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Comment on Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34
 
 
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Reply

Reply to Nayak, P.K. Comment on “Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34”

by
Rafael Block Samulewski
1,
Flávio F. Ivashita
2,
Andrea Paesano, Jr.
2 and
Dimas Augusto Morozin Zaia
1,*
1
Departamento de Química, Universidade Estadual de Londrina, Londrina CEP 86057-970, PR, Brazil
2
Departamento de Física-CCE, Universidade Estadual de Maringá, Maringá 87020-900, PR, Brazil
*
Author to whom correspondence should be addressed.
Life 2021, 11(12), 1416; https://doi.org/10.3390/life11121416
Submission received: 17 September 2021 / Accepted: 2 December 2021 / Published: 17 December 2021
(This article belongs to the Collection What's on Board in the Journal Life)
We have considered the criticisms raised by Pranaba K. Nayak [1] regarding the Mössbauer analysis presented in our paper “Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions” [2] and, in our opinion, the issues addressed make sense. However, we do not believe that any of them implied mistakes regarding the final conclusions of the paper.
First of all, we recognize that the Mössbauer spectra of the MG4P, MG4CN, and MG4SC samples should be fitted considering three sextets and a doublet (thus performing 20 lines and not 18, as pointed out by Nayak). In this sense, we believe that the complainant is correct. Therefore, new fits were performed—for the spectra of samples containing goethite—and the spectra are provided in Figure 1, with hyperfine parameters presented in Table 1 (sextet A + sextet B for magnetite, sextet C or a hyperfine field distribution/Bhf Dist. for goethite, and a doublet for ferrihydrite). The uncertainties of the fitted parameters, subspectral areas, and linewidths have been included in the new table. It can be observed that goethite amounts, if any, are not small at all, justifying the point raised by the questioner. It is also worth noting the (large) linewidths found for the goethite discrete sextets, indicating some degree of hyperfine field distribution.
Finally, we emphasize that the Mössbauer analysis—in spite of the recognized problems in the fit methodology—accomplished its role as a fingerprint technique, since it confirmed the presence of magnetite, goethite, and ferrihydrite phases. In conclusion, after correcting the fits and fixing the table of hyperfine parameters, the main conclusions of the paper are exactly the same as before.

Funding

This research received no external funding.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Nayak, P.K. Comment on Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34. Life 2021, 11, 1361. [Google Scholar] [CrossRef]
  2. Samulewski, R.B.; Gonçalves, J.M.; Urbano, A.; da Costa, A.C.S.; Ivashita, F.F.; Paesano, A., Jr.; Zaia, D.A.M. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34. [Google Scholar] [CrossRef] [Green Version]
Figure 1. Mössbauer spectra of all magnetite samples.
Figure 1. Mössbauer spectra of all magnetite samples.
Life 11 01416 g001
Table 1. Mössbauer hyperfine parameters of all samples and iron mineral correspondence.
Table 1. Mössbauer hyperfine parameters of all samples and iron mineral correspondence.
SampleMineralSub
Spectrum
Γ/
mm s−1
IS/
mm s−1
QS/
mm s−1
Bhf/
T
A/
%
MGPMagnetiteSext A0.520.34−0.0848.552.2
Sext B0.460.65−0.0145.147.8
MGP4MagnetiteSext A0.530.330.0047.932.0
Sext B0.640.62−0.1244.517.8
FerrihydriteDoublet0.570.370.78-----31.0
GoethiteSext C1.990.35 *0.07 *39.0 *19.2
MGCN4MagnetiteSext A0.500.33−0.0249.230.0
Sext B0.670.550.0845.312.8
FerrihydriteDoublet0.520.360.69-----42.8
GoethiteSext C1.60 *0.360.0739.014.4
MGSCN4MagnetiteSext A0.500.33−0.0249.230.2
Sext B0.700.510.0745.213.4
FerrihydriteDoublet0.520.360.69-----42.9
GoethiteSext C1.60 *0.35 *0.0838.613.5
MGCNMagnetiteSext A0.520.33−0.0848.559.7
Sext B0.480.65−0.0945.440.3
MGSCNMagnetiteSext A0.470.32−0.0448.523.7
Sext B1.090.470.0244.230.5
FerrihydriteDoublet0.510.370.63-----7.3
GoethiteDist.0.30 *0.390.00 *25.138.5
* Fixed parameters. (Γ—Line width; IS—Isomer shift; QS—Quadrupole splitting; Bhf—Magnetic hyperfine field; A—Subspectrum area).
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Samulewski, R.B.; Ivashita, F.F.; Paesano, A., Jr.; Zaia, D.A.M. Reply to Nayak, P.K. Comment on “Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34”. Life 2021, 11, 1416. https://doi.org/10.3390/life11121416

AMA Style

Samulewski RB, Ivashita FF, Paesano A Jr., Zaia DAM. Reply to Nayak, P.K. Comment on “Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34”. Life. 2021; 11(12):1416. https://doi.org/10.3390/life11121416

Chicago/Turabian Style

Samulewski, Rafael Block, Flávio F. Ivashita, Andrea Paesano, Jr., and Dimas Augusto Morozin Zaia. 2021. "Reply to Nayak, P.K. Comment on “Samulewski et al. Magnetite Synthesis in the Presence of Cyanide or Thiocyanate under Prebiotic Chemistry Conditions. Life 2020, 10, 34”" Life 11, no. 12: 1416. https://doi.org/10.3390/life11121416

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