion
 3.1. Comparison of sample preparation procedures
The analytical characteristic of sample preparation procedurescompared here was evaluated by assessing the precision and theaccuracy of ICP OES measurements of Ba, Ca, Cd, Cr, Cu, Fe, Mg,Mn, Ni, P, Pb, Sr and Zn concentrations in sample solutions of one selected instant coffee brand (
Slim Coffee Classic 
). The relativestandard deviation (RSD) for three independently prepared sam-ples was used to express the precision of the determination of ele-ment concentrations. The accuracy was evaluated by comparingtotal concentrations of elements obtained using different samplepreparation procedures (P2, P3, P4, P5, P6) with those achievedusing the microwave-assisted wet digestion procedure (P1), re-garded as a well-established tool that provides the total sampledecomposition without losses of analytes and treated as a refer-ence method (Kingston & Jassie, 1988). In addition, the recoverystudy was carried out.
 3.1.1. Accuracy
The accuracy of examined sample preparation procedures wasverified by the recovery test. Accordingly, samples of 
 Slime CoffeeClassic 
 were spiked with a multi-element standard solution attwo different concentrations (0.5 and 1.0
l
g mL 
1
) and subjectedtoallsamplepreparationprocedures.Experimentswereperformedin triplicate and resulting sample solutions were analysed to assessrecoveries of elements added. It was established that, indepen-dently of the spike level, recoveries are, in general, between96.5–106% (P1), 93.7–108% (P2), 97.9–104% (P3), 88.9–123% (P4),79.1–105% (P5) and 84.7–116% (P6). As it can be seen, results forthree first procedures, i.e., microwave-assisted (P1) and hot-plate(P2) digestions in the mixture of HNO
3
 and H
2
O
2
 and the solubili-sation in
 aqua regia
 (P3), show the most adequate accuracy andprovide quantitatively recoveries for all elements studied. Addi-tionally, for these procedures, slopes of standard additions’ calibra-tion curves are comparable to those found by the externalcalibration curves with simple standard solutions. Hence, in prac-tice, it can be concluded that matrix effects are not observed forthese procedures. Recovery values for other procedures investi-gated here, i.e., the solubilisation in TMAH (P4), and dissolutionsin a diluted HNO
3
 solution (P5) and H
2
O only (P6), indicate thatthey are not suitable for direct ICP OES measurements of elementconcentrations in resulting sample solutions.Elemental contents of coffee sample obtained using differentsampletreatmentsarelistedinTable1. Consideringconcentrationsofallelementsstudied,itwasfoundthattheapplicationofthesolu-bilisationin
aquaregia
(P3)leadstoresultscomparabletothoseob-tainedafterbothwetaciddigestions(P1,P2).Accordingtothe
-testatthe95%levelofthesignificance,whichwasemployedtocompareconcentrationsofelementsresultedfromdifferentsampleprepara-tionprocedures to those resulted from the microwave-assisted wetdigestion(P1),differencesbetweenresultsobtainedusingtherefer-enceprocedure(P1)andthoseachievedusingthesecond(P2)orthe
222
 A. Szymczycha-Madeja et al./Food Chemistry 146 (2014) 220–225

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