scholarly journals Boron isotope fractionation during brucite deposition from artificial seawater

2011 ◽  
Vol 7 (3) ◽  
pp. 693-706 ◽  
Author(s):  
J. Xiao ◽  
Y. K. Xiao ◽  
C. Q. Liu ◽  
Z. D. Jin

Abstract. Experiments involving boron incorporation into brucite (Mg(OH)2) from magnesium-free artificial seawater with pH values ranging from 9.5 to 13.0 were carried out to better understand the incorporation behavior of boron into brucite and the influence of it on Mg/Ca-SST proxy and δ11B-pH proxy. The results show that both the concentration of boron in deposited brucite ([B]d) and its boron partition coefficient (Kd) between deposited brucite and final seawater are controlled by the pH of the solution. The incorporation capacity of boron into brucite is almost the same as that into corals, but much stronger than that into oxides and clay minerals. The isotopic compositions of boron in deposited brucite (δ11Bd) are higher than those in the associated artificial seawater (δ11Bisw) with fractionation factors ranging between 1.0177 and 1.0569, resulting from the preferential incorporation of B(OH)3 into brucite. Both boron adsorptions onto brucite and the precipitation reaction of H3BO3 with brucite exist during deposition of brucite from artificial seawater. The simultaneous occurrence of both processes determines the boron concentration and isotopic fractionation of brucite. The isotopic fractionation behaviors and mechanisms of boron incorporated into brucite are different from those into corals. The existence of brucite in corals can affect the δ11B and Mg/Ca in corals and influences the Mg/Ca-SST proxy and δ11B-pH proxy negatively. The relationship between δ11B and Mg/Ca in corals can be used to judge the existence of brucite in corals, which should provide a reliable method for better use of δ11B and Mg/Ca in corals to reconstruct paleo-marine environment.

2011 ◽  
Vol 7 (2) ◽  
pp. 887-920 ◽  
Author(s):  
J. Xiao ◽  
Y. K. Xiao ◽  
C. Q. Liu ◽  
Z. D. Jin

Abstract. Experiments involving boron incorporation into brucite (Mg(OH)2) from magnesium-free artificial seawater with pH values ranging from 9.5 to 13.0 were carried out to better understand the incorporation behavior of boron into brucite. The results show that both concentration of boron in deposited brucite ([B]d) and its boron partition coefficient (Kd) between deposited brucite and final seawater are controlled by pH of the solution. The incorporation capacity of boron into brucite is much stronger than that into oxides and clay minerals. The isotopic compositions of boron in deposited brucite (δ11Bd) are higher than those in the associated artificial seawater (δ11Bisw) with fractionation factors ranging between 1.0177 and 1.0569, resulting from the preferential incorporation of B(OH)3 into brucite. Both boron adsorptions onto brucite and precipitation reaction of H3BO3 with brucite exist during deposition of brucite from artificial seawater. The simultaneous occurrence of both processes determines the boron concentration and isotopic fractionation of brucite. The isotopic fractionation behaviors and mechanisms of boron incorporated into brucite are different from those into carbonates. Furthermore, the isotopic compositions of boron in modern corals might be affected by the existence of brucite in madrepore and the preferential incorporation of B(OH)3 into brucite. An exploratory study for the influence of brucite on the boron isotopic composition in modern corals is justifiable.


2008 ◽  
Vol 8 (5) ◽  
pp. 1353-1366 ◽  
Author(s):  
T. S. Rhee ◽  
C. A. M. Brenninkmeijer ◽  
T. Röckmann

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.


2013 ◽  
Vol 40 (2) ◽  
pp. 145-152 ◽  
Author(s):  
Barbara Sensuła ◽  
Anna Pazdur

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.


2007 ◽  
Vol 7 (4) ◽  
pp. 12715-12750 ◽  
Author(s):  
T. S. Rhee ◽  
C. A. M. Brenninkmeijer ◽  
T. Röckmann

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.


Author(s):  
Andrew Clarke

Temperature is that property of a body which determines whether it gains or loses energy in a particular environment. In classical thermodynamics temperature is defined by the relationship between energy and entropy. Temperature can be defined only for a body that is in thermodynamic and thermal equilibrium; whilst organisms do not conform to these criteria, the errors in assuming that they do are generally small. The Celsius and Fahrenheit temperature scales are arbitrary because they require two fixed points, one to define the zero and the other to set the scale. The thermodynamic (absolute) scale of temperature has a natural zero (absolute zero) and is defined by the triple point of water. Its unit of temperature is the Kelvin. The Celsius scale is convenient for much ecological and physiological work, but where temperature is included in statistical or deterministic models, only thermodynamic temperature should be used. Past temperatures can only be reconstructed with the use of proxies, the most important of which are based on isotope fractionation.


