scholarly journals Measurement on Diffusion Coefficients and Isotope Fractionation Factors by a Through-Diffusion Experiment

Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 208
Author(s):  
Takuma Hasegawa ◽  
Kotaro Nakata ◽  
Rhys Gwynne
Keyword(s):  
Groundwater Flow ◽  
Diffusion Coefficients ◽  
Isotope Fractionation ◽  
Free Water ◽  
Effective Porosity ◽  
Diffusion Experiment ◽  
Fractionation Factor ◽  
Through Diffusion ◽  
Geological Formations ◽  
Fractionation Factors

For radioactive waste disposal, it is important that local groundwater flow is slow as groundwater flow is the main transport medium for radioactive nuclides in geological formations. When the groundwater flow is very slow, diffusion is the dominant transport mechanism (diffusion-dominant domain). Key pieces of evidence indicating a diffusion-dominant domain are the separation of components and the fractionation of isotopes by diffusion. To prove this, it is necessary to investigate the different diffusion coefficients for each component and the related stable isotope fractionation factors. Thus, in this study, through-diffusion and effective-porosity experiments were conducted on selected artificial materials and natural rocks. We also undertook measurements relating to the isotope fractionation factors of Cl and Br isotopes for natural samples. For natural rock samples, the diffusion coefficients of water isotopes (HDO and H218O) were three to four times higher than those of monovalent anions (Cl−, Br- and NO3−), and the isotope fractionation factor of 37Cl (1.0017–1.0021) was slightly higher than that of free water. It was experimentally confirmed that the isotope fractionation factor of 81Br was approximately 1.0007–1.0010, which is equivalent to that of free water. The enrichment factor of 81Br was almost half that of 37Cl. The effective porosity ratios of HDO and Cl were slightly different, but the difference was not significant compared to the ratio of their diffusion coefficients. As a result, component separation was dominated by diffusion. For artificial samples, the diffusion coefficients and effective porosities of HDO and Cl were almost the same; it was thus difficult to assess the component separation by diffusion. However, isotope fractionation of Cl and Br was confirmed using a through-diffusion experiment. The results show that HDO and Cl separation and isotope fractionation of Cl and Br can be expected in diffusion-dominant domains in geological formations.

scholarly journals Hydrogen isotope fractionation in the photolysis of formaldehyde

2008 ◽  
Vol 8 (5) ◽  
pp. 1353-1366 ◽  
Author(s):  
T. S. Rhee ◽  
C. A. M. Brenninkmeijer ◽  
T. Röckmann
Keyword(s):  
Isotope Ratio ◽  
Isotope Fractionation ◽  
Isotopic Fractionation ◽  
Photochemical Oxidation ◽  
Atmospheric Conditions ◽  
Isotopic Enrichment ◽  
Fractionation Factor ◽  
Removal Processes ◽  
Molecular Channel ◽  
Fractionation Factors

Abstract. Experiments investigating the isotopic fractionation in the formation of H2 by the photolysis of CH2O under tropospheric conditions are reported and discussed. The deuterium (D) depletion in the H2 produced is 500(±20)‰ with respect to the parent CH2O. We also observed that complete photolysis of CH2O under atmospheric conditions produces H2 that has virtually the same isotope ratio as that of the parent CH2O. These findings imply that there must be a very strong concomitant isotopic enrichment in the radical channel (CH2O+hν → CHO+H) as compared to the molecular channel (CH2O+hν → H2+CO) of the photolysis of CH2O in order to balance the relatively small isotopic fractionation in the competing reaction of CH2O with OH. Using a 1-box photochemistry model we calculated the isotopic fractionation factor for the radical channel to be 0.22(±0.08), which is equivalent to a 780(±80)‰ enrichment in D of the remaining CH2O. When CH2O is in photochemical steady state, the isotope ratio of the H2 produced is determined not only by the isotopic fractionation occurring during the photolytical production of H2 (αm) but also by overall fractionation for the removal processes of CH2O (αf), and is represented by the ratio of αm/αf. Applying the isotopic fractionation factors relevant to CH2O photolysis obtained in the present study to the troposphere, the ratio of αm/αf varies from ~0.8 to ~1.2 depending on the fraction of CH2O that reacts with OH and that produces H2. This range of αm/αf can render the H2 produced from the photochemical oxidation of CH4 to be enriched in D (with respect to the original CH4) by the factor of 1.2–1.3 as anticipated in the literature.

scholarly journals Bromine Isotope Variations in Magmatic and Hydrothermal Sodalite and Tugtupite and the Estimation of Br Isotope Fractionation between Melt and Sodalite

