scholarly journals Sulfur isotope fractionation during heterogeneous oxidation of SO<sub>2</sub> on mineral dust

2012 ◽  
Vol 12 (11) ◽  
pp. 4867-4884 ◽  
Author(s):  
E. Harris ◽  
B. Sinha ◽  
S. Foley ◽  
J. N. Crowley ◽  
S. Borrmann ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Clay Minerals ◽  
Aqueous Phase ◽  
Isotope Fractionation ◽  
Mineral Dust ◽  
Surface Oxidation ◽  
Sulfur Cycle ◽  
Fractionation Factor ◽  
Sulfate Production ◽  
Aqueous Oxidation

Abstract. Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH) had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals resulted in a very distinct fractionation factor of α34 = 1.085±0.013. The fractionation factors measured in this study will be particularly useful in combination with field and modelling studies to understand the role of surface oxidation on clay minerals and aqueous oxidation by mineral dust and its leachate in global and regional sulfur cycles.

scholarly journals Sulfur isotope fractionation during heterogeneous oxidation of SO<sub>2</sub> on mineral dust

2012 ◽  
Vol 12 (1) ◽  
pp. 2303-2353 ◽  
Author(s):  
E. Harris ◽  
B. Sinha ◽  
S. Foley ◽  
J. N. Crowley ◽  
S. Borrmann ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Clay Minerals ◽  
Aqueous Phase ◽  
Isotope Fractionation ◽  
Mineral Dust ◽  
Surface Oxidation ◽  
Sulfur Cycle ◽  
Fractionation Factor ◽  
Sulfate Production ◽  
Aqueous Oxidation

Abstract. Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~ 60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917 ± 0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH) had an overall fractionation factor of αhet = 1.0096 ± 0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~ 40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012 ± 0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals resulted in a very distinct fractionation factor of α34 = 1.085 ± 0.013. The fractionation factors measured in this study will be particularly useful in combination with field and modelling studies to understand the role of surface oxidation on clay minerals and aqueous oxidation by mineral dust and its leachate in global and regional sulfur cycles.

scholarly journals Aqueous phase oxidation of bisulfite influenced by nitrate photolysis

2020 ◽  
Author(s):  
Lu Chen ◽  
Lingdong Kong ◽  
Songying Tong ◽  
Kejing Yang ◽  
Shengyan Jin ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Cloud Droplets ◽  
Radical Chain ◽  
Sulfate Production ◽  
Halogen Chemistry ◽  
Phase Oxidation ◽  
Aqueous Oxidation ◽  
Insight Into ◽  
Solid Aerosol

Abstract. Nitrate aerosol is ubiquitous in the atmosphere, and it can exit in both solid aerosol particles and fog and cloud droplets. Nitrate in the aqueous and particulate phase can undergo photolysis to produce oxidizing active radicals, which will inevitably affect various atmospheric chemical processes. However, the role of nitrate aerosols in these atmospheric photochemical processes remains unclear. In this study, the effects of nitrate photolysis on the aqueous phase oxidation of bisulfite under different conditions were investigated. Results show that nitrate photolysis can significantly promote the oxidation of bisulfite to sulfate. It is found that pH plays a significant role in the reaction, and ammonium sulfate has significant impacts on regulating the pH of solution and the enhancement of sulfate production. We also found an apparent synergism among halogen chemistry, nitrate and its photochemistry and S(IV) aqueous oxidation, especially the oxidation of halide ions by the nitrate photolysis and by the intermediate peroxymonosulfuric acid (HSO5−) produced by the free radical chain oxidation of S(IV) in acidic solution leads to the coupling of the redox cycle of halogen with the oxidation of bisulfite, which promotes the continuous aqueous oxidation of bisulfite and the formation of sulfate. In addition, it is also found that O2 is of great significance on nitrate photolysis for the conversion of HSO3−, and H2O2 generation during the nitrate photolysis is verified. These results provide a new insight into the heterogeneous aqueous phase oxidation pathways and mechanisms of SO2 in cloud and fog droplets and haze particles.

