The Radiolysis of Water Vapor at Very High Dose Rates. I. Hydrogen Yields from H2O, H2O–HCl, and H2O–HBr Mixtures

1973 ◽  
Vol 51 (24) ◽  
pp. 4048-4055 ◽  
Author(s):  
A. W. Boyd ◽  
C. Willis ◽  
O. A. Miller

The plateau yields of hydrogen from the Febetron radiolysis of mixtures of water vapor with up to 8 mol% of HCl or HBr are G(H2) = 7.9 ± 0.2 and G(H2) = 4.6 ± 0.2 with 1 mol% SF6. These yields are consistent with G(H) = 7.45 in pure water vapor and G(H) = 4.15 in water vapor with SF6. In the Febetron radiolysis of pure water vapor at 2 × 1027 eV g−1 s−1 and densities of ~1 mg ml−1G(H2) = 1.65 + 0.05 from 164 to 190 °C. This yield is reduced to G(H2) = 0.90 ± 0.05 on the addition of 1 mol% SF6. Using a second order equivalent rate constant for the disappearance of the OH radicals in water vapor at 1 mg ml−1 of 2 × 1010 M−1 s−1 these yields are consistent with ate constant values for the reactions H + OH (+H2O) → H2O, OH + OH (+H2O) → H2O2, and H + H (+H2O) → H2, of 1.7 ± 0.1 × 1010 M−1 s−1, 1.5 ± 0.5 × 109M−1 s−1, and 3 ± 1 × 108 M−1 s−1, respectively.

1973 ◽  
Vol 51 (24) ◽  
pp. 4056-4061 ◽  
Author(s):  
A. W. Boyd ◽  
C. Willis ◽  
O. A. Miller

The isotope effect in the formation of hydrogen has been measured for H2O–D2O mixtures (10–90% H2O, 0.5–1.0 mg ml−1, 412–138 °C) with and without 1 mol% SF6 at 2 × 1027 eV g−1 s−1. The values of α ((H/D) radiolytic hydrogen/(H/D) H2O–D2O) for the reactions of hydrogen atoms are in the range 3–6 varying with H/D ratio of the substrate. Consideration of possible mechanisms for these large α values leads to the conclusions that reaction of the hydrogen atoms to form hydrogen involves the substrate and that the species H3O may be formed as an intermediate.


1973 ◽  
Vol 51 (18) ◽  
pp. 3132-3142 ◽  
Author(s):  
John W. Purdie ◽  
Hugh A. Gillis ◽  
Norman V. Klassen

Aqueous solutions of penicillamine (RSH) and penicillamine disulfide (RSSR) have been pulse irradiated at several pH's and the ensuing reactions studied. The rate constant for the reaction of solvated electrons with penicillamine disulfide decreases from 7.3 × 10−9 M−1 s−1 at pH 7 to 0.8 × 109 M−1 s−1 at pH 10. The first-order rate constant for the decomposition of the resulting radical anion, RSSR−, increases from 1.77 × 106 s−1 at pH 7 to 6.5 × 106 s−1 at pH 10. Both of these pH effects are attributed to deprotonation of the two amino groups of the disulfide which have microscopic pK values of 7.9 and 8.5. The equilibrium constant for the reaction[Formula: see text]is (2.31 ± 0.2) × 102 M−1 at pH 8 but increases to 3.04 × 102 M−1 at pH 7 and decreases to 0.96 × 102 M−1 at pH 9. Measured from the kinetics of the build-up of RSSR−, k−2 = 1.83 × 106 s−1 at pH 8.Decay of RSSR− in the presence of RSH follows second-order kinetics at high dose rates and first-order kinetics at low dose rates. At high dose rates two second-order reactions[Formula: see text]appear to be involved with rate constants of 1.7 × 109 M−1 s−1 and 6.4 × 109 M−1 s−1 respectively at pH 8, At low dose rates the decay appears to be due to a pseudo first-order reaction between RSSR− and H2O, k ~ 2 × 103 s−1, with valine (RH) and penicillamine trisulfide (RSSR) as principal products. These products are obtained in similar yields by gamma radiolysis of penicillamine solutions. At pH 5, the thiyl radical decays by second-order kinetics, 2k = (2.85 ± 0.15) × 109 M−1 s−1.Studies of solutions containing penicillamine and methanol showed that penicillamine repairs methanol radicals very efficiently by hydrogen transfer. k = (1.1 ± 0.1) × 108M−1 s−1. The implications of the results for chemical radioprotection are discussed.