Minerals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 370
Author(s):  
Hans G. M. Eggenkamp ◽  
Michael A. W. Marks ◽  
Pascale Louvat ◽  
Gregor Markl
Keyword(s):  
Late Stage ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Fractionation Factor ◽  
Data Set ◽  
Geothermal Fluids ◽  
A Value ◽  
Isotope Fractionation Factor ◽  
Very High ◽  
Fractionation Factors

We determined the bromine isotope compositions of magmatic and hydrothermal sodalite (Na8Al6Si6O24Cl2) and tugtupite (Na8Al2Be2Si8O24Cl2) from the Ilímaussaq intrusion in South Greenland, in order to constrain the Br isotope composition of the melt and hydrothermal fluids from which these minerals were formed. Early formed magmatic sodalite has high Br contents (138 ± 10 µg/g, n = 5) and low δ81Br values (+0.23 ± 0.07‰). Late stage hydrothermal sodalite has lower Br contents (53±10 µg/g, n = 5) and higher δ81Br values (+0.36 ± 0.08‰). Tugtupite that forms at even later stages shows the lowest Br contents (26 ± 2 µg/g, n = 2) and the highest δ81Br values (+0.71 ± 0.17‰). One hydrothermal sodalite has a Br concentration of 48 ± 9 µg/g and an exceptionally high δ81Br of 0.82 ± 0.12‰, very similar to the δ81Br of tugtupites. We suggest that this may be a very late stage sodalite that possibly formed under Be deficient conditions. The data set suggests that sodalite crystallises with a negative Br isotope fractionation factor, which means that the sodalite has a more negative δ81Br than the melt, of −0.3 to −0.4‰ from the melt. This leads to a value of +0.5 to +0.6‰ relative to SMOB for the melt from which sodalite crystallises. This value is similar to a recently published δ81Br value of +0.7‰ for very deep geothermal fluids with very high R/Ra He isotope ratios, presumably derived from the mantle. During crystallisation of later stage hydrothermal sodalite and the Be mineral tugtupite, δ81Br of the residual fluids (both melt and hydrothermal fluid) increases as light 79Br crystallises in the sodalite and tugtupite. This results in increasing δ81Br values of later stage minerals that crystallise with comparable fractionation factors from a fluid with increasingly higher δ81Br values.

Hydrogen isotope fractionation between methanol and diphenylphosphine or dimethylphosphine in the gas phase and in aprotic solvents

1996 ◽  
Vol 74 (8) ◽  
pp. 1465-1469
Author(s):  
Andrzej Wawer ◽  
Jerzy Szydtlowski
Keyword(s):  
Interaction Energy ◽  
Gas Phase ◽  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Solvent Polarity ◽  
Exchange Reactions ◽  
Fractionation Factor ◽  
The Given ◽  
Fractionation Factors

D/H fractionation factors between MeOH and Ph2PH in dilute solutions of tetrachloroethylene, benzene, tetrahydrofuran, pyridine, and acetonitrile and T/H fractionation factors between MeOH and Me2PH vapors were measured. The experimental results agree very well with values calculated from the statistical theory of isotope effects formulated by Bigeleisen and Mayer. There are correlations between observed fractionation factors and solvent polarity, and the interaction energy of methanol with the given solvent. Another correlation has been found between enthalpy of the exchange reactions and the interaction energy between methanol and the given solvent. Key words: isotope effects, fractionation factor, diphenylphosphine, methanol.

HTO Diffusion in Oxfordian Limestone and Callovo-Oxfordian Argillite Formations

2004 ◽  
Vol 824 ◽  
Author(s):  
M. Descostes ◽  
V. Blin ◽  
B. Grenut ◽  
P. Meier ◽  
E. Tevissen
Keyword(s):  
Pore Water ◽  
Diffusion Coefficients ◽  
Effective Diffusion ◽  
Effective Diffusion Coefficients ◽  
Rock Laboratory ◽  
Diffusion Technique ◽  
Through Diffusion ◽  
Two Parameters ◽  
Geological Formations

AbstractDiffusion coefficients and accessible porosities for HTO were measured on 30 samples from the Andra Underground Rock Laboratory in Meuse/Haute-Marne (France) using the through diffusion technique. Two distinct geological formations were studied: Oxfordian limestone and Callovo-oxfordian argillite between 166 and 477 m depth. The experiences were carried out with synthetic pore-water from each formation. The measured values of the effective diffusion coefficients (De) are ranging from 2.6× 10-12 to 12.4 × 10-11 m2 s-1 while accessible porosities (ε) are between 2.4 and 24%. Good correlations are found between these two parameters.