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 Laboratory study on heterogeneous decomposition of methyl chloroform on various standard aluminosilica clay minerals as a potential tropospheric sink

2003 ◽  
Vol 3 (2) ◽  
pp. 1843-1891
Author(s):  
S. Kutsuna ◽  
L. Chen ◽  
O. Ohno ◽  
N. Negishi ◽  
K. Takeuchi ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Clay Minerals ◽  
Reaction Rate ◽  
Ground Surface ◽  
Reaction Rate Constant ◽  
Pseudo First Order Reaction ◽  
Dry Air ◽  
Reaction Rate Constants ◽  
Methyl Chloroform ◽  
Bet Equation

Abstract. Methyl chloroform (1,1,1-trichloroethane, CH3CCl3) was found to decompose heterogeneously on seven types of standard clay minerals (23 materials) in dry air at 313 K in the laboratory. All reactions proceeded through the elimination of HCl; CH3CCl3 was converted quantitatively to CH2=CCl2. The activities of the clay minerals were compared via their pseudo-first-order reaction rate constants (k1). A positive correlation was observed between the k1 value and the specific surface area (S) of clay minerals, where the S value was determined by means of the general Brunauer-Emmett-Teller (BET) equation. The k1 value was anti-correlated with the value of n, a parameter of the general BET equation, and correlated with the water content that can be removed easily from the clay minerals. The reaction required no special pretreatment of clay minerals, such as heating at high temperatures; hence, the reaction can be expected to occur in the environment. Photoillumination by wavelengths present in the troposphere did not accelerate the decomposition of CH3CCl3, but it induced heterogeneous photodecomposition of CH2=CCl2. The temperature dependence of k1, the adsorption constants of CH3CC3 and CH2=CCl2, and a surface reaction rate constant were determined for an illite sample. The k1 value increased with increasing temperature. The amount of CH3CCl3 adsorbed on the illite during the reaction was proportional to the partial pressure of CH3CCl3. The reaction was sensitive to relative humidity and the k1 value decreased with increasing relative humidity. However, the reaction was found to proceed at a relative humidity of 22% at 313 K, although the k1 value was about one-twentieth of the value in dry air. The conditions required for the reaction may be present in major desert regions of the world. A simple estimation indicates that the possible heterogeneous decomposition of CH3CC3 on the ground surface in arid regions is worth taking into consideration when inferring the tropospheric lifetime of CH3CC3 and global OH concentration from the global budget concentration of CH3CCl3.

An occurrence of polymorphic halloysite in granite saprolite of the Bayerischer Wald, Germany

Clay Minerals ◽  
1978 ◽  
Vol 13 (1) ◽  
pp. 67-77 ◽  
Author(s):  
B.-M. Wilke ◽  
U. Schwertmann ◽  
E. Murad
Keyword(s):  
Trace Elements ◽  
Clay Minerals ◽  
Iron Oxides ◽  
Aqueous Phase ◽  
Mixed Layer ◽  
Thin Plates ◽  
Low Crystallinity

AbstractXRD, DTA and IR patterns showed clay veins filling fissures in a granite of the Bayerischer Wald (eastern Bavaria) to consist mainly of hydrated halloysite of low crystallinity with traces of gibbsite, 2:1 (mixed layer) clay minerals and iron oxides. The halloysite forms thin plates which exhibit varying degrees and types of enrolment, resulting in platy, tubular and spheroidal crystals within the same sample. Concentrations of the trace elements Rb, Sr, Ba, Zr, Y, Ce, Pb, Zn and Cu indicate halloysite formation to have taken place via an aqueous phase under the influence of vadose waters circulating in fissures.

scholarly journals Quantifying molecular oxygen isotope variations during a Heinrich stadial

2015 ◽  
Vol 11 (11) ◽  
pp. 1527-1551 ◽  
Author(s):  
C. Reutenauer ◽  
A. Landais ◽  
T. Blunier ◽  
C. Bréant ◽  
M. Kageyama ◽  
...  
Keyword(s):  
Isotope Fractionation ◽  
Water Cycle ◽  
Atmospheric Oxygen ◽  
Dominant Role ◽  
Climatic Conditions ◽  
Fractionation Factor ◽  
Last Glacial Period ◽  
Main Driver ◽  
The Last Glacial

