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 Wyspianskiego 27, 50-370 Wroclaw, Poland
a r t i c l e i n f o
Article history:
Received 8 February 2013
Received in revised form 14 August 2013
Accepted 8 September 2013
Available online 18 September 2013
Keywords:
Slim instant coffee
Sample preparation
Major and trace elements
ICP 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 or
tetramethyl 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 using
inductively 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 0.11108 ng mL
1
, the precision of 0.65% and the accuracy better than 5%. Elements
concentrations agree with those after the wet digestion in the HNO
3
and H
2
O
2
mixture, therefore this pro-
cedure is a simple and fast alternative to complete sample decomposition procedures and can be easily
applied for routine analyses. Six commercial slim coffee products were analysed with the proposed
procedure.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Nowadays coffee brewed from ground roasted coffee beans or
prepared from soluble (instant) powder is one of the most widely
and habitually consumed non-alcoholic beverage in the world. Its
increasing popularity is mainly owing to unique avour, taste, ar-
oma as well as recognised health effects (Grembecka, Malinowska,
& Szefer, 2007; Oliveira et al., 2012). Additionally, coffee beverage
is acknowledged as a rich source of elements, including those being
essential to the human health, as well as non-essential and toxic
that 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 may
cause to the human health (dos Santos & de Oliveira, 2001; dos
Santos, dos Santos, & Conti, 2010). An extended literature review
devoted 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 in
the consumption of specic coffees, e.g., slim coffees, can be ob-
served. These particular coffees, being a mixture of instant coffee
and various additional bioactive components, are preferred by
the people, who wish to reduce their weight. So far, however, there
have been no reports at all devoted to the analysis of elements in
such products.
The assessment of total concentrations of elements in coffee
samples is primary performed using spectrochemical methods
such as ame or graphite furnace atomic absorption spectrometry
(FAAS or GFAAS) (Ashu & Chandravanshi, 2011; dos Santos, dos
Santos, 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 emission
spectrometry (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 neutron
activation analysis (INNA) (Krivan et al., 1993; Vega-Carrillo, Iskan-
der, & Manzanares-Acuna, 2002; Zaidi, Fatima, Arif, & Qureshi,
2006).
Unfortunately, for atomic spectrometry measurements have to
be samples of coffee initially prepared, i.e., brought into the solu-
tion by appropriate digestion and/or dissolution treatments. A
common method of the coffee sample preparation is the total
decomposition 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; Fernandes
et 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: anna.szymczycha@pwr.wroc.pl (A. Szymczycha-Madeja).
Food Chemistry 146 (2014) 220225
Contents lists available at ScienceDirect
Food Chemistry
j our nal homepage: www. el sevi er . com/ l ocat e/ f oodchem
Cernohorsky, 2003; Oleszczuk et al., 2007), pressurised closed ves-
sels, i.e., Parr bombs (Anthemidis & Pliatsika, 2005; Castro et al.,
2009), a Berghof apparatus (Krivan et al., 1993), and open vessel
systems facilitated by heating (Anderson & Smith, 2002; dos Santos
et al., 2009; Filho et al., 2007; Magalhaes et al., 1999; Martin et al.,
1998, 1999; Rajwanshi et al., 1997; Ribeiro et al., 2003) or a Kjel-
dahl apparatus (Ashu & Chandravanshi, 2011). Normally aggressive
acids, i.e., HNO
3
alone (Anderson & Smith, 2002; Anthemidis & Pli-
atsika, 2005; Frankova et al., 2009; Krejcova & Cernohorsky, 2003)
as well as its mixtures with H
2
O
2
(Asfaw & Wibetoe, 2005; Castro
et al., 2009; dos Santos & de Oliveira, 2001; Fernandes et al., 2005;
Filho et al., 2007; Magalhaes et al., 1999; Oleszczuk et al., 2007;
Ribeiro et al., 2003), H
2
SO
4
(Martin et al., 1998, 1999), HF (Krivan
et al., 1993) or HClO
4
(Ashu & Chandravanshi, 2011; dos Santos
et al., 2009; Rajwanshi et al., 1997), are used for the decomposition
of the coffee matrix. The dry ashing at the step of coffee sample
decomposition has also been utilised (Grembecka et al., 2007; Oni-
anwa et al., 1999; Santos et al., 2004; Suseela et al., 2001). Among
various strategies, closed vessel wet digestions facilitated by the
microwave energy are approved and recommended to be the most
effective for the mineralisation of coffee samples (Castro et al.,
2009; Filho et al., 2007).
Dry or wet digestions, although excellent and effective, are
time-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 analytes
or the contamination of analysed samples. In order to minimise
the use of concentrated reagents, digestion procedures with
diluted solutions of HNO
3
and employing pressurised closed ves-
sels microwave-assisted heating have been proposed for the
advantageous decomposition of ground coffee samples prior to
ICP OES measurements (Castro et al., 2009; dos Santos et al.,
2010).
