scholarly journals Atmospheric Effects on the Isotopic Composition of Ozone

Atmosphere ◽  
2021 ◽  
Vol 12 (12) ◽  
pp. 1673
Author(s):  
Mao-Chang Liang ◽  
Yi-Chun Chen ◽  
Yi-Qin Gao ◽  
Xi Zhang ◽  
Yuk L. Yung
Keyword(s):  
Isotopic Composition ◽  
Isotope Composition ◽  
Laboratory Data ◽  
Isotopic Fractionation ◽  
Isotopic Signature ◽  
Atmospheric Effects ◽  
Ozone Sensitivity ◽  
Sensitivity Studies ◽  
Oxygen Isotopic ◽  
The Difference

The delta values of the isotope composition of atmospheric ozone is ~100‰ (referenced to atmospheric O2). Previous photochemical models, which considered the isotope fractionation processes from both formation and photolysis of ozone, predicted δ49O3 and δ50O3 values, in δ49O3 versus δ50O3 space, that are >10‰ larger than the measurements. We propose that the difference between the model and observations could be explained either by the temperature variation, Chappuis band photolysis, or a combination of the two and examine them. The isotopic fractionation associated with ozone formation increases with temperature. Our model shows that a hypothetical reduction of ~20 K in the nominal temperature profile could reproduce the observations. However, this hypothesis is not consistent with temperatures obtained by in situ measurements and NCEP Reanalysis. Photolysis of O3 in the Chappuis band causes O3 to be isotopically depleted, which is supported by laboratory measurements for 18O18O18O but not by recent new laboratory data made at several wavelengths for 49O3 and 50O3. Cloud reflection can significantly enhance the photolysis rate and affect the spectral distribution of photons, which could influence the isotopic composition of ozone. Sensitivity studies that modify the isotopic composition of ozone by the above two mechanisms are presented. We conclude isotopic fractionation occurring in photolysis in the Chappuis band remains the most plausible solution to the model-observation discrepancy. Implications of our results for using the oxygen isotopic signature for constraining atmospheric chemical processes related to ozone, such as CO2, nitrate, and the hydroxyl radical, are discussed.

scholarly journals Stratospheric carbon isotope fractionation and tropospheric histories of CFC-11, CFC-12 and CFC-113 isotopologues

2020 ◽  
Author(s):  
Max Thomas ◽  
Johannes C. Laube ◽  
Jan Kaiser ◽  
Samuel Allin ◽  
Patricia Martinerie ◽  
...  
Keyword(s):  
Isotopic Composition ◽  
Carbon Isotope ◽  
Ozone Depletion ◽  
Isotope Composition ◽  
Stratospheric Ozone ◽  
Isotopic Fractionation ◽  
Base Case ◽  
Model Base ◽  
The Difference ◽  
First Time