Abstract. δ18O of atmospheric oxygen (δ18Oatm) undergoes millennial-scale variations during the last glacial period, and systematically increases during Heinrich stadials (HSs). Changes in δ18Oatm combine variations in biospheric and water cycle processes. The identification of the main driver of the millennial variability in δ18Oatm is thus not straightforward. Here, we quantify the response of δ18Oatm to such millennial events using a freshwater hosing simulation performed under glacial boundary conditions. Our global approach takes into account the latest estimates of isotope fractionation factor for respiratory and photosynthetic processes and make use of atmospheric water isotope and vegetation changes. Our modeling approach allows to reproduce the main observed features of a HS in terms of climatic conditions, vegetation distribution and δ18O of precipitation. We use it to decipher the relative importance of the different processes behind the observed changes in δ18Oatm. The results highlight the dominant role of hydrology on δ18Oatm and confirm that δ18Oatm can be seen as a global integrator of hydrological changes over vegetated areas.

scholarly journals Synergistic effect of water-soluble species and relative humidity on morphological changes in aerosol particles in the Beijing megacity during severe pollution episodes

2019 ◽  
Vol 19 (1) ◽  
pp. 219-232 ◽  
Author(s):  
Xiaole Pan ◽  
Baozhu Ge ◽  
Zhe Wang ◽  
Yu Tian ◽  
Hang Liu ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Synergistic Effect ◽  
Mineral Dust ◽  
Water Soluble ◽  
Dust Particles ◽  
Urban Site ◽  
Chemical Compositions ◽  
Aerodynamic Diameter ◽  
Soluble Species ◽  
Pollution Episodes

Abstract. Depolarization ratio (δ) of backscattered light is an applicable parameter for distinguishing the sphericity of particles in real time, which has been widely adopted by ground-based lidar observation systems. In this study, δ values of particles and chemical compositions in both PM2.5 (aerodynamic diameter less than 2.5 µm) and PM10 (aerodynamic diameter less than 10 µm) were concurrently measured on the basis of a bench-top optical particle counter with a polarization detection module (POPC) and a continuous dichotomous aerosol chemical speciation analyzer (ACSA-14) from November 2016 to February 2017 at an urban site in Beijing megacity. In general, measured δ values depended on both size and sphericity of the particles. During the observation period, mass concentrations of NO3- in PM2.5 (fNO3) were about an order of magnitude higher than that in PM2.5−10 (cNO3) with a mean fNO3∕cNO3 ratio of 14±10. A relatively low fNO3∕cNO3 ratio (∼5) was also observed under higher relative humidity conditions, mostly due to heterogeneous processes and particles in the coarse mode. We found that δ values of ambient particles in both PM2.5 and PM2.5−10 obviously decreased as mass concentration of water-soluble species increased at unfavorable meteorological conditions. This indicated that the morphology of particles was changed as a result of water-absorbing processes. The particles with optical size (Dp) of Dp = 5 µm were used to represent mineral dust particles, and its δ values (δDp=5) decreased by 50 % as the mass fraction of cNO3 increased from 2 % to 8 % and ambient relative humidity increased up to 80 %, suggesting that mineral dust particles were likely to be spherical during humid pollution episodes. During the observation, relative humidity inside the POPC measuring chamber was stable at 34±2 %, lower than the ambient condition. Its influence on the morphology was estimated to be limited and did not change our major conclusion. This study highlights the evident alteration of non-sphericity of mineral dust particles during their transport owing to a synergistic effect of both pollutant coatings and hygroscopic processes, which plays an important role in the evaluation of its environmental effect.

scholarly journals Nitrogen cycling in shallow low-oxygen coastal waters off Peru from nitrite and nitrate nitrogen and oxygen isotopes

2016 ◽  
Vol 13 (5) ◽  
pp. 1453-1468 ◽  
Author(s):  
Happy Hu ◽  
Annie Bourbonnais ◽  
Jennifer Larkum ◽  
Hermann W. Bange ◽  
Mark A. Altabet
Keyword(s):  
Isotope Fractionation ◽  
Coastal Upwelling ◽  
Isotope Effects ◽  
Low Oxygen ◽  
N Loss ◽  
Fractionation Factor ◽  
High Productivity ◽  
O Isotopes ◽  
Subsequent Loss ◽  
Matter Flux