Therefore, the development and the application of alternative
sample preparation procedures, which do not require the complete
sample decomposition, are so important and can arouse a consid-
erable interest among analysts and food chemists. Such methods
can considerably diminish the time of the analysis and eliminate
all inconveniences of dry and wet ashing treatments. Nevertheless,
alternative procedures of the sample preparation of coffee prior to
the determination of concentrations of elements are not very often
developed and used. So far, in case of instant coffee, the alkaline
solubilisation in a solution of TMAH has been proposed by Ribeiro
et 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 dissolution
with a 0.36 mol L
1
HNO
3
solution and the solubilisation in aqua
regia 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 were
analysed for total element contents after the dissolution in hot
water only, followed by appropriate dilution and centrifugation
(Oliveira et al., 2012). This procedure was found to be reliable for
the determination of Ca, Mg, K, Na, Fe, Mn, Cr an Ni by high-reso-
lution continuum source ame (HR-CS-FAAS) and graphite furnace
(HR-CS-GFAAS) atomic absorption spectrometry. Finally, to avoid a
complete digestion step, the direct analysis of coffee samples using
the slurry sampling (SS) technique has also been proposed. For in-
stance, Magalhaes et al. (1999) prepared slurries of soluble coffee
samples 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 the
determination of Al by GFAAS. Anthemidis and Pliatsika (2005)
determined Al, Ca, Co, Cr, Cu, Fe, Mg, Mn, Ni and Zn by ICP OES
in 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 coffees
by ICP OES with the least demanding and simple sample prepara-
tion procedure. According to our best knowledge, the present work
reports for the rst time results of the analysis of such coffee prod-
ucts referred to their mineral composition (macro-, micro- and
trace-elements) as well as the comparison of several alternative
sample 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 on
the 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 for
the analysis of six different instant slim coffees commercially avail-
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 (Wrocaw,
Poland). A detailed description of analysed coffee products is pre-
sented below:
1. Slim Coffee Classic (VitaDirect, Poland). Ingredients: instant chic-
ory, maltodextrin, guarana extract, Garcinacambogia extract con-
taining hydroxycitric acid, green tea extract, tiramisu aroma.
2. Slim Coffee Detox (VitaDirect, Poland). Ingredients: instant chic-
ory, maltodextrin, wheat dextrin Nutriose

, guarana extract
containing caffeine, g prickly pear cactus extract CactilNea,
Bacillus coagulans LactoSpore culture, ginger.
3. Slim Coffee Diabetic (VitaDirect, Poland). Ingredients: instant
chicory, palatinose (isomaltulose), white mulberry extract, gin-
seng extract, cinnamon bark extract, cinnamon.
4. Slim Coffee (VitaDirect, Poland). Ingredients: caffeine, guarana
extract, Camelia sinesis extract, Garcina cambogia fruits extract
containing hydroxycitric acid, instant chicory.
5. Coffee Slimmer (Natural Beauty Norge, Norway). Ingredients:
instant coffee (coffea arabica), green coffee extract (coffea
robusta), chromium chloride.
6. Green Coffee (Bio-Active, Poland). Ingredients: instant coffee
substitute (roasted barley and rye), bre (inulin), instant coffee,
green coffee extract containing chlorogenic acid, L-carnitine,
aroma.
2.2. Reagents
All chemicals were of analytical grade. Concentrated HNO
3
(Merck, Darmstadt, Germany) and HCl (POCh, Gliwice, Poland) solu-
tions, in addition to a 30% (m/v) H
2
O
2
solution (POCh) and solid tet-
ramethyl ammoniumhydroxide (TMAH) (SigmaAldrich, Germany)
were used for the sample preparation. Working standard solutions
were prepared by dilutions of a multi-element (1000 lg mL
1
) ICP
standard (Merck). Deionised water (18.3 MXcm
1
) was obtained
froman EASYpurewater purication system(Baenstead, Thermo-
lyne Corporation, USA). Glassware and plastic bottles were cleaned
witha 10%(m/v) HNO
3
solutionandrinsedseveral times withdeion-
ised water.
2.3. Sample preparation procedures
The following sample preparation procedures were tested:
Microwave-assisted digestion (P1): 0.5 g of coffee samples were
accurately weighed into Teon digestion vessels, and 6 mL of
A. Szymczycha-Madeja et al. / Food Chemistry 146 (2014) 220225 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 microwave
heating with a maximum power of 600 W for 45 min. After
cooling, colourless solutions were quantitatively transferred
into 25-mL volumetric asks and made up to the volume with
deionised water.
Hot plate heating digestion (P2): 0.5 g of coffee samples were
placed into 150-mL Pyrex beakers and 10 mL of a concentrated
HNO
3
solution was added. Solutions were heated on a hot plate
at 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 continued
until clear solutions were obtained and their volumes were
reduced to about 2 mL. Resulting aliquots were quantitatively
transferred into 25-mL volumetric asks and made up to the
volume with deionised water.
Solubilisation in aqua regia (P3): 0.5 g of coffee samples were
weighed into 30-mL polypropylene (PP) centrifuge tubes and
2 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 nally centrifuged for 10 min at
12,000 rpm.