Cancers ◽  
2021 ◽  
Vol 13 (19) ◽  
pp. 4942
Author(s):  
Maria Grazia Ronga ◽  
Marco Cavallone ◽  
Annalisa Patriarca ◽  
Amelia Maia Leite ◽  
Pierre Loap ◽  
...  

The development of innovative approaches that would reduce the sensitivity of healthy tissues to irradiation while maintaining the efficacy of the treatment on the tumor is of crucial importance for the progress of the efficacy of radiotherapy. Recent methodological developments and innovations, such as scanned beams, ultra-high dose rates, and very high-energy electrons, which may be simultaneously available on new accelerators, would allow for possible radiobiological advantages of very short pulses of ultra-high dose rate (FLASH) therapy for radiation therapy to be considered. In particular, very high-energy electron (VHEE) radiotherapy, in the energy range of 100 to 250 MeV, first proposed in the 2000s, would be particularly interesting both from a ballistic and biological point of view for the establishment of this new type of irradiation technique. In this review, we examine and summarize the current knowledge on VHEE radiotherapy and provide a synthesis of the studies that have been published on various experimental and simulation works. We will also consider the potential for VHEE therapy to be translated into clinical contexts.


The electron beam generated by a 15 MeV linear accelerator has been employed to induce reactions in aerated aqueous solutions of 1 to 25 mM ferrous sulphate, and of 0⋅1 to 1 mM ceric sulphate. The radiation was delivered in pulses of 1⋅3 μ s duration and over a range of dose rates from 0⋅5 to 20000 rads/pulse. Radiation yields at constant dose rate were compared with the aid of a chemical dose monitor. A system of two thin, widely spaced, irradiation vessels was employed to determine the variation of yield of any one system over successive known ranges of dose rate. The yield of ferric sulphate in the iron system was found to decrease with increasing dose rate in the range 0⋅01 to 10 krads/pulse by an overall factor of 0⋅85, and was appreciably dependent on the initial concentrations of dissolved oxygen and of ferrous sulphate at high dose rates. Yields of hydrogen and of hydrogen peroxide were practically independent of dose rate. The observations have been interpreted on the basis of inter-radical reactions which occur when the reaction zones of neighbouring clusters overlap. The following reactions can account for all the data: OH + Fe 2+ → Fe 3+ + OH ¯ , (1) H + O 2 → HO 2 , (2) H + OH → H 2 O. (7) The values k 1 / k 7 = 0⋅0062, and k 2 / k 7 = 0⋅22 are reasonably consistent with the observations. In the ceric sulphate system the yield of cerous sulphate increases progressively over the range 0⋅01 to 10 krads/pulse by an overall factor of 1⋅4. The data accord with the view that at high dose rates OH radicals react with them selves ultimately to form hydrogen peroxide, in competition with their normal reaction with cerous sulphate.


1969 ◽  
Vol 47 (16) ◽  
pp. 3007-3016 ◽  
Author(s):  
C. Willis ◽  
A. W. Boyd ◽  
O. A. Miller

Ammonia vapor has been irradiated with single pulses of electrons at a very high dose rate (1027 eV g−1 s−1) with a Febetron 705. At this dose rate radical–product reactions are not significant. In pure ammonia, hydrogen, nitrogen, and hydrazine are produced and the yields found at 1027 eV g−1 s−1 are: G(H2) = 3.58 ± 0.08; G(N2) = 1.00 ± 0.05; G(N2H4) = 0.58 ± 0.05. The yields are independent of pressure from 1 to 5 atm and of temperature between 20 and 200 °C. Above 250 °C the yields of all three products increase significantly and this is due to reaction [1] competing with radical–radical reactions.[Formula: see text]A rate constant for this reaction has been determined,[Formula: see text]Product yields have been measured for ammonia–propene mixtures. These yields have allowed determination of the primary radiation yields GNH = 0.74; [Formula: see text]; GH = 4.8; and G(−NH3) = 5.4.


1970 ◽  
Vol 48 (19) ◽  
pp. 3029-3033 ◽  
Author(s):  
C. Willis ◽  
O. A. Miller

Carbon monoxide has been irradiated with single intense pulses from an electron accelerator at a dose rate of ~ 2 × 1027 eV g−1 s−1. The yield of carbon dioxide obtained was G(CO2) = 0.7 ± 0.1 with a very small yield of carbon suboxide, G(C3O2) ≤ 0.02.Addition of propene reduces the carbon dioxide yield to almost zero while addition of propane has no effect. This suggests that propene is acting as an oxygen atom scavenger rather than as a quencher of an excited state of carbon monoxide. However, rate constant data do not support this suggestion and it is concluded that the residual yield of carbon dioxide observed at high dose rates arises from reaction 9[Formula: see text]where CO+ is in an A2Π or B2Σ+ state.