Abstract. We present novel measurements of the carbon isotope composition of CFC-11 (CCl3F), CFC-12 (CCl2F2), and CFC-113 (CF2ClCFCl2), three atmospheric trace gases that are important for both stratospheric ozone depletion and global warming. These measurements were carried out on air samples collected in the stratosphere – the main sink region for these gases – and on air extracted from deep polar firn snow. We quantify, for the first time, the apparent isotopic fractionation, εapp(13C), for these gases as they are destroyed in the high- and mid-latitude stratosphere: εapp(CFC-12, high-lat) = (−20.2 ± 4.4) ‰ and εapp(CFC-113, high-lat) = (−9.4 ± 4.4) ‰, εapp(CFC-12, mid-lat) = (−30.3 ± 10.7) ‰, and εapp(CFC-113, mid-lat) = (−34.4 ± 9.8) ‰. Our CFC-11 measurements were not sufficient to calculate εapp(CFC-11) so we instead used previously reported photolytic fractionation for CFC-11 and CFC-12 to scale our εapp(CFC-12), resulting in εapp(CFC-11, high-lat) = (−7.8 ± 1.7) ‰ and εapp(CFC-11, mid-lat) = (−11.7 ± 4.2) ‰. Measurements of firn air were used to construct histories of the tropospheric isotopic composition, δT(13C), for CFC-11 (1950s to 2009), CFC-12 (1950s to 2009), and CFC-113 (1970s to 2009) – with δT(13C) increasing for each gas. We used εapp(high-lat), which were derived from more data, and a constant isotopic composition of emissions, δE(13C), to model δT(13C, CFC-11), δT(13C, CFC-12), and δT(13C, CFC-113). For CFC-11 and CFC-12, modelled δT(13C) was consistent with measured δT(13C) for the entire period covered by the measurements, suggesting no dramatic change in δE(13C, CFC-11) or δE(13C, CFC-12) has occurred since the 1950s. For CFC-113, our modelled δT(13C, CFC-113) did not agree with our measurements earlier than 1980. While this discrepancy may be indicative of a change in δE(13C, CFC-113), it is premature to assign one. Our modelling predicts increasing δT(13C, CFC-11), δT(13C, CFC-12), and δT(13C, CFC-113) into the future. We investigated the effect of recently reported new CFC-11 emissions on background δT(13C, CFC-11) by fixing model emissions after 2012, and comparing δT(13C, CFC-11) in this scenario to the model base case. The difference in δT(13C, CFC-11) between these scenarios was 1.4 ‰ in 2050. This difference is smaller than our model uncertainty envelope and would therefore require improved modelling and measurement precision, as well as better quantified isotopic source compositions, to detect.

Changes of Ionic and Oxygen Isotopic Composition of the Snowpack at the Glacier Austre Okstindbreen, Norway, 1995

1998 ◽  
Vol 29 (1) ◽  
pp. 1-20 ◽  
Author(s):  
Peter Raben ◽  
Wilfred H. Theakstone
Keyword(s):  
Isotopic Composition ◽  
Sea Level ◽  
Oxygen Isotopes ◽  
Oxygen Isotopic Composition ◽  
Isotopic Ratios ◽  
Vertical Variations ◽  
Oxygen Isotopic ◽  
The Difference ◽  
Liquid Precipitation ◽  
Different Altitudes

Marked vertical variations of ions and oxygen isotopes were present in the snowpack at the glacier Austre Okstindbreen during the pre-melting phase in 1995 at sites between 825 m and 1,470 m above sea level. As the first meltwater percolated from the top of the pack, ions were moved to a greater depth, but the isotopic composition remained relatively unchanged. Ions continued to move downwards through the pack during the melting phase, even when there was little surface melting and no addition of liquid precipitation. The at-a-depth correlation between ionic concentrations and isotopic ratios, strong in the pre-melting phase, weakened during melting. In August, concentrations of Na+ and Mg2+ ions in the residual pack were low and vertical variations were slight; 18O enrichment had occurred. The difference of the time at which melting of the snowpack starts at different altitudes influences the input of ions and isotopes to the underlying glacier.

scholarly journals <sup>2</sup>H and <sup>18</sup>O depletion of water close to organic surfaces

2016 ◽  
Vol 13 (10) ◽  
pp. 3175-3186 ◽  
Author(s):  
Guo Chen ◽  
Karl Auerswald ◽  
Hans Schnyder
Keyword(s):  
Isotopic Composition ◽  
Soil Water ◽  
Filter Paper ◽  
Surface Effect ◽  
Isotope Composition ◽  
Isotopic Fractionation ◽  
Adsorbed Water ◽  
Organic Soil ◽  
Surface Areas ◽  
Isotope Composition Of Water