Solubilisation in TMAH(P4): 0.5 g of coffee samples were weighed
into 30-mL PP centrifuge tubes and 0.5 mL of a 25% (m/v) TMAH
aqueous solution was added. Tubes were shaken at 80 C for
30 min, cooled, made up to 25 mL with deionised water and then
centrifuged for 10 min at 12,000 rpm.
Dissolution in HNO
3
(P5): 1.0 g of coffee samples were weighted
into 30-mL PP centrifuge tubes and dissolved in 10 mL of a 2.0%
(m/v) HNO
3
solution added. Resulting sample solutions were cen-
trifuged for 10 min at 12,000 rpm to remove any solid particles.
Dissolution in H
2
O (P6): 1.0 g of coffee samples were weighted
into 30-mL PP centrifuge tubes and dissolved in 10 mL of H
2
O
added. Resulting sample solutions were centrifuged for
10 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 different
sample preparation procedures. With each set of sample solutions,
blank sample solutions were prepared and subjected to all sample
treatments to correct nal results. The chosen sample preparation
procedure was applied then to other coffee products prior to the
determination of 13 elements in these samples by ICP OES against
the 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 ow rate, 0.2 L min
1
of a sheath-gas ow
rate and 0.38 L min
1
of a carrier-gas ow rate. Sample solutions
were introduced into the plasma using a V-groove nebuliser and
a Scott type spray chamber at a ow 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 II
267.72 nm, Cu I 324.75 nm, Fe II 259.94 nm, Mg I 285.21 nm, Mn II
259.37 nm, Ni II 221.65 nm, P I 214.65 nm, Pb II 220.35 nm, Sr II
407.77 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 used
for 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) were
used for experiments with aqua regia and TMAH based sample
solubilisations. AMPW-350centrifuge (MPWMed. Instruments, Po-
land) was used to accelerate the separationof liquid phases fromso-
lid particles.
2.5. Statistical methods
Statistical analysis of the obtained results was performed
according to t-test at the 95% signicance level. The degree of the
relationship between concentration of elements in analysed slim
coffees was evaluated by calculating Pearsons r correlation coef-
cients (Ellison, Barwick, & Farrank, 2009).
3. Results and discussion
3.1. Comparison of sample preparation procedures
The analytical characteristic of sample preparation procedures
compared here was evaluated by assessing the precision and the
accuracy 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 relative
standard 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 comparing
total concentrations of elements obtained using different sample
preparation procedures (P2, P3, P4, P5, P6) with those achieved
using the microwave-assisted wet digestion procedure (P1), re-
garded as a well-established tool that provides the total sample
decomposition without losses of analytes and treated as a refer-
ence method (Kingston & Jassie, 1988). In addition, the recovery
study was carried out.
3.1.1. Accuracy
The accuracy of examined sample preparation procedures was
veried by the recovery test. Accordingly, samples of Slime Coffee
Classic were spiked with a multi-element standard solution at
two different concentrations (0.5 and 1.0 lg mL
1
) and subjected
to all sample preparation procedures. Experiments were performed
in triplicate and resulting sample solutions were analysed to assess
recoveries of elements added. It was established that, indepen-
dently of the spike level, recoveries are, in general, between
96.5106% (P1), 93.7108% (P2), 97.9104% (P3), 88.9123% (P4),
79.1105% (P5) and 84.7116% (P6). As it can be seen, results for
three rst 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 and
provide 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 external
calibration curves with simple standard solutions. Hence, in prac-
tice, it can be concluded that matrix effects are not observed for
these procedures. Recovery values for other procedures investi-
gated here, i.e., the solubilisation in TMAH (P4), and dissolutions
in a diluted HNO
3
solution (P5) and H
2
O only (P6), indicate that
they are not suitable for direct ICP OES measurements of element
concentrations in resulting sample solutions.
Elemental contents of coffee sample obtained using different
sample treatments are listed in Table 1. Considering concentrations
of all elements studied, it was found that the application of the solu-
bilisation in aqua regia (P3) leads to results comparable to those ob-
tained after both wet acid digestions (P1, P2). According to the t-test
at the 95% level of the signicance, which was employed to compare
concentrations of elements resulted fromdifferent sample prepara-
tion procedures to those resulted from the microwave-assisted wet
digestion (P1), differences between results obtained using the refer-
ence procedure (P1) and those achieved using the second (P2) or the
222 A. Szymczycha-Madeja et al. / Food Chemistry 146 (2014) 220225
third procedure (P3) are statistically insignicant. In this case, for all
compared elements, calculated values of the t-test (t
calculated
) are be-
lowthe critical value of this test (t
critical
) equal to 4.303 (see Table 2).
Therefore, the solubilisation of coffee samples in aqua regia (P3) can
be used as a much simpler and faster but reliable alternative to usu-
ally applied sample preparation procedures based on acidic diges-
tions but prone to contaminations of analysed samples and/or
losses of analytes.
