scholarly journals Evidence for a major missing source in the global chloromethane budget from stable carbon isotopes

2018 ◽  
Author(s):  
Enno Bahlmann ◽  
Frank Keppler ◽  
Julian Wittmer ◽  
Markus Greule ◽  
Heinz Friedrich Schöler ◽  
...  
Keyword(s):  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Stable Carbon Isotopes ◽  
Tropical Rainforest ◽  
Isotope Effects ◽  
Stratospheric Ozone ◽  
Mixing Ratios ◽  
Promising Tool ◽  
Kinetic Isotope ◽  
Phase Out

Abstract. Chloromethane (CH3Cl) is the most important natural input of reactive chlorine to the stratosphere, contributing about 16 % to stratospheric ozone depletion. Due to the phase out of anthropogenic emissions of chlorofluorocarbons, CH3Cl will largely control future levels of stratospheric chlorine. The tropical rainforest is commonly assumed to be the strongest single CH3Cl source, contributing over half of the global annual emissions of about 4000 to 5000 Gg (1 Gg = 109 g). This source shows a characteristic carbon isotope fingerprint, making isotopic investigations a promising tool for improving its atmospheric budget. Applying carbon isotopes to better constrain the atmospheric budget of CH3Cl requires sound information on the kinetic isotope effects for the main sink processes e.g. the reaction with OH and Cl in the troposphere. We conducted photochemical CH3Cl degradation experiments in a 3500 L smog chamber to determine the carbon isotope fractionation (ε) for the reaction of CH3Cl with OH and Cl. For the reaction of CH3Cl with OH, we determined a ε of (−11.2 ± 0.8) ‰ (n = 3) and for the reaction with Cl we found a ε of (−10.2 ± 0.5) ‰ (n = 1) being five to six times smaller than previously reported. Our smaller isotope effects are strongly supported by the lack of any significant seasonal covariation in previously reported tropospheric δ13C(CH3Cl) values with the OH driven seasonal cycle in tropospheric mixing ratios. Applying these new fractionation factors to the global CH3Cl budget using a simple two hemispheric box model, we derive a tropical rainforest CH3Cl source of (670 ± 200) Gg a−1, which is considerably smaller than previous estimates. A revision of previous bottom up estimates, using above ground biomass instead of rainforest area, strongly supports this lower estimate. Finally, our results suggest a large unknown tropical CH3Cl source of (1230 ± 200) Gg a−1.

scholarly journals Evidence for a major missing source in the global chloromethane budget from stable carbon isotopes

2019 ◽  
Vol 19 (3) ◽  
pp. 1703-1719 ◽  
Author(s):  
Enno Bahlmann ◽  
Frank Keppler ◽  
Julian Wittmer ◽  
Markus Greule ◽  
Heinz Friedrich Schöler ◽  
...  
Keyword(s):  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Isotope Effect ◽  
Stable Carbon Isotopes ◽  
Tropical Rainforest ◽  
Isotope Effects ◽  
Stratospheric Ozone ◽  
Mixing Ratios ◽  
Promising Tool ◽  
Carbon Isotope Effect

Abstract. Chloromethane (CH3Cl) is the most important natural input of reactive chlorine to the stratosphere, contributing about 16 % to stratospheric ozone depletion. Due to the phase-out of anthropogenic emissions of chlorofluorocarbons, CH3Cl will largely control future levels of stratospheric chlorine. The tropical rainforest is commonly assumed to be the strongest single CH3Cl source, contributing over half of the global annual emissions of about 4000 to 5000 Gg (1 Gg = 109 g). This source shows a characteristic carbon isotope fingerprint, making isotopic investigations a promising tool for improving its atmospheric budget. Applying carbon isotopes to better constrain the atmospheric budget of CH3Cl requires sound information on the kinetic isotope effects for the main sink processes: the reaction with OH and Cl in the troposphere. We conducted photochemical CH3Cl degradation experiments in a 3500 dm3 smog chamber to determine the carbon isotope effect (ε=k13C/k12C-1) for the reaction of CH3Cl with OH and Cl. For the reaction of CH3Cl with OH, we determined an ε value of (-11.2±0.8) ‰ (n=3) and for the reaction with Cl we found an ε value of (-10.2±0.5) ‰ (n=1), which is 5 to 6 times smaller than previously reported. Our smaller isotope effects are strongly supported by the lack of any significant seasonal covariation in previously reported tropospheric δ13C(CH3Cl) values with the OH-driven seasonal cycle in tropospheric mixing ratios. Applying these new values for the carbon isotope effect to the global CH3Cl budget using a simple two hemispheric box model, we derive a tropical rainforest CH3Cl source of (670±200) Gg a−1, which is considerably smaller than previous estimates. A revision of previous bottom-up estimates, using above-ground biomass instead of rainforest area, strongly supports this lower estimate. Finally, our results suggest a large unknown CH3Cl source of (1530±200) Gg a−1.