scholarly journals Influence of climate change on carbon and oxygen isotope fractionation factors between glucose and α-cellulose of pine wood

2013 ◽  
Vol 40 (2) ◽  
pp. 145-152 ◽  
Author(s):  
Barbara Sensuła ◽  
Anna Pazdur
Keyword(s):  
Climate Change ◽  
Oxygen Isotope ◽  
Isotope Fractionation ◽  
Mean Value ◽  
Fractionation Factor ◽  
Oxygen Isotope Fractionation ◽  
Climate Signal ◽  
Carbon And Oxygen Isotope ◽  
The Relationship ◽  
Fractionation Factors

Abstract We present the first analysis of the influence of climate change on carbon and oxygen isotope fractionation factors for two saccharides (glucose and α-cellulose) of pine wood. The conifers grew in the Niepołomice Forest in Poland and the annual rings covered a time span from 1935 to 2000 AD. Glucose samples from acid hydrolysis of α-cellulose were extracted from annual tree rings. The carbon and oxygen isotope fractionation factors between glucose and α-cellulose were not stable over time. The mean value for the carbon isotope fractionation factors between glucose and α-cellulose was greater than unity. The mean value for the oxygen isotope fractionation factors between glucose and α-cellulose was lower than unity. We established, with respect to climate change, the significance of the interannual and intraannual variation in the carbon and oxygen isotope fractionation factors between both saccharides. We used moving interval correlation results for May of the previous year through September of the current year using a base length of 48 years. The relationship with summer temperature is the main climate signal in the carbon isotope fractionation factor between glucose and α-cellulose. The relationship with autumn sunshine is the main climate signal in the oxygen isotope fractionation factor between glucose and α-cellulose for the tree ring chronology.

scholarly journals Experiments on Cu-isotope fractionation between chlorine-bearing fluid and silicate magma: implications for fluid exsolution and porphyry Cu deposits

2020 ◽  
Vol 7 (8) ◽  
pp. 1319-1330
Author(s):  
Haihao Guo ◽  
Ying Xia ◽  
Ruixia Bai ◽  
Xingchao Zhang ◽  
Fang Huang
Keyword(s):  
Inductively Coupled Plasma ◽  
Hydrothermal Fluid ◽  
Isotope Fractionation ◽  
Aqueous Fluid ◽  
Pressure Vessels ◽  
Experimental Results ◽  
Fractionation Factor ◽  
Cu Isotopes ◽  
Fractionation Factors ◽  
Cu Isotope

Abstract Hydrothermal fluid is essential for transporting metals in the crust and mantle. To explore the potential of Cu isotopes as a tracer of hydrothermal-fluid activity, Cu-isotope fractionation factors between Cl-bearing aqueous fluids and silicate magmas (andesite, dacite, rhyolite dacite, rhyolite and haplogranite) were experimentally calibrated. Fluids containing 1.75–14 wt.% Cl were mixed together with rock powders in Au95Cu5 alloy capsules, which were equilibrated in cold-seal pressure vessels for 5–13 days at 800–850°C and 2 kbar. The elemental and Cu-isotopic compositions of the recovered aqueous fluid and solid phases were analyzed by (LA-) ICP–MS and multi-collector inductively coupled plasma mass spectrometry, respectively. Our experimental results show that the fluid phases are consistently enriched in heavy Cu isotope (65Cu) relative to the coexisting silicates. The Cu-isotope fractionation factor (Δ65CuFLUID-MELT) ranges from 0.08 ± 0.01‰ to 0.69 ± 0.02‰. The experimental results show that the Cu-isotopic fractionation factors between aqueous fluids and silicates strongly depend on the Cu speciation in the fluids (e.g. CuCl(H2O), CuCl2– and CuCl32−) and silicate melts (CuO1/2), suggesting that the exsolved fluids may have higher δ65Cu than the residual magmas. Our results suggest the elevated δ65Cu values in Cu-enriched rocks could be produced by addition of aqueous fluids exsolved from magmas. Together with previous studies on Cu isotopes in the brine and vapor phases of porphyry deposits, our results are helpful for better understanding Cu-mineralization processes.

scholarly journals Isotope Fractionation of Toluene: A Perspective to Characterise MicrobialIn SituDegradation