Abstract. O2 deficient zones (ODZs) of the world's oceans are important locations for microbial dissimilatory nitrate (NO3−) reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. ODZs are generally coupled to regions of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N and O isotope ratios can be used as natural tracers of ODZ N-cycling because of distinct kinetic isotope effects associated with microbially mediated N-cycle transformations. Here we present NO3− and nitrite (NO2−) stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface oxygen was generally depleted below about 30 m depth with concentrations less than 10 µM, while NO2− concentrations were high, ranging from 6 to 10 µM, and NO3− was in places strongly depleted to near 0 µM. We observed for the first time a positive linear relationship between NO2−δ15N and δ18O at our coastal stations, analogous to that of NO3− N and O isotopes during NO3− uptake and dissimilatory reduction. This relationship is likely the result of rapid NO2− turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2− facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ε) for N-loss as calculated from the δ15N of NO3−, dissolved inorganic N, or biogenic N2, values for ε are generally much lower than previously reported, reaching as low as 6.5 ‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation.

scholarly journals Technical note: Lithium isotopes in dolostone as a palaeo-environmental proxy – an experimental approach

2019 ◽  
Vol 15 (2) ◽  
pp. 635-646 ◽  
Author(s):  
Holly L. Taylor ◽  
Isaac J. Kell Duivestein ◽  
Juraj Farkas ◽  
Martin Dietzel ◽  
Anthony Dosseto
Keyword(s):  
Isotope Fractionation ◽  
Isotope Composition ◽  
Relative Proportion ◽  
Significant Proportion ◽  
Technical Note ◽  
Fractionation Factor ◽  
Calcium Carbonates ◽  
Marine Carbonates ◽  
Li Isotope ◽  
Environmental Proxy

Abstract. Lithium (Li) isotopes in marine carbonates have considerable potential as a proxy to constrain past changes in silicate weathering fluxes and improve our understanding of Earth's climate. To date the majority of Li isotope studies on marine carbonates have focussed on calcium carbonates. The determination of the Li isotope fractionation between dolomite and a dolomitizing fluid would allow us to extend investigations to deep times (i.e. Precambrian) when dolostones were the most abundant marine carbonate archives. Dolostones often contain a significant proportion of detrital silicate material, which dominates the Li budget; thus, pretreatment needs to be designed so that only the isotope composition of the carbonate-associated Li is measured. This study aims to serve two main goals: (1) to determine the Li isotope fractionation between Ca–Mg carbonates and solution, and (2) to develop a method for leaching the carbonate-associated Li out of dolostone while not affecting the Li contained within the detrital portion of the rock. We synthesized Ca–Mg carbonates at high temperatures (150 to 220 ∘C) and measured the Li isotope composition (δ7Li) of the precipitated solids and their respective reactive solutions. The relationship of the Li isotope fractionation factor with temperature was obtained: 103ln⁡αprec-sol=-(2.56±0.27)106(1)/T2+(5.8±1.3) Competitive nucleation and growth between dolomite and magnesite were observed during the experiments; however, there was no notable effect of their relative proportion on the apparent Li isotope fractionation. We found that Li isotope fractionation between the precipitated solid and solution is higher for Ca–Mg carbonates than for Ca carbonates. If the temperature of a precipitating solution is known or can be estimated independently, the above equation could be used in conjunction with the Li isotope composition of dolostones to derive the composition of the solution and hence make inferences about the past Li cycle. In addition, we also conducted leaching experiments on a Neoproterozoic dolostone and a Holocene coral. Results show that leaching with 0.05 M hydrochloric acid (HCl) or 0.5 % acetic acid (HAc) at room temperature for 60 min releases Li from the carbonate fraction without a significant contribution of Li from the siliciclastic detrital component. These experimental and analytical developments provide a basis for the use of Li isotopes in dolostones as a palaeo-environmental proxy, which will contribute to further advance our understanding of the evolution of Earth's surface environments.

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