scholarly journals Anaerobic methane oxidation by nitrate: kinetic isotope effect

2018 ◽  
Vol 10 (1) ◽  
Author(s):  
Vasiliy A. Vavilin
Keyword(s):  
Dynamic Model ◽  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Isotope Effect ◽  
Isotope Fractionation ◽  
Kinetic Isotope Effect ◽  
Stable Carbon Isotopes ◽  
Stable Carbon ◽  
Fractionation Factor ◽  
Kinetic Isotope

The ratio of stable carbon isotopes (13C/12C) in different environments serves as a significant limitation in estimating the global balance of methane [Hornibrook et al., 2000]. In this case, the value of 13C/12C largely depends on the kinetic isotope effect associated with the metabolism of microorganisms that produce and consume CH4. The article suggests a dynamic model of the processes of methane formation and its anaerobic oxidation with nitrate by methanotrophic denitrifying microorganisms (DAOM), which allowed estimating the fractionation factor of stable carbon isotopes. In the experiment with peat from the minerotrophic bog [Smemo, Yavitt, 2007], the dynamics of the amount of methane and was measured. The dynamic model showed that the introduction of nitrate leads to a slow decrease in the partial pressure of methane. Since methane in the DAOM process is a substrate, methane is enriched with heavier carbon 13C in the system under study. This leads to an increase in the value . The carbon isotope fractionation factor during methane oxidation with nitrate was equal to 1.018 and comparable with the fraction of carbon isotope fractionation in the process of acetoclastic methanogenesis (1.01). Model calculations have shown that during incubation the apparent fractionation factor of carbon isotopes with the simultaneous formation of methane and DAOM slowly decreases. The ratio of 13C/12C isotopes in dissolved and gaseous methane practically does not differ. The model showed that an increase in the initial concentration of nitrate increases the rate of DAOM, which leads to a decrease in the concentration of dissolved methane. In this case, the value of 13C/12C increases. In field studies, Shi et al. (2017) showed that the presence of DAOM in peat bogs in which fertilizers penetrate can be controlled by the amount of nitrate used and the depth of penetration into the anoxic layer. Two MATLAB files describing DAOM are attached to the article.

scholarly journals Dependence between the photochemical age of light aromatic hydrocarbons and the carbon isotope ratios of atmospheric nitrophenols

2019 ◽  
Vol 19 (8) ◽  
pp. 5495-5509
Author(s):  
Marina Saccon ◽  
Anna Kornilova ◽  
Lin Huang ◽  
Jochen Rudolph
Keyword(s):  
Carbon Isotope ◽  
Organic Compounds ◽  
Mechanistic Model ◽  
Isotope Effects ◽  
Isotope Ratios ◽  
Kinetic Isotope Effects ◽  
Laboratory Studies ◽  
Carbon Isotope Ratios ◽  
Kinetic Isotope ◽  
Volatile Organic

Abstract. Concepts were developed to establish relationships between the stable carbon isotope ratios of nitrophenols in the atmosphere and the photochemical processing of their precursors, light aromatic volatile organic compounds. These concepts were based on the assumption that nitrophenols are formed dominantly from the photo-oxidation of aromatic volatile organic compounds (VOCs). A mass balance model as well as various scenarios based on the proposed mechanism of nitrophenol formation were formulated and applied to derive the time-integrated exposure of the precursors to processing by OH radicals (∫[OH]dt) from ambient observations made between 2009 and 2012 in Toronto, Canada. The mechanistic model included the possibility of isotopic fractionation during intermediate steps, rather than only during the initial reaction step. This model takes kinetic isotope effects for the reaction of the precursor VOC with the hydroxyl radical and their respective rate constants into account, as well as carbon isotope ratio source signatures. While many of these values are known, there are some, such as the kinetic isotope effects of reactions of first- and second-generation products, which are unknown. These values were predicted in this study based on basic principles and published laboratory measurements of kinetic carbon isotope effects and were applied to the mechanistic model. Due to the uncertainty of the estimates based on general principles, three scenarios were used with different values for isotope effects that were not known from laboratory studies. Comparison of the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt with published results of laboratory studies and ambient observations was used to narrow the range of plausible scenarios for the mechanistic model. The results also suggests that mass-balance-based models do not adequately describe the dependence between nitrophenol carbon isotope ratios and ∫[OH]dt.

