Natural Radioactive Environments as Sources of Local Disequilibrium for the Emergence of Life.

Certain subterranean environments of Earth have naturally accumulated long-lived radionuclides, such as 238U, 232Th, and 40K, near the presence of liquid water. In these natural radioactive environments, water radiolysis can produce chemical species of biological importance, such as H2. Although the proposal of radioactive decay as an alternative source of energy for living systems has existed for >30 years, this hypothesis gained strength after the recent discovery of a peculiar ecosystem in a gold mine in South Africa, whose existence is dependent on chemical species produced by water radiolysis. In this study, we calculate the chemical disequilibrium generated locally by water radiolysis due to gamma radiation. We then analyze the possible contribution of this disequilibrium for the emergence of life, considering conditions of early Earth and having as reference the alkaline hydrothermal vent theory. Results from our kinetic model point out the similarities between the conditions caused by water radiolysis and those found on alkaline hydrothermal systems. Our model produces a steady increase of pH with time, which favors the formation of a natural electrochemical gradient and the precipitation of minerals with catalytic activity for protometabolism in this aqueous environment. We conclude by describing a possible free-energy conversion mechanism based on protometabolism, which could be a requisite for the emergence of life in Hadean Earth.

Valine Radiolysis by H+, He+, N+, and S15+ MeV Ions.

Radiolysis of biomolecules by fast ions has interest in medical applications and astrobiology. The radiolysis of solid D-valine (0.2-2 µm thick) was performed at room temperature by 1.5 MeV H+, He+, N+, and 230 MeV S15+ ion beams. The samples were prepared by spraying/dropping valine-water-ethanol solution on ZnSe substrate. Radiolysis was monitored by infrared spectroscopy (FTIR) through the evolution of the intensity of the valine infrared 2900, 1329, 1271, 948, and 716 cm-1 bands as a function of projectile fluence. At the end of sample irradiation, residues (tholins) presenting a brownish color are observed. The dependence of the apparent (sputtering + radiolysis) destruction cross section, σd, on the beam stopping power in valine is found to follow the power law σd = aSen, with n close to 1. Thus, σd is approximately proportional to the absorbed dose. Destruction rates due to the main galactic cosmic ray species are calculated, yielding a million year half-life for solid valine in space. Data obtained in this work aim a better understanding on the radioresistance of complex organic molecules and formation of radioproducts.

Oxidant and Antioxidant Effects of Gentisic Acid in a 177Lu-Labelled Methionine-Containing Minigastrin Analogue.

BACKGROUND: The radiolabelling of receptor-binding peptides for therapy is a challenge since the peptide itself is exposed (during labelling, storage and transport) to radiation-induced damage, directly or indirectly, in aqueous solution. Hence, the use of radiostabilizers seems to be mandatory, especially in peptide molecules that contain radiation-sensitive amino acids. OBJECTIVE: The aim of this study was to investigate the effect of two stabilizers, gentisic acid and methionine, to delve into how each of them affects the radiolabelling and stability of the minigastrin analogue [177Lu]Lu-DOTA-His-His-Glu-Ala-Tyr-Gly-Trp-Met-Asp-Phe-NH2 through the analysis of the 22 species distinguished over time by an optimized HPLC system. METHODS: The stabilizers, in different combinations, were present from the beginning of the labelling process carried out at 96 °C for 15 min. The stability was studied for up to 7 days. RESULTS: The unexpected selective oxidation of the methionine residue of the radiolabelled peptide, promoted by gentisic acid, led to studying the effect of pH, from 3.5 to 6.0, in the presence of only this stabilizer. A pH-dependent antioxidant behaviour was revealed, showing a decrease in peptide impurities but an increase in the selective oxidation as the pH was increased. CONCLUSION: The selective oxidation of the methionine residue could be induced by oxidizing species probably produced in the reaction between gentisic acid and free radicals of water, during the protection of the radiolabelled peptide from the attack of these harmful species. Therefore, the addition of methionine becomes necessary to effectively decrease this selective oxidation in the methioninecontaining peptide.

Degradation and acute toxicity removal of the antidepressant Fluoxetine (Prozac(®)) in aqueous systems by electron beam irradiation.

Electron beam irradiation (EBI) has been considered an advanced technology for the treatment of water and wastewater, whereas very few previous investigations reported its use for removing pharmaceutical pollutants. In this study, the degradation of fluoxetine (FLX), an antidepressant marketed as Prozac(®), was investigated by using EBI at FLX initial concentration of 19.4 ± 0.2 mg L(-1). More than 90 % FLX degradation was achieved at 0.5 kGy, with FLX below the detection limit (0.012 mg L(-1)) at doses higher than 2.5 kGy. The elucidation of organic byproducts performed using direct injection mass spectrometry, along with the results of ion chromatography, indicated hydroxylation of FLX molecules with release of fluoride and nitrate anions. Nevertheless, about 80 % of the total organic carbon concentration remained even for 7.5 kGy or higher doses. The decreases in acute toxicity achieved 86.8 and 9.6 % for Daphnia similis and Vibrio fischeri after EBI exposure at 5 kGy, respectively. These results suggest that EBI could be an alternative to eliminate FLX and to decrease residual toxicity from wastewater generated in pharmaceutical formulation facilities, although further investigation is needed for correlating the FLX degradation mechanism with the toxicity results.