For three remaining methods (P4, P5, P6) a lowering of the con-
tent of the majority of elements can be observed. This effect is
more pronounced in case of dissolution in a diluted HNO
3
solution
(P5) and H
2
O (P6) procedures. The use of the solubilisation in
TMAH (P4) seems to be justied, however only in case of some se-
lected elements, i.e., Ba, Ca, Mg, Mn, P and Pb. For these elements
differences between their concentrations determined in sample
solutions resulted from the microwave-assisted wet digestion
(P1) and the solubilisation in TMAH (P4) are statistically insigni-
cant (Table 2). Unfortunately, dissolution procedures using a di-
luted HNO
3
solution (P5) or water only (P6), although very
simple and fast, were found not to be suitable for the treatment
of instant coffee samples prior to their analysis by ICP OES. Both
procedures can lead to analytical errors during the determination
of 8 (Ba, Cd, Cr, Fe, Mg, Mn, Ni and Pb) out of 13 elements investi-
gated here.
3.1.2. Limits of detection
Limits of detection (LODs) of elements achieved with ICP OES
and different sample preparation procedures were calculated as
concentrations corresponding to signals equal to three times stan-
dard deviations of ten replicates of respective blank solutions (3r
criterion), which were prepared in the same way as those of coffee
samples.
As can be seen from Table 3, LOD values are varied likely due to
differences in values of respective blanks. It seems that the detect-
ability of elements attained using both wet digestions (P1, P2) and
the solubilisation in aqua regia (P3) is better than this achieved
using the solubilisation in TMAH (P4) or dissolutions in a diluted
HNO
3
solution (P5) or H
2
O (P6). Wet acid digestions of coffee
(P1, P2) show comparable LODs for most elements, except for Cd,
Cr and Ni, for which LOD values are higher using the hot-plate
heating digestion (P2). Satisfactorily, the lowest LODs of all ele-
ments are achieved when the solubilisation in aqua regia (P3)
was used. In contrast, LODs resulted from the use of the dissolution
in H
2
O (P6) are up to three times higher on average, while in case
of Cu and Sr an increase in LOD values of these elements even by
one order of the magnitude can be observed.
3.1.3. Precision
As it can be seen in Table 1, in terms of the precision of the
determination of all elements, differences between total wet
digestion procedures (P1, P2) are not observed in practice. RSD
values vary from 1.2% to 5.9% and from 1.7% to 6.4% for
microwave-assisted (P1) and hot-plate (P2) wet digestions,
Table 2
Calculated valuesCalculated values of the t-test (t
calculated
) for the comparison of
average concentrations of elements determined by ICP OES using the standard
procedure (P1) and other alternative procedures: the hot-plate digestion in HNO
3
with H
2
O
2
(P2), the solubilisation in aqua regia (P3) and TMAH (P4), the dissolution in
HNO
3
(P5) and H
2
O (P6).
P2 P3 P4 P5 P6
Ba 0.346 2.041 2.840
20.44 17.32
Ca 0.216 0.084 0.371 2.441 1.781
Cd 0.548 1.837
30.01 43.48 33.15
Cr 2.164 0.153
5.545 10.33 11.78
Cu 0.608 0.266
8.059
0.225 3.917
Fe 0.202 0.251
8.904 9.925 7.899
Mg 0.272 0.160 0.874
15.80 7.596
Mn 0.001 0.408 1.188
10.07 6.928
Ni 1.922 1.225
4.804 11.30 12.34
P 0.334 0.134 1.056 0.662 0.364
Pb 0.181 0.203 1.077
23.90 21.64
Sr 2.185 0.703
10.66
2.178 0.837
Zn 0.472 0.544
4.619
1.659 1.561
Critical value of the t-test (t
critical
): 4.303 (p = 0.05, n = 3).
Signicant differences are under lined.
Table 3
Limits of detection (in ng mL
1
) of elements for ICP OES with different sample
preparation procedures: the microwave-assisted digestion in HNO
3
with H
2
O
2
(P1),
the hot-plate digestion in HNO
3
with H
2
O
2
(P2), the solubilisation in aqua regia (P3)
and TMAH (P4), the dissolution in HNO
3
(P5) and H
2
O (P6).
P1 P2 P3 P4 P5 P6
Ba 0.99 1.22 0.94 2.20 1.37 2.61
Ca 12.5 12.6 10.2 15.1 11.2 16.3
Cd 0.91 2.45 0.85 0.88 0.97 1.75
Cr 0.82 1.41 1.11 3.34 1.74 1.99
Cu 0.72 0.97 0.67 8.82 6.06 5.22
Fe 1.86 1.89 0.891 1.46 2.87 3.57
Mg 3.25 2.84 2.36 3.15 2.61 4.78
Mn 0.42 0.43 0.42 0.61 0.76 0.95
Ni 2.16 3.25 2.13 5.90 3.88 7.50
P 88.5 96.4 87.4 100 83.1 134
Pb 33.4 33.6 32.8 62.3 34.7 55.4
Sr 0.16 0.17 0.13 0.20 0.23 5.22
Zn 0.90 1.07 0.87 1.17 1.34 2.12
Table 1
Concentrations (in lg g
1
) of elements determined by ICP OES in samples of Slim Coffee Classic prepared using different sample preparation procedures: the microwave-assisted
digestion in HNO
3
with H
2
O
2
(P1), the hot-plate digestion in HNO
3
with H
2
O
2
(P2), the solubilisation in aqua regia (P3) and TMAH (P4), the dissolution in HNO
3
(P5) and H
2
O (P6).