Vertical stratification of Neotropical leaf-nosed bats (Chiroptera: Phyllostomidae) revealed by stable carbon isotopes

2011 ◽  
Vol 27 (03) ◽  
pp. 211-222 ◽  
Author(s):  
Katja Rex ◽  
Robert Michener ◽  
Thomas H. Kunz ◽  
Christian C. Voigt
Keyword(s):  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Species Interactions ◽  
Rain Forest ◽  
Stable Carbon Isotopes ◽  
Stable Carbon Isotope ◽  
The Body ◽  
Vertical Stratification ◽  
Forest Site ◽  
Stable Carbon

Abstract:Tropical rain forests harbour the most diverse plant and animal assemblages known to science, but our understanding of assemblage structure and species interactions is limited. Bats, as the only flying mammals, have the potential to exploit resources from all strata in forest communities. Thus, fruit-eating phyllostomid bats often have been categorized into canopy-, subcanopy- and understorey-foraging species, based largely upon the height at which they were most frequently captured. Here we challenge this classification and use stable carbon isotopes to assess foraging height of bat species at an Amazonian rain-forest site in Ecuador and at a Caribbean lowland rain-forest site in Costa Rica for comparison with data from mist-net captures. The proportion of the heavy stable carbon isotope13C in relation to the lighter12C isotope increases in plants from ground level to the canopy (0.12‰ m−1–0.18‰ m−1), and these differences in stable carbon isotope signatures are reflected in the body tissue of phytophagous bats. We used the stable carbon isotope ratio (δ13C) of wing tissue to estimate the foraging heights of 54 phyllostomid species in two Neotropical bat assemblages. Based on stable isotope data, phyllostomid species exploit food resources at all vertical strata of the forest. Capture height was not a reliable predictor of foraging height and suggests that bats most likely use lower strata to commute between foraging sites to avoid predators. Vertical stratification is likely to be a key factor promoting niche partitioning, thus promoting high local species richness in many tropical animal assemblages.

scholarly journals Degradation changes stable carbon isotope depth profiles in palsa peatlands

2014 ◽  
Vol 11 (1) ◽  
pp. 1383-1412 ◽  
Author(s):  
J. P. Krüger ◽  
J. Leifeld ◽  
C. Alewell
Keyword(s):  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Stable Carbon Isotopes ◽  
Stable Carbon Isotope ◽  
Stable Carbon ◽  
Δ13c Values ◽  
Depth Profiles ◽  
Degradation Rates ◽  
Aerobic Decomposition ◽  
Permafrost Thawing

Abstract. Palsa peatlands are a significant carbon pool in the global carbon cycle and are projected to change by global warming due to accelerated permafrost thaw. Our aim was to use stable carbon isotopes as indicators of palsa degradation. Depth profiles of stable carbon isotopes generally reflect organic matter dynamics in soils with an increase of δ13C values during aerobic decomposition and stable or decreasing δ13C values with depth during anaerobic decomposition. Stable carbon isotope depth profiles of undisturbed and degraded sites of hummocks as well as hollows at three palsa peatlands in northern Sweden were used to investigate the degradation processes. The depth patterns of stable isotopes clearly differ between intact and degraded hummocks at all sites. Erosion and cryoturbation at the degraded sites significantly changes the stable carbon isotope depth profiles. At the intact hummocks the uplifting of peat material by permafrost is indicated by a turning in the δ13C depth trend and this assessment is supported by a change in the C / N ratios. For hollows isotope patterns were less clear, but some hollows and degraded hollows in the palsa peatlands show differences in their stable carbon isotope depth profiles indicating enhanced degradation rates. We conclude that the degradation of palsa peatlands by accelerated permafrost thawing could be identified with stable carbon isotope depth profiles. At intact hummocks δ13C depth patterns display the uplifting of peat material by a change in peat decomposition processes.

scholarly journals Stable carbon isotope fractionation in the UV photolysis of CFC-11 and CFC-12

2011 ◽  
Vol 11 (12) ◽  
pp. 33173-33189
Author(s):  
A. Zuiderweg ◽  
J. Kaiser ◽  
J. C. Laube ◽  
T. Röckmann ◽  
R. Holzinger
Keyword(s):  
Isotope Fractionation ◽  
Stable Carbon Isotopes ◽  
Isotope Effects ◽  
Stratospheric Ozone ◽  
Stable Carbon Isotope ◽  
Montreal Protocol ◽  
Stable Carbon ◽  
Chlorine Isotopes ◽  
Before And After ◽  
Stable Carbon Isotope Fractionation