2016 ◽  
Vol 61 (14) ◽  
pp. N349-N361 ◽  
Author(s):  
P Fournier ◽  
J C Crosbie ◽  
I Cornelius ◽  
P Berkvens ◽  
M Donzelli ◽  
...  

2021 ◽  
Author(s):  
Alessio Sarti ◽  
Patrizia De Maria ◽  
Battistoni Giuseppe ◽  
Micol De Simoni ◽  
Cinzia Di Felice ◽  
...  

Abstract Prostate cancer is among the most common cancers in men and one of the leading causes of death worldwide. Different therapies are adopted for its treatment and generally radiotherapy with photons (RT) is the preferred solution in almost all cases. Up to now, in addition to photons, only protons have been implemented as alternative radiotherapy. The use of Very High Energy Electron (VHEE) beams (100-200 MeV) has been suggested in literature but the needed accelerators are more demanding, as far as space and cost are concerned, with respect to standard photon devices, with only limited advantages when compared to protons or other heavy ions. In this contribution we investigate how recent developments in electron beam therapy could reshape the landscape of prostate treatments. The VHEE Treatment Planning System obtained combining an accurate Monte Carlo (MC) simulation with a simple modelling of the FLASH effect (healthy tissues sparing at very high dose rates) is compared with conventional RT. The results demonstrate that FLASH therapy with VHEE beams of 70-130 MeV could represent a valid alternative to standard RT allowing a better sparing of the healthy tissues surrounding the tumour, in the framework of an affordable technological development.


Author(s):  
Abida Sultana ◽  
Ahmed Alanazi ◽  
Jintana Meesungnoen ◽  
Jean-Paul Jay-Gerin

Monte Carlo multi-track chemistry simulations were carried out to study the effects of high dose rates on the transient yields of hydronium ions (H<sub>3</sub>O<sup>+</sup>) formed during low linear energy transfer (LET) radiolysis of both pure, deaerated and aerated liquid water at 25 °C, in the interval ~1 ps–10 μs. Our simulation model consisted of randomly irradiating water with <i>N</i> interactive tracks of 300-MeV incident protons (LET ~ 0.3 keV/μm), which simultaneously impact perpendicularly on the water within a circular surface. The effect of the dose rate was studied by varying <i>N</i>. Our calculations showed that the radiolytic formation of H<sub>3</sub>O<sup>+</sup> causes the entire irradiated volume to temporarily become very acidic. The magnitude and duration of this abrupt “acid-spike” response depend on the value of <i>N</i>. It is most intense at times less than ~10–100 ns, equal to ~3.4 and 2.8 for <i>N</i> = 500 and 2000 (<i>i.e.</i>, for dose rates of ~1.9 × 10<sup>9</sup> and 8.7 × 10<sup>9</sup> Gy/s, respectively). At longer times, the pH gradually increases for all <i>N</i> values and eventually returns to the neutral value of seven, which corresponds to the non-radiolytic, pre-irradiation concentration of H<sub>3</sub>O<sup>+</sup>. It is worth noting that these early acidic pH responses are very little dependent on the presence or absence of oxygen. Finally, given the importance of pH for many cellular functions, this study suggests that these acidic pH spikes may contribute to the normal tissue-sparing effect of FLASH radiotherapy.


1990 ◽  
Vol 201 ◽  
Author(s):  
E. Cortesi ◽  
F. Namavar ◽  
R. F. Pinizzotto ◽  
H. Yang

AbstractWe have studied Separation by IMplantation of OXygen (SIMOX) processes using very high dose rates (40–60 μA/cm2). For a dose of 4 × 1017 O+/cm2 at 160 keV, the structure formed by implantation at 50 μA/cm2 is very similar to that associated with lower dose rates. The same dose implanted at a dose rate of 60 μA/cm2, however, results in the formation of pits in the silicon surface as well as a somewhat different oxide structure. Implantation through a surface oxide layer appears to result in a structure similar to that associated with lower dose rate implantation. These and higher dose samples suggest that the threshold for pit formation is related to both dose rate and dose.


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