P1 P2 P3 P4 P5 P6
Ba 1.64 (1.8) 1.65 (2.4) 1.69 (1.8) 1.53 (3.9) 1.05 (3.8) 1.14 (3.5)
Ca 931 (1.7) 934 (1.9) 932 (1.4) 925 (2.5) 896 (2.1) 907 (1.9)
Cd 0.095 (2.1) 0.093 (6.4) 0.098 (2.0) 0.046 (4.4) 0.024 (8.3) 0.026 (11)
Cr 0.282 (2.8) 0.298 (3.4) 0.283 (2.8) 0.241 (4.2) 0.191 (6.8) 0.184 (6.5)
Cu 0.915 (2.5) 0.900 (4.0) 0.920 (2.5) 0.684 (6.4) 0.909 (4.4) 0.776 (7.4)
Fe 80.1 (2.5) 80.6 (4.7) 80.5 (2.4) 60.7 (5.3) 57.0 (6.1) 66.2 (3.5)
Mg 515 (1.7) 513 (1.7) 514 (1.2) 503 (4.4) 411 (1.7) 456 (2.2)
Mn 17.6 (1.7) 17.6 (2.8) 17.7 (1.7) 17.2 (2.9) 13.7 (4.4) 15.6 (2.6)
Ni 1.26 (1.6) 1.30 (2.3) 1.28 (1.6) 1.36 (2.2) 0.997 (3.5) 0.954 (4.0)
P 1572 (2.0) 1563 (2.2) 1569 (1.4) 1530 (4.0) 1547 (3.7) 1588 (4.4)
Pb 2.22 (5.9) 2.24 (6.3) 2.20 (5.0) 2.11 (5.7) 0.385 (7.3) 0.505 (8.7)
Sr 7.27 (1.2) 7.06 (2.0) 7.31 (0.55) 6.14 (2.6) 7.05 (2.1) 7.10 (4.8)
Zn 7.08 (1.3) 7.13 (2.2) 7.04 (1.3) 8.33 (5.5) 6.78 (4.4) 6.93 (2.0)
Average values (n = 3) with relative standard of deviation (RSD) in brackets.
A. Szymczycha-Madeja et al. / Food Chemistry 146 (2014) 220225 223
respectively. The precision of measurements obtained with both
total wet digestions is, however, lower than this achieved in case
of partially decomposed samples resulted from the solubilisation
in aqua regia (P3). Indeed, the latter procedure provides the best
precision that ranges between 0.6% and 2.8% for practically all
elements; the only exception is Pb for which a much higher RSD
value was obtained (5.0%). Noteworthy, the precision of the Pb
determination for all sample preparation procedures examined
here is the lowest as compared to the precision obtained for other
elements studied. The precision attained for the solubilisation in
TMAH procedure (P4) (2.26.4%) is quite comparable to this
achieved for the hot-plate wet digestion (P2). Finally, the precision
of the determination of elements using dissolution in a diluted
HNO
3
solution (P5) or H
2
O (P6) procedures is nearly two times
poorer than this achieved when the aqua regia based procedure
(P3) was used. Accordingly, RSD values up to 8.3% and 11% for dis-
solution in a diluted HNO
3
solution (P5) and H
2
O (P6) procedures
were found, respectively.
Considering the precision and the accuracy, the solubilisation in
aqua regia was chosen as a simple, fast and reliable method of the
direct multi-element analysis of instant coffee samples by ICP OES.
3.2. Application to the analysis of slim coffee products
Considering the analytical performance of sample preparation
procedures investigated here, the solubilisation in aqua regia (P3)
was found to be the most suitable prior to the multi-element anal-
ysis of slim coffee products by ICP OES. The proposed method was
applied to six various coffees and results of this analysis, i.e., total
concentrations of 13 elements (in lg g
1
), are presented in Table 4.
They are mean values for three replicates with RSDs.
As it can be seen, the precision of measurements is good and
varies from 0.3% to 4.8%. Only in two cases, i.e., for Cr in Slim Coffee
Detox and for Ca in Slim Coffee, RSDs are slightly higher, i.e., 5.6%
and 5.3%, respectively.
It was observed that mineral contents depend on the coffee
brand. Discrepancies between the highest and the lowest
concentrations of elements change from 32% (Sr) and 45% (Zn) to
more than 5-fold (Mg). For most of elements these differences
are about 23 times. The highest discrepancy (2 orders of magni-
tude) is noticed for Cr. In general, the highest concentrations of ele-
ments are in Coffee Slimmer (Ba, Cd, Cr, Cu, Mg, Ni, P, Sr) and Slim
Coffee (Ca, Cd, Fe, Mn, Sr, Zn). In contrast, the lowest amounts of
examined elements are found in Slim Coffee Classic (Ba, Ca, Cd,
Cu, Ni, P, Sr) and Green Coffee (Ca, Cd, Cr, Fe, Mg, Mn, Pb, Sr, Zn).