Abstract. The chlorofluorocarbons CFC-11 (CCl3F) and CFC-12 (CCl2F2) are stable atmospheric compounds that are produced at the earth's surface, but removed only at high altitudes in the stratosphere, where their removal liberates atomic chlorine that then catalytically destroys stratospheric ozone. For such long-lived compounds, isotope effects in the stratospheric removal reactions have a large effect on their global isotope budgets. We have determined the photolytic isotope fractionation for stable carbon isotopes of CFC-11 and CFC-12 in laboratory experiments. 13C/12C isotope fractionations (ϵ) range from (−23.7 ± 0.9) to (−17.5 ± 0.4)‰ for CFC-11 and (−69.2 ± 3.4) to (−49.4 ± 2.3)‰ for CFC-12 between 203 and 288 K, a temperature range relevant to conditions in the troposphere and stratosphere. These results suggest that CFCs should become strongly enriched in 13C with decreasing mixing ratio in the stratosphere, similar to what has been recently observed for CFC chlorine isotopes. In conjunction with the strong variations in CFC emissions before and after the Montréal Protocol, the stratospheric enrichments should also lead to a significant temporal increase in the 13C content of the CFCs at the surface over the past decades, which should be recorded in atmospheric air archives such as firn air.

Late Precambrian marbles of unusual carbon-isotope composition, southeastern British Columbia

1985 ◽  
Vol 22 (3) ◽  
pp. 324-329 ◽  
Author(s):  
Edward D. Ghent ◽  
James R. O'Neil
Keyword(s):  
British Columbia ◽  
Carbon Isotope ◽  
Isotope Composition ◽  
Isotope Effects ◽  
Large Reservoir ◽  
Kinetic Isotope ◽  
Carbon And Oxygen Isotope ◽  
Isotope Equilibrium ◽  
Mineralogical Phase ◽  
Isotope Analyses

Carbon- and oxygen-isotope analyses were made of both carbonates and graphites from several Precambrian metamorphic samples from British Columbia. The carbon-isotope data are unusual in that the δ13C values of many marbles are very high, up to 9.9, and the most positive values occur in the sillimanite-zone rocks. The δ13C values of graphite are also relatively high, and the 13C fractionations between calcite and graphite suggest that (1) the rocks attained and retained carbon-isotope equilibrium during metamorphism, and (2) the temperature of graphite equilibration in marbles from the sillimanite zone is 650–690 °C, in agreement with temperatures estimated from mineralogical phase equilibria.Possible precursor carbonates for the 13C-rich marbles in British Columbia include (1) Precambrian carbonate-secreting organisms such as algae that participate in reactions with large kinetic isotope effects, (2) carbonates that exchanged carbon isotopes with a large reservoir of organic material prior to metamorphism, and (3) travertines.

Seedling growth, leaf water status and signature of stable carbon isotopes in C3 perennials exposed to natural phytochemicals

2012 ◽  
Vol 60 (8) ◽  
pp. 676 ◽  
Author(s):  
M. Iftikhar Hussain ◽  
Manuel J. Reigosa
Keyword(s):  
Water Use Efficiency ◽  
Carbon Isotope ◽  
Carbon Isotopes ◽  
Water Use ◽  
Stable Carbon Isotopes ◽  
Carbon Isotope Discrimination ◽  
Water Status ◽  
Perennial Species ◽  
Stable Carbon ◽  
Use Efficiency

In the present study, we evaluated the seedling growth, water status and signature of stable carbon isotopes in C3 perennial species exposed to natural phytochemicals. Three perennial species, cocksfoot (Dactylis glomerata), perennial ryegrass (Lolium perenne) and common sorrel (Rumex acetosa), were grown for 30 days in perlite, watered with Hoagland solution and exposed to the phytochemicals benzoxazolin-2(3H)-one (BOA) and cinnamic acid (CA) at 0, 0.1, 0.5, 1.0 and 1.5 mM concentrations. BOA markedly decreased the leaf and root fresh weights of D. glomerata and L. perenne in a concentration-dependent manner. The leaf fresh weight (LFW) of plants treated with CA (1.5 mM) was similarly affected by showing a decrease of LFW, being the lowest in L. perenne (56%) followed by D. glomerata (46%). The relative water contents of L. perenne, D. glomerata and R. acetosa were decreased while maximum RWC reduction was observed in L. perenne. Carbon isotope discrimination in L. perenne, D. glomerata and R. acetosa were reduced following treatment with BOA and CA at 1.5 mM. BOA at 1.5 mM decreased the ratio of intercellular to ambient CO2 concentration relative to control in L. perenne, D. glomerata and R. acetosa. There was an increase in water-use efficiency in L. perenne, D. glomerata and R. acetosa after treatment with BOA and CA. The dry weight of plants treated with CA (1.5 mM) showed different patterns of variation, being lowest in L. perenne (33%) followed by D. glomerata (3%) and R. acetosa (2%). Phytotoxicity was higher for the perennial grass than for the perennial broadleaf. These results clearly demonstrate a widespread occurrence of phytotoxicity among the three species, their tolerance and relationship between carbon isotope discrimination and intrinsic water-use efficiency.

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