1979 ◽  
Vol 182 (2) ◽  
pp. 455-464 ◽  
Author(s):  
E J Harris ◽  
M Al-Shaikhaly ◽  
H Baum

Respiring rat heart mitochondria were loaded with Ca2+ and then treated with Ruthenium Red. The factors affecting the subsequent Ca2+-efflux were studied. Addition of rotenone or antimycin led to a decline of efflux except at pH values above 7.2, provided the load was less than about 80 nmol per mg of protein. Oligomycin reversed the effect of the respiratory inhibitors. Independently of respiration, efflux was stimulated by the uncoupler trifluoromethyltetrachlorbenzimadazole, by mersalyl and by thyroid hormones. The stimulated efflux could be diminished by ADP, with Mg2+ as cofactor if efflux was rapid. With respiration in progress, efflux could be stimulated by N-ethylmaleimide and 5,5′-dithiobis-(2-nitrobenzoate). The effects of mersalyl and of thyroid hormones could be diminished with dithiothreitol. In the absence of stimulating agents, the Ca2+ efflux was proportional to the load up to some critical amount, this critical amount was decreased by the agents. Thyroxine and mersalyl caused not only loss of Ca2+, but also simultaneous, but not necessarily proportional, loss of internal adenine nucleotides. Both efflux rates were kept at a low value by bongkrekic acid added before the stimulating agent. It is concluded that Ca2+ efflux is a measure of a permeability controlled by the binding of ADP (an Mg2+) to the inner membrane, and that this in turn depends on the maintenance of certain thiol gropus in a reduced form by a reaction that uses NADH and ATP and the energy-linked transhydrogenase.


2020 ◽  
Vol 117 (35) ◽  
pp. 21125-21131 ◽  
Author(s):  
Jing-Liang Guo ◽  
Zaicong Wang ◽  
Wen Zhang ◽  
Frédéric Moynier ◽  
Dandan Cui ◽  
...  

Zircons widely occur in magmatic rocks and often display internal zonation finely recording the magmatic history. Here, we presented in situ high-precision (2SD <0.15‰ for δ94Zr) and high–spatial-resolution (20 µm) stable Zr isotope compositions of magmatic zircons in a suite of calc-alkaline plutonic rocks from the juvenile part of the Gangdese arc, southern Tibet. These zircon grains are internally zoned with Zr isotopically light cores and increasingly heavier rims. Our data suggest the preferential incorporation of lighter Zr isotopes in zircon from the melt, which would drive the residual melt to heavier values. The Rayleigh distillation model can well explain the observed internal zoning in single zircon grains, and the best-fit models gave average zircon–melt fractionation factors for each sample ranging from 0.99955 to 0.99988. The average fractionation factors are positively correlated with the median Ti-in-zircon temperatures, indicating a strong temperature dependence of Zr isotopic fractionation. The results demonstrate that in situ Zr isotope analyses would be another powerful contribution to the geochemical toolbox related to zircon. The findings of this study solve the fundamental issue on how zircon fractionates Zr isotopes in calc-alkaline magmas, the major type of magmas that led to forming continental crust over time. The results also show the great potential of stable Zr isotopes in tracing magmatic thermal and chemical evolution and thus possibly continental crustal differentiation.


Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 208
Author(s):  
Takuma Hasegawa ◽  
Kotaro Nakata ◽  
Rhys Gwynne

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.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Elaheh Lotfi-Kalahroodi ◽  
Anne-Catherine Pierson-Wickmann ◽  
Olivier Rouxel ◽  
Rémi Marsac ◽  
Martine Bouhnik-Le Coz ◽  
...  

AbstractAlthough redox reactions are recognized to fractionate iron (Fe) isotopes, the dominant mechanisms controlling the Fe isotope fractionation and notably the role of organic matter (OM) are still debated. Here, we demonstrate how binding to organic ligands governs Fe isotope fractionation beyond that arising from redox reactions. The reductive biodissolution of soil Fe(III) enriched the solution in light Fe isotopes, whereas, with the extended reduction, the preferential binding of heavy Fe isotopes to large biological organic ligands enriched the solution in heavy Fe isotopes. Under oxic conditions, the aggregation/sedimentation of Fe(III) nano-oxides with OM resulted in an initial enrichment of the solution in light Fe isotopes. However, heavy Fe isotopes progressively dominate the solution composition in response to their binding with large biologically-derived organic ligands. Confronted with field data, these results demonstrate that Fe isotope systematics in wetlands are controlled by the OM flux, masking Fe isotope fractionation arising from redox reactions. This work sheds light on an overseen aspect of Fe isotopic fractionation and calls for a reevaluation of the parameters controlling the Fe isotopes fractionation to clarify the interpretation of the Fe isotopic signature.


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