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was two and a half hours. A fundamental parameter method was used to determine the concentration of elements. Detection limits were obtained in ppm: 0.4 for Mn, 0.4 for Fe, 0.4 for Ni, 0.2 for Rb, 0.2 for Sr, and 0.8 for Ba. Table 3.3 shows the concentrations of elements in coffee zeroes by country of cultivation. The maximum levels of Mn (47 ppm), Sr (12 ppm), Ba (9 ppm) were recorded in coffee samples from Colombia, Fe (53 ppm), Ni (3 ppm) in Vietnamese coffee, Rb in coffee from Indonesia (82 ppm) and from Tanzania (67 ppm). It has been found that roasting does not affect the content of analytes in coffee. The use of analysis results for Fe, Mn, Ni, Rb, Sr, and Ba allowed for the successful identification coffee's country of origin.
Table 3.3 Concentrations (mean ± standard deviation) of some elements in coffee beans, depending on the country of origin (ppm) Adapted from [84].
| Element | Concentration (mean ± standard deviation) | |||||
|---|---|---|---|---|---|---|
| Mn | 39.7 ± 4.9 | 47.1 ± 8.5 | 29.3 ± 2.3 | 34.6 ± 20.1 | 37.5 ± 4.8 | 39.7 ± 10.1 |
| Fe | 35.5 ± 3.8 | 30.7 ± 1.4 | 52.9 ± 13.2 | 32.8 ± 3.5 | 28.3 ± 2.7 | 29.7 ± 1.5 |
| Ni | nd | 0.5 ± 0.3 (n = 10) | 3.5 ± 0.9 | nd | nd | nd |
| Rb | 22.2 ± 5.7 | 23.5 ± 7.4 | 42.7 ± 13.8 | 82.5 ± 13.4 | 67.2 ± 9.5 | 37.7 ± 7.7 |
| Sr | 3.4 ± 0.7 | 11.8 ± 8.3 | 3.3 ± 0.7 | 5.7 ± 1.1 | 6.4 ± 2.9 | 6.6 ± 1.8 |
| Ba | 3.1 ± 1.0 | 8.6 ± 3.8 | 2.3 ± 1.4 (n = 15) | 4.3 ± 2.8 | 7.7 ± 4.1 | 6.3 ± 2.3 |
| Number of samples (n) | 17 | 17 | 17 | 10 | 7 | 7 |
| Production country | Brazil | Colombia | Vietnam | Indonesia | Tanzania | Guatemala |
Note – nd: not detected; n: number of samples
Debastiani et al. [85] used the PIXE version to investigate the elemental composition of roasted coffee grains and roasted ground coffee. The chemical composition of the packaged roasted ground coffee and the composition of the similarly roasted coffee grains ground immediately prior to the analysis were also compared. Measurements were performed at the Institute of Physics of the Federal University of Rio Grandi do Sul (Brazil, Ion Implantation Laboratory). A beam of protons with an energy of 2 MeV and Si (Li) a detector with energy resolution of 160 eV for radiation with an energy of 5.9 keV were used. C, O, and N are measured by the Rutherford Backscatter (RBS) method. The results showed that the coffee grain matrix consisted mainly of C, followed by O and N. PIXE results for roasted ground coffee and roasted coffee grains showed that K and Mg are the elements with the highest concentration, Zn and Sr are trace elements. Comparison of these two types of coffee showed that the contents of certain elements, particularly Mg, Cl, Ca, Fe, Zn, and Rb, are statistically significantly different. No clear picture of the origin of such differences has been revealed. Because of this, the correlation between these differences and the quality of the final drink has not been established. The authors note the possibility that factors such as processing and negligent harvesting leading to the inclusion of twigs and defective beans in frying processes and crushing may have influenced the results. The results obtained by the authors for Cl showed that packaged ground roasted coffee contained more of this element, compared with fresh ground coffee. Cl‐based compounds such as chloroanisoles are known to impart unpleasant odors to beverages such as wine and coffee, and these results are consistent with the fact that freshly ground coffee is generally thought to produce a better‐quality beverage. Green and roasted grains have the same chemical composition, indicating that none of the elements studied in this work are lost during the roasting process. All elements except Fe have the same concentrations in both kinds of grains. The distribution of elements over the surface of the grains is uniform, while the distribution within the grains shows certain patterns for different elements.
In the work of Hernández et al. [86], an ED X‐ray spectrometer (Rh anode, silicon drift detector) was used to determine the contents of several elements from 11 to 38: Na, P, S, Cl, K, Ca, Mn, Fe, Cu, Zn, Br, Rb, and Sr. The sample material was dried at room temperature and the tablets were pelletized. The authors analyzed 11 samples of commercial ground coffee and compared the obtained data with a sample of instant coffee and two other samples of ground coffee. Calibration and validation of content determination accuracy was assessed by analyzing CRM‐certified NIST 1547 (peach leaves), 1570a (spinach leaves), 1573a (tomato leaves), and 1571 (orchid leaves). Generally, the measured content of the elements was little different for all coffee samples and did not exceed toxic levels. Nevertheless, differences between the contents of the elements are shown and discussed. The authors recommend collecting a more complete collection of coffee samples for future work. In such a collection it is necessary to significantly expand the range of samples for instant coffee.
In a recently published article Debastiani et al. [87] continued research on Brazilian coffee by PIXE version. The authors investigated the change in the chemical composition of Brazilian coffee at various stages of the drip brewing process. For this purpose, more than 140 samples of 8 different Brazilian brands of ground coffee (original samples of ground coffee, material of spent coffee, and coffee beverage after paper filtration) were analyzed. Major conclusions from Debastiani et al. [87] are:
Confirmed the remark of Debastiani et al. [85] about significant differences in concentrations of certain elements between coffee samples of different brands and between different batches of the same brand.
K, Mg, P, Ca, and S proved to be elements with a higher concentration in Brazilian coffee.
Analysis of spent coffee showed that the extraction coefficients are specific for each element (the highest extraction coefficients from ground coffee are obtained for Cl and K, then Rb and P).
Paper filters do not transfer elements to coffee beverage.
3.6 Determination of the Elemental Composition of Krasnodar Tea Samples by TXRF and WDXRF
The paper Maltsev et al. [88], analyzed samples of several varieties of Krasnodar tea. This tea is the singular Russian tea product, the chemical composition of which was