Abstract. Hydrophilic surfaces influence the structure of water close to them and may thus affect the isotope composition of water. Such an effect should be relevant and detectable for materials with large surface areas and low water contents. The relationship between the volumetric solid : water ratio and the isotopic fractionation between adsorbed water and unconfined water was investigated for the materials silage, hay, organic soil (litter), filter paper, cotton, casein and flour. Each of these materials was equilibrated via the gas phase with unconfined water of known isotopic composition to quantify the isotopic difference between adsorbed water and unconfined water. Across all materials, isotopic fractionation was significant (p<0.05) and negative (on average −0.91 ± 0.22 ‰ for 18∕16O and −20.6 ± 2.4 ‰ for 2∕1H at an average solid : water ratio of 0.9). The observed isotopic fractionation was not caused by solutes, volatiles or old water because the fractionation did not disappear for washed or oven-dried silage, the isotopic fractionation was also found in filter paper and cotton, and the fractionation was independent of the isotopic composition of the unconfined water. Isotopic fractionation became linearly more negative with increasing volumetric solid : water ratio and even exceeded −4 ‰ for 18∕16O and −44 ‰ for 2∕1H. This fractionation behaviour could be modelled by assuming two water layers: a thin layer that is in direct contact and influenced by the surface of the solid and a second layer of varying thickness depending on the total moisture content that is in equilibrium with the surrounding vapour. When we applied the model to soil water under grassland, the soil water extracted from 7 and 20 cm depth was significantly closer to local meteoric water than without correction for the surface effect. This study has major implications for the interpretation of the isotopic composition of water extracted from organic matter, especially when the volumetric solid : water ratio is larger than 0.5 or for processes occurring at the solid–water interface.

scholarly journals Technical Note: Silica stable isotopes and silicification in a carnivorous sponge \\textit{Asbestopluma} sp.

2014 ◽  
Vol 11 (12) ◽  
pp. 16573-16597
Author(s):  
K. R. Hendry ◽  
G. E. A. Swann ◽  
M. J. Leng ◽  
H. J. Sloane ◽  
C. Goodwin ◽  
...  
Keyword(s):  
Isotopic Composition ◽  
Oxygen Isotope ◽  
Isotope Composition ◽  
Isotopic Signature ◽  
The Body ◽  
Oxygen Isotope Composition ◽  
Silicon Isotope ◽  
Deep Seawater ◽  
Differential Distribution ◽  
Sponge Spicule

Abstract. The stable isotope composition of benthic sponge spicule silica is a potential source of palaeoceanographic information about past deep seawater chemistry. The silicon isotopic composition of spicules has been shown to relate to the silicic acid concentration of ambient water, although existing calibrations do exhibit a degree of scatter in the relationship. Less is known about how the oxygen isotope composition of sponge spicule silica relates to environmental conditions during growth. Here, we investigate the biological vital effects on silica silicon and oxygen isotope composition in a carnivorous sponge, Asbestopluma sp., from the Southern Ocean. We find significant variations in silicon and oxygen isotopic composition within the specimen that appear related to unusual spicule silicification. The largest variation in both isotope systems was associated to the differential distribution of an unconventional, hypersilicified spicule type (desma) along the sponge body. The absence of an internal canal in the desmas suggests an unconventional silicification pattern leading to an unusually heavy isotopic signature. Additional internal variability derives from a systematic offset between the peripheral skeleton of the body having systematically a higher isotopic composition than the internal skeleton. A simplified silicon isotope fractionation model, in which desmas were excluded, suggests that the lack of a system for seawater pumping in carnivorous sponges favours a low replenishment of dissolved silicon within the internal tissues, causing kinetic fractionation during silicification that impacts the isotopic signature of the internal skeleton. Analysis of multiple spicules should be carried out to "average out" any artefacts in order to produce more robust downcore measurements.

scholarly journals Oxygen isotopic fractionation in rat bones as a result of consuming thermally processed water – bioarchaeological applications

2020 ◽  
Vol 47 (1) ◽  
pp. 1-12 ◽  
Author(s):  
Aleksandra Lisowska-Gaczorek ◽  
Krzysztof Szostek ◽  
Jacek Pawlyta ◽  
Beata Cienkosz-Stepańczak
Keyword(s):  
Isotopic Composition ◽  
Environmental Variability ◽  
Isotope Analysis ◽  
Isotopic Fractionation ◽  
Migration Routes ◽  
Laboratory Rats ◽  
Regular Consumption ◽  
Thermally Processed ◽  
Oxygen Isotopic