Track structure modeling in liquid water: A review of the Geant4-DNA very low energy extension of the Geant4 Monte Carlo simulation toolkit.

Understanding the fundamental mechanisms involved in the induction of biological damage by ionizing radiation remains a major challenge of today's radiobiology research. The Monte Carlo simulation of physical, physicochemical and chemical processes involved may provide a powerful tool for the simulation of early damage induction. The Geant4-DNA extension of the general purpose Monte Carlo Geant4 simulation toolkit aims to provide the scientific community with an open source access platform for the mechanistic simulation of such early damage. This paper presents the most recent review of the Geant4-DNA extension, as available to Geant4 users since June 2015 (release 10.2 Beta). In particular, the review includes the description of new physical models for the description of electron elastic and inelastic interactions in liquid water, as well as new examples dedicated to the simulation of physicochemical and chemical stages of water radiolysis. Several implementations of geometrical models of biological targets are presented as well, and the list of Geant4-DNA examples is described.

Influence of concentration on the radiolytic decomposition of thiamine, riboflavin, and pyridoxine in aqueous solution / Influencia de la concentración en la descomposición radiolítica de tiamina, riboflavina y piridoxina en solución acuosa / Influência da concentração na decomposição radiolítica de tiamina, riboflavina e piridoxina em solução aquosa

Vitamin loss during irradiation has been claimed as a critical area in food irradiation technology, especially that of thiamine (B1), which has been considered as the most sensitive to radiation. Although it has been suggested that no vitamin deficiency could result from consuming irradiated food, a long debate on the loss of vitamins and other nutrients during food irradiation has been maintained by the lack of experimental studies monitoring decomposition rates at different concentrations and doses. Since thiamine, riboflavin, and pyridoxine are labile vitamins, this study has focused on their radiolytic decomposition in dilute aqueous solutions in the presence of air. The decomposition process was followed by HPLC and UV-spectroscopy. The results obtained in aqueous solutions showed a dependence of the decomposition as a nonlinear function of the dose. Of these three compounds, the decomposition was higher for thiamine than for riboflavin and even less in pyridoxine.

La pérdida de vitaminas durante procesos de irradiación ha sido considerada como un área crítica en la tecnología de irradiación de alimentos, especialmente la tiamina (B1), que ha sido considerada como la más sensible a la radiación ionizante. La deficiencia de vitaminas en humanos no es producida por el consumo de alimentos irradiados, sin embargo, existen debates sobre la pérdida de vitaminas y otros nutrientes provocada por la irradiación de alimentos, esta discusión sigue latente debido a que hay pocos estudios experimentales de la descomposición de vitaminas a diferentes dosis y concentraciones. Esta investigación se centró en el estudio de la descomposición radiolítica de tiamina, riboflavina y piridoxina en soluciones acuosas y en presencia de aire. El proceso de descomposición fue seguido por cromatografía líquida con detección UV. Los resultados obtenidos en soluciones acuosas mostraron una dependencia no lineal entre la descomposición en función de la dosis. De estos tres compuestos, la descomposición fue mayor en tiamina que en riboflavina y menor en la piridoxina.

A perda de vitaminas durante processos de irradiação tem sido considerada uma área crítica na tecnologia de irradiação de alimentos, especialmente no caso da tiamina (B1), que tem sido considerada como a mais sensível à radiação ionizante. Embora a deficiência de vitaminas em seres humanos não seja produzida pelo consumo de alimentos irradiados, longos debates sobre as perdas de vitaminas e outros nutrientes causadas pela irradiação de alimentos tem sido mantidos devido aos estudos experimentais limitados monitorando a proporção da decomposição em diferentes concentrações de vitaminas e doses de radiação aplicadas. Considerando que a tiamina, riboflavina e piridoxina são vitaminas instáveis, o presente estudo focalizou a decomposição radiolítica dessas vitaminas em soluções aquosas diluídas e na presença de ar. O processo de decomposição foi analizado por cromatografia líquida com detecção UV. Os resultados obtidos em soluções aquosas mostraram uma dependência da decomposição como função não linear da dose. Destes três compostos, a descomposição foi mais alta para tiamina que na riboflavina e menor para piridoxina.