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Article history: Total sulfur concentrations in vinegars were determined using molecular absorption of carbon monosul-
Received 3 July 2015 fide (CS) determined with a high-resolution continuum source flame atomic absorption spectrometer.
Received in revised form 29 June 2016 The molecular absorption of CS was measured at 258.056 nm in an airacetylene flame. Due to non-
Accepted 3 July 2016
spectral interference, as well as the different sensitivities to some sulfur compounds, all sulfur species
Available online 5 July 2016
were oxidized to sulfate using a HNO3 and H2O2 mixture and the analyte addition technique was applied
for quantification. The limit of detection (LOD) and limit of quantification (LOQ) were 11.6 and
Keywords:
38.6 mg L 1, respectively. The concentrations of sulfur in various vinegars ranged from 6LOD to
Carbon monosulfide
Sulfur
163.6 mg L 1.
Vinegar 2016 Elsevier Ltd. All rights reserved.
High-resolution continuum source
molecular absorption spectrometry
http://dx.doi.org/10.1016/j.foodchem.2016.07.007
0308-8146/ 2016 Elsevier Ltd. All rights reserved.
530 N. Ozbek, S. Akman / Food Chemistry 213 (2016) 529533
Therefore, a systematic study would be needed to optimize instru- vided by LGC Standards (Teddington, UK).
mental conditions for the graphite furnace as well as selection of Different types of vinegars (grape, apple, balsamic, pomegra-
an appropriate calibrant with similar sensitivity and thermal nate and fig), produced in 2015 by different factories, were pur-
behavior to those of the analyte in the sample. In case of the flame chased from markets in Istanbul. The samples were chosen from
atomizer, since the sample is not thermally treated prior to the amongst the most commonly consumed brands in Turkey.
molecule formation, such problems (i.e. removal of the volatile
compounds at lower temperatures) do not occur. Moreover, non- 2.3. Procedure
spectral interferences, due to reactions with sulfur, are less likely
in the flame environment. Finally, optimization and analysis using The analyte addition technique was applied to determine sulfur
the flame technique are faster and more practical than the graphite in vinegar. Standards were prepared from sodium metabisulfite
furnace. daily. Vinegars were analyzed seven days after opening the bottle.
Until now, sulfur was determined by flame HR-CS AAS (HR-CS In order to convert the sulfur forms to sulfate, 0.20 mL of H2O2
FAAS) in foods (Ozbek & Baysal, 2015; Zambrzycka & God (30%) and 0.20 mL HNO3 (65%) were added to 5 mL of vinegar
_
lewska-Zykiewicz, 2014), coal samples (Baysal & Akman, 2011), and the mixture was made up to 10 mL with distilled water or
plant leaves (Oliveira, Gomes Neto, Nbrega, & Jones, 2010), agri- standards. In order to prepare the analyte addition graph, three
cultural samples (Virgilio, Raposo, Cardoso, Nbrega, & Gomes solutions were used. While the first was made up to volume with
Neto, 2011), petroleum products (Kowalewska, 2011) and by gra- distilled water, the others were made up to volume with 20 mg L 1
phite furnace HR-CS AAS (HR-CS GFAAS) in food samples and 50 mg L 1 of sodium metabisulfite, respectively. For each sam-
(Gunduz & Akman, 2014; Ozbek & Akman, 2013), biological sam- ple type (grape vinegar, apple vinegar etc.), different standard
ples (Ferreira, Lepri, Welz, Carasek, & Huang, 2010), coal samples addition graphs were developed since their matrices were different
(Mior, Mors, Welz, Carasek, & de Andrade, 2013) and airborne from one another. After standing for 30 min, the solutions were
particulates (Ozbek & Baysal, 2016). Moreover determination of aspirated into the fuel-rich airacetylene flame. The results were
sulfur in water samples was done by molecular absorption of SnS evaluated as the mean of triplicate analysis.
by HR-CS GFAAS (Baumbach, Limburg, & Einax, 2013). Sulfur deter-
mination methods, based on molecular absorption of carbon
3. Results and discussion
monosulfide (CS) using high resolution-continuum source atomic
absorption spectrometers, were extensively reviewed (Butcher,
3.1. Selection of atomizer
2013; Resano, Flrez, & Garca-Ruiz, 2014; Welz et al., 2009). The
aim of this study was, therefore, to develop and optimize a proce-
In this study, the flame technique was selected because it was
dure for the determination of total sulfur in vinegars based on
anticipated that the sulfur concentrations in most of the vinegars
molecular absorption of CS using HR-CS FAAS, and to discuss the
samples would be higher than the LOD. Sulfur determination, even
effects of different sulfur species on the CS sensitivity and elimina-
in a flame, is not completely free of problems. It has been reported
tion of errors due to interference.
that the sensitivities of CS obtained from different compounds
might not always be the same (Huang et al., 2008). However, the
2. Experimental problems are less significant and their elimination is less trouble-
some compared to the graphite furnace.