AbstractStable isotope analyses of oxygen are used in anthropology for such purposes as determination of origin of individuals, tracking migration routes or dynamics of human community relocation. The methodology related to oxygen isotope analysis has been founded on the relationship between its isotopic composition within phosphate groups of bone tissue (δ18Op) in individuals being analysed and the water consumed by such individuals (δ18Ow). Such a relationship has been observed in many species of mammals, including humans. However, the influence of culinary practices on the isotopic delta values of apatite phosphates of individuals has not yet been researched. The present study, which was conducted using laboratory rats, is an investigation of the influence of the thermal processing of water drank by such rats on the isotopic composition (δ18Op) of bone apatite. Increasing the value of the isotopic composition of water by about 6.1 ‰ during boiling resulted in an increase in the oxygen isotopic value δ18Op of rats drinking the water by about 4 ‰ (29%). It can be expected that regular consumption of heavily isotopic drinks and foods by humans may cause the δ18Op of individuals to exceed the range of isotopic environmental variability, even by a few per mille.

Stable carbon isotope analysis of faecal and blood samples of sheep in relation to the diet

2003 ◽  
Vol 2003 ◽  
pp. 159-159
Author(s):  
A. Balcaen ◽  
E. Claeys ◽  
V. Fievez ◽  
P. Boeckx ◽  
O. van Cleemput ◽  
...  
Keyword(s):  
Isotopic Composition ◽  
Carbon Isotope ◽  
Carbon Fixation ◽  
Isotope Composition ◽  
Stable Carbon Isotope ◽  
Isotope Analysis ◽  
Calvin Cycle ◽  
Isotopic Fractionation ◽  
Woody Species ◽  
Stable Carbon

Stable isotopes have been extraordinarily helpful in understanding animal migration, diet, food webs and nutrient flow (Hilderbrand et al., 1996), based on the property that C3 and C4 plants possess distinctly different 13C/12C ratios (δ13C value) due to isotopic fractionation during photosynthetic carbon fixation (Smith & Epstein, 1971). Most woody species and temperate graminoids assimilate carbon via the Calvin cycle (C3), which discriminates stronger against the heavier isotope (13C) than Hatch-Slack (C4) species (tropical and subtropical graminoids and some shrubs). C3 and C4 plant species have mean δ13C values of -27 ‰ and -13 ‰ respectively (O’Leary, 1981). DeNiro & Epstein (1978) were one of the first to show that the isotopic composition of the whole animal body is similar to that of its diet. Other authors have also found relationships between the isotopic composition of animal tissues and the diet (González-Martin et al., 1999; Jones et al., 1979). The aim of this study was to investigate stable carbon isotope composition in sheep fed diets consisting of either C3 or C3+C4 plants.

Effect of Changes in Leaf Water Oxygen Isotopic Composition on Discrimination Against C18O16O During Photosynthetic Gas Exchange

1994 ◽  
Vol 21 (2) ◽  
pp. 221 ◽  
Author(s):  
LB Flanagan ◽  
SL Phillips ◽  
JR Ehleringer ◽  
J Lloyd ◽  
GD Farquhar
Keyword(s):  
Gas Exchange ◽  
Isotopic Composition ◽  
Vapour Pressure ◽  
Mechanistic Model ◽  
Isotopic Fractionation ◽  
Oxygen Isotopic Composition ◽  
Leaf Water ◽  
Photosynthetic Gas Exchange ◽  
Oxygen Isotopic ◽  
Environment Chamber

Photosynthetic gas exchange measurements were combined with measurements of the carbon and oxygen stable isotopic composition of CO2 after it passed over a leaf of Phaseolus vulgaris or Senecio spp. plants held in a controlled environment chamber. Calculations were then made of discrimination by the leaf against 13CO2 and C18O16O. Leaves were maintained at different vapour pressure gradients in order to generate a range of leaf water 18CO/16CO ratios. The 18CO content of leaf water increased when plants were exposed to higher vapour pressure deficits. The observed C18O16O discrimination values also increased with an increase in the leaf-air vapour pressure gradient and the associated change in leaf water 18/CO16CO values. In addition, the observed C18O16O discrimination values were strongly correlated with values predicted by a mechanistic model of isotopic fractionation.

Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes

2005 ◽  
Vol 52 (3) ◽  
pp. 229-237 ◽  
Author(s):  
J. De Bénédittis ◽  
J.-L. Bertrand-Krajewski
Keyword(s):  
Drinking Water ◽  
Isotopic Composition ◽  
Water Level ◽  
Urban Area ◽  
Oxygen Isotopes ◽  
Flow Rate ◽  
Infiltration Rates ◽  
Sewer Systems ◽  
Oxygen Isotopic ◽  
The Difference

The paper presents the principle of a method to measure infiltration rates in sewer systems based on the use of oxygen isotopes and its application in Lyon (France). In the urban area of Lyon, significant differences in δ18O that can reach 3‰ are observed between the oxygen isotopic compositions of groundwater originating from Rhone, Saone and from their associated alluvial aquifers. Drinking water supplying Lyon results mainly from pumping in the Rhone alluvial aquifer. Therefore, in some areas, the difference of isotopic composition between wastewater resulting from the consumption of drinking water and local groundwater can be used to measure infiltration in sewer systems. The application in the catchment of Ecully shows that the infiltration flow rate presents strong fluctuations at an hourly scale: it varies between 15 and 40 m3/h. This variability could be explained by non-constant discharges of pumping and by variations of the water level in the sewer.

scholarly journals Isotopic signatures of production and uptake of H<sub>2</sub> by soil

2015 ◽  
Vol 15 (22) ◽  
pp. 13003-13021 ◽  
Author(s):  
Q. Chen ◽  
M. E. Popa ◽  
A. M. Batenburg ◽  
T. Röckmann
Keyword(s):  
Isotope Effects ◽  
Deposition Velocity ◽  
Isotopic Fractionation ◽  
Isotopic Signature ◽  
Deuterium Content ◽  
Forest Site ◽  
Fractionation Factor ◽  
Isotopic Signatures ◽  
The Difference ◽  
Isotope Equilibrium

Abstract. Molecular hydrogen (H2) is the second most abundant reduced trace gas (after methane) in the atmosphere, but its biogeochemical cycle is not well understood. Our study focuses on the soil production and uptake of H2 and the associated isotope effects. Air samples from a grass field and a forest site in the Netherlands were collected using soil chambers. The results show that uptake and emission of H2 occurred simultaneously at all sampling sites, with strongest emission at the grassland sites where clover (N2 fixing legume) was present. The H2 mole fraction and deuterium content were measured in the laboratory to determine the isotopic fractionation factor during H2 soil uptake (αsoil) and the isotopic signature of H2 that is simultaneously emitted from the soil (δDsoil). By considering all net-uptake experiments, an overall fractionation factor for deposition of αsoil = kHD / kHH = 0.945 ± 0.004 (95 % CI) was obtained. The difference in mean αsoil between the forest soil 0.937 ± 0.008 and the grassland 0.951 ± 0.026 is not statistically significant. For two experiments, the removal of soil cover increased the deposition velocity (vd) and αsoil simultaneously, but a general positive correlation between vd and αsoil was not found in this study. When the data are evaluated with a model of simultaneous production and uptake, the isotopic composition of H2 that is emitted at the grassland site is calculated as δDsoil = (−530 ± 40) ‰. This is less deuterium depleted than what is expected from isotope equilibrium between H2O and H2.

Sign in / Sign up

Export Citation Format

Share Document