2002 ◽  
Vol 2 ◽  
pp. 1227-1234 ◽  
Author(s):  
H.H. Richnow ◽  
A. Vieth ◽  
M. Kastner ◽  
M. Gehre ◽  
R.U. Meckenstock
Keyword(s):  
Groundwater Flow ◽  
Carbon Isotope ◽  
Organic Contaminants ◽  
Isotope Fractionation ◽  
Isotope Composition ◽  
Flow Path ◽  
Groundwater Hydrology ◽  
Ground Water Flow ◽  
Fractionation Factor

A concept to assessin situbiodegradation of organic contaminants in aquifers is presented. The alteration of the carbon isotope composition of contaminants along the groundwater flow path indicates microbial degradation processes and can be used as an indicator forin situbiodegradation. The Rayleigh equation was applied to calculate the percentage of thein situbiodegradation (B[%]) using the change in the isotopic composition of contaminants (Rt/R0) along the ground water flow path and a kinetic carbon isotope fractionation factor (αC) derived from defined biodegradation experiments in the laboratory. When the groundwater hydrology is known and a representative source concentration (C0) for a groundwater flow path can be determined, the extent ofin situbiodegradation can be quantified.

scholarly journals Hydrogen isotope fractionation in the photolysis of formaldehyde

2007 ◽  
Vol 7 (4) ◽  
pp. 12715-12750 ◽  
Author(s):  
T. S. Rhee ◽  
C. A. M. Brenninkmeijer ◽  
T. Röckmann
Keyword(s):  
Isotope Fractionation ◽  
Isotopic Ratio ◽  
Isotopic Fractionation ◽  
Photochemical Oxidation ◽  
Atmospheric Conditions ◽  
Isotopic Enrichment ◽  
Fractionation Factor ◽  
Removal Processes ◽  
Molecular Channel ◽  
Fractionation Factors

Abstract. Experiments investigating the isotopic fractionation in the formation of H2 by the photolysis of CH2O under tropospheric conditions are reported and discussed. The deuterium (D) depletion in H2 produced is 500(±20)‰ with respect to the parent CH2O. We also observed that complete photolysis of CH2O under atmospheric conditions produces H2 that has virtually the same isotopic ratio as that of the parent CH2O. These findings imply that there must be a very strong concomitant isotopic enrichment in the radical channel (CH2O + hν → CHO + H) as compared to the molecular channel (CH2O + hν → H2 + CO) of the photolysis of CH2O in order to balance the relatively small isotopic fractionation in the competing reaction of CH2O with OH. Using a 1-box photochemistry model we calculated the isotopic fractionation factor for the radical channel to be 0.22(±0.08), which is equivalent to a 780(±80)‰ enrichment in D of the remaining CH2O. When CH2O is in photochemical steady state, the isotopic ratio of the H2 produced is determined not only by the isotopic fractionation occurring during the photolytical production of H2 (αm) but also by overall fractionation for the removal processes of CH2O (αf), and is represented by the ratio of αm/αf. Applying the isotopic fractionation factors relevant to CH2O photolysis obtained in the present study to the troposphere, the ratio of αm/αf varies from ~0.8 to ~1.2 depending on the fraction of CH2O that reacts with OH and that produces H2. This range of αm/αf can render the H2 produced from the photochemical oxidation of CH4 to be enriched in D (with respect to the original CH4) by the factor of 1.2–1.3 as anticipated in the literature.

Calculations of the Oxygen Isotope Fractionation between Hydration Water of Cations and Free Water

1974 ◽  
Vol 29 (11) ◽  
pp. 1608-1613 ◽  
Author(s):  
P. Bopp ◽  
K. Heinzinger ◽  
P. C. Vogel
Keyword(s):  
Water Molecule ◽  
Oxygen Isotope ◽  
Gas Phase ◽  
Isotope Fractionation ◽  
Pure Water ◽  
Free Water ◽  
Oxygen Isotope Fractionation ◽  
Free Water Molecule ◽  
Separation Factors ◽  
Fractionation Factors

The oxygen isotope fractionation factors between the hydration complex of the alkali ions in the gas phase and a free water molecule have been computed on the basis of the energy surfaces calculated by Kistenmacher, Popkie and Clementi for a water molecule in the field of an alkali ion. For comparison with recently measured oxygen isotope fractionation factors in aqueous alkali halide solutions, the gas phase values are multiplied with the corresponding separation factors between water vapor and liquid water thus relating the hydration complex in the gas phase with pure water. Qualitative agreement between computed and observed fractionation factors has been found for H2O and D2O even neglecting the isotope effect connected with the transfer of the hydration complex from the gas phase to the solution. This transfer effect is estimated for H2O by a quantitative comparison of computed and observed oxygen isotope fractionation factors.

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