2.1. Instrumentation
3.2. Selection of wavelength
An Analytik Jena ContrAA 700 High-Resolution Continuum
Source Flame Atomic Absorption Spectrometer (Analytik Jena, Jena, The primary CS lines, 257.593, 257.959 and 258.056 nm, are
Germany) equipped with an airacetylene-flame, 300 W xenon well documented in the literature with respect to sensitivity
short-arc lamp (XBO 301, GLE, Jena, Germany), a high-resolution (Ferreira et al., 2010; Huang, Becker-Ross, Florek, Heitmann, &
double monochromator with a prism pre-monochromator, a Okruss, 2006; Huang et al., 2005; Virgilio et al., 2011). The highest
high-resolution echelle monochromator and a charge coupled sensitivity was obtained at 258.056 nm, corresponding to one of
device (CCD) array as a detector was used. The molecular absorp- the Dm = 0 vibrational sequences of the electronic transition X1R
tion of CS was measured at 258.056 nm (central pixel 1). All mea- + ? A1P (Kowalewska, 2011). The wavelength resolved absorption
surements were made in at least three replicates. Samples were spectrum of a vinegar sample in the vicinity of 258.056 nm is
prepared using Eppendorf pipettes in polyethylene wares. shown in Fig. 1. No molecular and atomic absorption signal
N. Ozbek, S. Akman / Food Chemistry 213 (2016) 529533 531
tivities of some sulfur species in the vinegar (free and bound sulfur
dioxide, sulfite, bisulfite, sulfate etc.), and those of the standards
added to the samples, might not be the same, even with the ana-
lyte addition technique.
In a series of experiments, we compared the sensitivities for CS
in aqueous solutions of sulfur prepared from potassium pyrosul-
fate (K2S2O7), potassium sulfate (K2SO4), magnesium sulfate
(MgSO4), sodium sulfate (Na2SO4.), sodium thiosulfate (Na2S2O3),
sodium sulfite (Na2SO3), sodium persulfate (Na2S2O8) and sodium
metabisulfite (Na2S2O5) and similar sensitivities were obtained.
As examples, the calibration curves obtained from sodium salts
of sulfate, sulfite and metabisulfite are shown in Fig. 2. When the
standards were prepared in the acetic acid, which is the main com-
ponent of vinegar as well as an addition to vinegar, the CS sensitiv-
ities dramatically increased, depending on the acidity, whereas
sulfates hardly changed (Fig. 3).
Therefore, in this study, in order to eliminate the errors due to
Fig. 1. Wavelength resolved spectrum for CS at 258.056 nm of blank (black) and a different sensitivities of various sulfur forms, HNO3 and H2O2 were
vinegar sample (blue). (For interpretation of the references to color in this figure added to oxidize all the sulfur species to the sulfate. Since a certi-
legend, the reader is referred to the web version of this article.)
fied reference material (CRM) was not available, in order to test
some errors independent of the sample matrix, such as instrumen-
originating from the sample matrix was detected. Thus, tal errors, weighing errors, pipetting errors etc., sulfur in a waste
258.056 nm was used subsequently without any problems. water CRM sample was subjected to the same procedure as the
vinegar samples. The value was found to be within the uncertainty
limits for the CRM, which showed there were no major errors influ-
3.3. Flame conditions encing the accuracy of analysis.
Table 2 Ferreira, H. S., Lepri, F. G., Welz, B., Carasek, E., & Huang, M.-D. (2010).
Figures of merit for the proposed method. Determination of sulfur in biological samples using high-resolution molecular
absorption spectrometry in a graphite furnace with direct solid sampling.
Parameter Value Journal of Analytical Atomic Spectrometry, 25(7), 10391045.
1 Gunduz, S., & Akman, S. (2014). Sulfur determination in some nuts and dried fruits
Characteristic concentration, (mg L ) 44.0
sold in Turkey by high resolution graphite furnace molecular absorption
Limit of detection, (mg L 1) 11.6
spectrometry. LWT Food Science and Technology, 59(2, Part 1), 718723.
Limit of quantification, (mg L 1) 38.6 Heilmann, J., Boulyga, S., & Heumann, K. (2004). Accurate determination of sulfur in
1
Linearity up to 1000 mg L of S gasoline and related fuel samples using isotope dilution ICPMS with direct
Regression coefficient R2: 0.999 sample injection and microwave-assisted digestion. Analytical and Bioanalytical
Instrumental RSD (N:3 successive aspirations) 56% Chemistry, 380(2), 190197.