In the group of elements of interest (Table 4), Ca, Mg and P are
major elements, while Ba, Cd, Cr, Cu, Fe, Mn, Ni, Sr, and Zn are trace
elements. Concentrations of macro-elements full the following
order: Mg < Ca < P. The level of Ca is two times higher than this
of Mg, except for Coffee Slimmer for which an opposite relation is
noticed (Mg > Ca). The concentration of P is from 30% (Slim Coffee
Diabetic) up to 4 times (Green Coffee) higher than this of Ca. The
highest concentrations of Ca, Mg and P are in Coffee Slimmer (Mg,
P) and Slim Coffee (Ca).
Concentrations of trace essential elements, i.e., Cu, Fe, Mn and
Zn, can be arranged as follows: Cu < Zn < Mn < Fe. The concentra-
tion of Cu is signicantly reduced (0.9203.69 lg g
1
) in compari-
son to other aforementioned trace elements. The concentration of
Mn (4.9920.9 lg g
1
) is about twice than this of Zn
(5.888.54 lg g
1
) but 37 times lower than in case of Fe
(26.6107 lg g
1
). Except for Sr, concentrations of nonessential
elements are relatively low (Ba, Ni, Pb, Sr) and very low (Cr, Cd),
Table 4
Concentrations (in lg g
1
) of elements in analysed instant coffees: Slim Coffee Classic (SCC), Slim Coffee Detox (SCDe), Slim Coffee Diabetic (SCDi), Slim Coffee (SC), Coffee Slimmer (CS)
and Green Coffee (GC).
SCC SCDe SCDi SC CS GC
Ba 1.69 (1.8) 2.36 (3.0) 2.74 (2.2) 1.79 (2.2) 3.37 (3.3) 2.83 (0.35)
Ca 932 (1.4) 1063 (1.8) 1242 (2.6) 2680 (5.6) 1154 (3.4) 862 (3.1)
Cd 0.098 (2.0) 0.122 (2.3) 0.155 (2.6) 0.167 (3.6) 0.166 (3.0) 0.090 (4.4)
Cr 0.283 (2.8) 0.153 (5.3) 0.252 (2.8) 0.409 (2.9) 61.1 (2.6) 0.160 (2.5)
Cu 0.920 (2.5) 1.14 (3.5) 1.47 (1.4) 1.78 (3.9) 3.69 (2.7) 2.65 (3.4)
Fe 80.5 (2.4) 68.2 (2.9) 66.5 (2.4) 107 (1.9) 36.6 (3.6) 26.6 (3.8)
Mg 514 (1.2) 590 (2.4) 560 (3.9) 813 (3.2) 2700 (2.1) 448 (2.0)
Mn 17.7 (1.7) 10.4 (0.96) 11.4 (3.5) 20.9 (4.3) 12.5 (0.80) 4.99 (0.80)
Ni 1.28 (1.6) 1.51 (0.66) 1.45 (3.4) 2.96 (0.34) 3.13 (3.2) 3.28 (3.4)
P 1569 (1.4) 1668 (2.0) 1598 (1.4) 2377 (2.3) 4652 (2.8) 3482 (1.1)
Pb 2.20 (5.0) 1.69 (3.0) 1.99 (3.5) 0.925 (0.54) 1.88 (4.8) 1.17 (0.85)
Sr 7.31 (0.55) 11.6 (3.4) 9.70 (2.2) 11.8 (0.85) 11.5 (2.6) 7.02 (3.0)
Zn 7.04 (1.3) 6.54 (3.2) 9.67 (2.8) 9.54 (3.1) 5.92 (1.8) 5.88 (1.4)
Average values (n = 3) with relative standard of deviation (RSD) in brackets.
Table 5
Pearsons linear correlation coefcienorrelation coefcients (r).
Ba Ca Cd Cr Cu Fe Mg Mn Ni P Pb Sr Zn
Ba 1
Ca 0.422 1
Cd +0.229 +0.642 1
Cr +0.684 0.118 +0.472 1
Cu +0.795 0.055 +0.309 +0.817 1
Fe 0.844 +0.728 +0.317 0.459 0.669 1
Mg +0.624 +0.015 +0.568 +0.990 +0.797 0.350 1
Mn 0.688 +0.704 +0.439 0.038 0.332 +0.868 +0.064 1
Ni +0.426 +0.303 +0.202 +0.446 +0.831 0.386 +0.466 0.168 1
P +0.722 0.077 +0.213 +0.813 +0.986 0.661 +0.791 0.301 +0.847 1
Pb +0.116 0.626 0.101 +0.234 0.221 0.130 +0.164 0.004 0.701 0.236 1
Sr +0.125 +0.566 +0.819 +0.376 +0.159 +0.341 +0.478 +0.340 +0.114 +0.114 0.194 1
Zn 0.417 +0.683 +0.539 0.424 0.442 +0.728 0.335 +0.547 0.266 0.542 0.144 +0.268 1
Very high and high correlations are indicated in bold.
