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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.

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

      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.

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