Method RSD (N:3 independent analyses) 56% Huang, M. D., Becker-Ross, H., Florek, S., Heitmann, U., & Okruss, M. (2005). Direct
determination of total sulfur in wine using a continuum-source atomic-
absorption spectrometer and an airacetylene flame. Analytical and
Bioanalytical Chemistry, 382(8), 18771881.
4. Conclusion Huang, M. D., Becker-Ross, H., Florek, S., Heitmann, U., & Okruss, M. (2006).
Determination of sulfur by molecular absorption of carbon monosulfide using a
high-resolution continuum source absorption spectrometer and an air
The method described for the determination of total sulfur in acetylene flame. Spectrochimica Acta Part B, 61(2), 181188.
vinegars was based on measurement of the molecular absorption Huang, M. D., Becker-Ross, H., Florek, S., Heitmann, U., Okruss, M., & Patz, C.-D.
of carbon monosulfide (CS) using HR-CS FAAS. The method is rapid, (2008). Determination of sulfur forms in wine including free and total sulfur
dioxide based on molecular absorption of carbon monosulfide in the air
robust, practical and simple. The study describes the successful acetylene flame. Analytical and Bioanalytical Chemistry, 390(1), 361367.
application of an atomic absorption spectrometer for sulfur deter- International for the USDA National Organic Program ICF (2011). Sulphur dioxide,
mination that is not determined by a conventional AAS using a hol- Technical Evaluation Report.
Kendall, D. S., Schoenwald, S. D., Siao, M., & Hendricks, S. (1995). The determination
low cathode lamp. Most of the sulfur concentrations in vinegars of sulfur and chlorine in used oil by X-Ray fluorescence, ICP and ion
were above the limit of detection in flame avoiding the need for chromatography. Hazardous Waste and Hazardous Materials, 12(4), 373380.
the more time consuming and expensive graphite furnace Kowalewska, Z. (2011). Feasibility of high-resolution continuum source molecular
absorption spectrometry in flame and furnace for sulphur determination in
technique. petroleum products. Spectrochimica Acta Part B: Atomic Spectroscopy, 66(7),
546556.
Funding Metcalfe, D. D., Sampson, H. A., & Simon, R. A. (2009). Food allergy: Adverse reactions
to foods and food additives. Wiley.
Mior, R., Mors, S., Welz, B., Carasek, E., & de Andrade, J. B. (2013). Determination of
This study was not funded by any agencies/institutes. sulfur in coal using direct solid sampling and high-resolution continuum source
molecular absorption spectrometry of the CS molecule in a graphite furnace.
Talanta, 106, 368374.
Conflict of interest Nakayama, T. (1959). Studies on acetic acid-bacteria I. Biochemical studies on
ethanol oxidation. Journal of Biochemistry, 46(9), 12171225.
Oliveira, S. R., Gomes Neto, J. A., Nbrega, J. A., & Jones, B. T. (2010). Determination of
Nil Ozbek declares that she has no conflict of interest.
macro- and micronutrients in plant leaves by high-resolution continuum source
Suleyman Akman declares that he has no conflict of interest. flame atomic absorption spectrometry combining instrumental and sample
preparation strategies. Spectrochimica Acta Part B: Atomic Spectroscopy, 65(4),
Ethical approval 316320.
Ozbek, N., & Akman, S. (2013). Determination of total sulfur in food samples by solid
sampling high-resolution continuum source graphite furnace molecular
For this type of study formal consent is not required. This study
absorption spectrometry. Journal of Agricultural and Food Chemistry, 61(20),
does not contain any studies with human participants or animals 48164821.
performed by any of the authors. Ozbek, N., & Baysal, A. (2015). A new approach for the determination of sulphur in
food samples by high-resolution continuum source flame atomic absorption
spectrometer. Food Chemistry, 168, 460463.
Informed constent Ozbek, N., & Baysal, A. (2016). A new approach for the determination of sulphur in
airborne particles by HR-CS ETAAS. International Journal of Environmental
Analytical Chemistry, 96(6), 505514.
Not applicable. Quirs, C., Herrero, M., Garca, L. A., & Daz, M. (2012). Effects of SO2 on lactic acid
bacteria physiology when used as a preservative compound in malolactic
Acknowledgements fermentation. Journal of the Institute of Brewing, 118(1), 8996.
Republic of Turkey Ministry of Food Agriculture and Livestock (2004). Trk Gda
Kodeksi-Renklendiriciler ve Tatlandrclar Dsndaki Gda Katk Maddeleri Tebligi.
We are grateful to Mrs Ece Ozcelik for her helpful work for this Resano, M., Flrez, M. A., & Garca-Ruiz, E. (2014). Progress in the determination of
study. metalloids and non-metals by means of high-resolution continuum source
atomic or molecular absorption spectrometry. A critical review. Analytical and
Bioanalytical Chemistry, 406(910), 22392259.
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