224 A. Szymczycha-Madeja et al. / Food Chemistry 146 (2014) 220225
i.e., below 3.5 lg g
1
and 0.5 lg g
1
, respectively. The concentra-
tion of Sr range between 7.02 and 11.8 lg g
1
and is close to this
for Zn. A very high content of Cr determined in Coffee Slimmer
(61.1 lg g
1
) is justied due to the acknowledged composition of
CrCl
3
. Noteworthy, in this case our result is in a very good agree-
ment with the declared value on the package (60 lg g
1
).
Unfortunately, results on the elemental analysis of slim instant
coffees have never been reported so far. Therefore, concentrations
of elements assessed for these coffees were compared to those re-
ported for other instant coffees. It was found that results for all
studied elements, i.e., Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sr
and Zn, were within concentration ranges given for different in-
stant coffees (Pohl et al., 2012).
In addition, relationships between concentrations of elements
in analysed slim coffee products using the Pearsons linear correla-
tion coefcient (r) were assessed. As can be seen from Table 5, a
very high positive correlation (r > 0.9) is observed only for CrMg
and CuP pairs. High positive correlations (0.7 < r < 0.9) exhibit
the following pairs of elements: BaCu, BaFe, BaP, CaFe,
CaMn, CdSr, CrCu, CrP, CuMg, CuNi, FeMn, FeZn, MgP,
NiP and NiPb. For other pairs of elements, positive or negative
correlations are established and they are moderate (r 0.4 to
0.7), low (r 0.2 to 0.4) or almost negligible (r 0 to 0.2).
4. Conclusion
We evaluated the suitability of the sample preparation proce-
dure without the need of a previous digestion of the samples for
the determination of total concentrations of 13 elements by ICP
OES in various instant slim coffee products. The developed sample
preparation procedure based on the partial decomposition in aqua
regia is simple, safe, reproducible and reliable for the determina-
tion of total concentrations of Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni,
P, Pb, Sr and Zn. In addition, the use of aqua regia improves the
sample solubilisation, reduces the reagents consumption and the
time of the analysis. In addition, a much simpler sample handling
makes it a vital alternative to wet digestion procedures adequate
for routine analyses.
The use of TMAH to coffee sample solubilisation, although also
useful and justied for most of elements, cannot be used for the
determination of such elements as Cr, Cd, Cu, Fe, Ni, Sr and Zn.
Unfortunately, the dissolution of slim instant coffee samples in a
diluted HNO
3
solution or H
2
O is the least efcient and not applica-
ble in practice for the multi-element determination in this kind of
products.
Acknowledgement
The work was nanced by a statutory activity subsidy from the
Polish Ministry of Science and Higher Education for the Faculty of
Chemistry of Wrocaw University of Technology.
References
Anderson, K. A., & Smith, B. W. (2002). Chemical proling to differentiate
geographical growing origins of coffee. Journal of Agricultural Food Chemistry,
50, 20682075.
Anthemidis, A. N., & Pliatsika, V. G. (2005). On-line slurry formation and
nebulization for inductively coupled plasma atomic emission spectrometry.
Multi-element analysis of cocoa and coffee powder samples. Journal of
Analytical Atomic Spectrometry, 20, 12801286.
Asfaw, A., & Wibetoe, G. (2005). Simultaneous determination of hydride (Se) and
non-hydride-forming (Ca, Mg, K, P, S and Zn) elements in various beverages
(beer, coffee, and milk), with minimum sample preparation, by ICP-AES and use
of a dual-mode sample-introduction system. Analytical Bioanalytical Chemistry,
382, 173179.
Ashu, R., & Chandravanshi, B. S. (2011). Concentration levels of metals in
commercially available Ethiopian roasted coffee powders and their infusions.
Bulletin of the Chemical Society of Ethiopia, 25, 1124.
Castro, J. T., Santos, E. C., Santos, W. P. C., Costa, L. M., Korn, M., Nobrega, J. A., & Korn,
M. G. A. (2009). A critical evaluation of digestion procedures for coffee samples
using diluted nitric acid in closed vessels for inductively coupled plasma optical
emission spectrometry. Talanta, 78, 13781382.
dos Santos, E. J., & de Oliveira, E. (2001). Determination of mineral nutrients and
toxic elements in Brazilian soluble coffee by ICP-AES. Journal of Food
Composition and Analysis, 14, 523531.
dos Santos, J. S., dos Santos, M. L. P., & Conti, M. M. (2010). Comparative study of
metal contents in Brazilian coffees cultivated by conventional and organic
agriculture applying principal component analysis. Journal of the Brazilian
Chemical Society, 21, 14681476.
dos Santos, J. S., dos Santos, M. L. P., Conti, M. M., dos Santos, S. N., & de Oliveira, E.
(2009). Evaluation of some metals in Brazilian coffees cultivated during the
process of conversion from conventional to organic agriculture. Food Chemistry,
115, 14051410.
Ellison, S. L. R., Barwick, V. I., & Farrank, T. J. D. (2009). Practical statistics for the
analytical scientists. Cambridge: RSC Publishing.
Fernandes, A. P., Santos, M. C., Lemos, S. G., Ferreira, M. M. C., Nogueira, A. R. A., &
Nobrega, J. A. (2005). Pattern recognition applied to mineral characterization of
Brazilian coffees and sugar-cane spirits. Spectrochimica Acta, Part B, 60, 717724.
Filho, V. R. M., Polito, W. L., & Neto, J. A. G. (2007). Comparative studies of the
sample decomposition of green and roasted coffee for determination of
nutrients and data exploratory analysis. Journal of the Brazilian Chemistry
Society, 18, 4753.
Frankova, A., Drabek, O., Havlik, J., Szakova, J., & Vanek, A. (2009). The effect of
beverage method on aluminium content in coffee infusions. Journal of Inorganic
Biochemistry, 103, 14801485.
Grembecka, M., Malinowska, E., & Szefer, P. (2007). Differentiation of market coffee
and its infusions in view of their mineral composition. Science of the Total
Environment, 383, 5969.
Kingston, H. M., & Jassie, L. B. (1988). Introduction to microwave sample preparation
Theory and practice. Washington D.C.: American Chemical Society.
Krejcova, A., & Cernohorsky, T. (2003). The determination of boron in tea and coffee
by ICP-AES method. Food Chemistry, 82, 303308.
Krivan, V., Barth, P., & Morales, A. F. (1993). Multielement analysis of green coffee
and its possible use for the determination of origin. Microchimica Acta, 110,
217236.
Magalhaes, C. E. C., Lima, E. C., Krug, F. J., & Arruda, M. A. Z. (1999). Direct analysis of
coffee and tea for Al determination by electrothermal atomic absorption
spectrometry. Microchimica Acta, 132, 95100.
Martin, M. J., Pablos, F., & Gonzalez, A. G. (1998). Characterization of green coffee
varieties according to their metal content. Analytica Chimica Acta, 358, 177183.
Martin, M. J., Pablos, F., & Gonzalez, A. G. (1999). Characterization of arabica and
robusta roasted coffee varieties and mixture resolution according to their
mineral content. Food Chemistry, 66, 365370.
Oleszczuk, N., Castro, J. T., da Silva, M. M., Korn, M., Welz, B., & Vale, M. G. (2007).
Method development for the determination of manganese, cobalt and copper in
green coffee comparing direct solid sampling electrothermal atomic absorption
spectrometry and inductively coupled plasma optical emission spectrometry.
Talanta, 73, 862869.
Oliveira, M., Casal, S., Morais, S., Alves, C., Dias, F., Ramos, S., Mendes, E., Delerue-
Matosa, C., & Oliveira, M. B. P. P. (2012). Intra- and interspecic mineral
composition variability of commercial coffees and coffee substitutes.
Contribution to mineral intake. Food Chemistry, 130, 702709.
Onianwa, P. C., Adetola, G., Iwegbue, C. M. A., Ojo, M. F., & Tella, O. O. (1999). Trace
heavy metals composition of some Nigerian beverages and food drinks. Food
Chemistry, 66, 275279.
Pohl, P., Stelmach, E., Welna, M., & Szymczycha-Madej, A. (2012). Determination of
the elemental composition of coffee using instrumental methods. Food
Analytical Methods. http://dx.doi.org/10.1007/s12161-012-9467-6.
Rajwanshi, P., Singh, V., Gupta, M. K., Kumari, V., Shrivastav, R., Ramanamurthy, M.,
& Dass, S. (1997). Studies on aluminium leaching from cookware in tea and
coffee and estimation of aluminium content in toothpaste, baking powder and
paan masala. Science of the Total Environment, 193, 243249.
Ribeiro, A. S., Moretto, A. L., Arruda, M. A. Z., & Cadore, S. (2003). Analysis of
powdered coffee and milk by ICP OES after sample treatment with
tetramethylammonium hydroxide. Microchimica Acta, 141, 149155.
Santos, E. E., Lauria, D. C., & Porto da Silveira, C. L. (2004). Assessment of daily intake
of trace elements due to consumption of foodstuffs by adult inhabitants of Rio
de Janeiro city. Science of the Total Environment, 327, 6979.
Suseela, B., Bhalke, S., Vinod Kumar, A., Tripathi, R. M., & Sastry, V. N. (2001). Daily
intake of trace metals through coffee consumption in India. Food Additives and
Contaminants, Part A, 18, 115120.
Vega-Carrillo, H. R., Iskander, F. Y., & Manzanares-Acuna, E. (2002). Elemental
content in ground and soluble/instant coffee. Journal of Radioanalytical and
Nuclear Chemistry, 252, 7580.
Zaidi, J. H., Fatima, I., Arif, M., & Qureshi, I. H. (2006). Determination of trace
elements in coffee beans and instant coffee of various origins by INAA. Journal of
Radioanalytical Nuclear Chemistry, 267, 109112.
A. Szymczycha-Madeja et al. / Food Chemistry 146 (2014) 220225 225