scholarly journals Global modelling of H<sub>2</sub> mixing ratios and isotopic compositions with the TM5 model

2011 ◽  
Vol 11 (2) ◽  
pp. 5811-5866 ◽  
Author(s):  
G. Pieterse ◽  
M. C. Krol ◽  
A. M. Batenburg ◽  
L. P. Steele ◽  
P. B. Krummel ◽  
...  
Keyword(s):  
Isotopic Composition ◽  
Transport Model ◽  
Isotope Composition ◽  
Isotope Effects ◽  
Sensitivity Study ◽  
Global Scale ◽  
Reaction Scheme ◽  
Sufficient Information ◽  
Mixing Ratios ◽  
Independent Information

Abstract. The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For δD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended.

scholarly journals Global modelling of H<sub>2</sub> mixing ratios and isotopic compositions with the TM5 model

2011 ◽  
Vol 11 (14) ◽  
pp. 7001-7026 ◽  
Author(s):  
G. Pieterse ◽  
M. C. Krol ◽  
A. M. Batenburg ◽  
L. P. Steele ◽  
P. B. Krummel ◽  
...  
Keyword(s):  
Isotopic Composition ◽  
Transport Model ◽  
Isotope Composition ◽  
Isotope Effects ◽  
Sensitivity Study ◽  
Global Scale ◽  
Reaction Scheme ◽  
Sufficient Information ◽  
Mixing Ratios ◽  
Independent Information

Abstract. The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their stable isotopic composition and isotope fractionation constants, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For δD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended.

scholarly journals NO<sub>x</sub> cycle and the tropospheric ozone isotope anomaly: an experimental investigation

2014 ◽  
Vol 14 (10) ◽  
pp. 4935-4953 ◽  
Author(s):  
G. Michalski ◽  
S. K. Bhattacharya ◽  
G. Girsch
Keyword(s):  
Steady State ◽  
Isotopic Composition ◽  
Isotope Composition ◽  
Dominant Role ◽  
Isotope Effects ◽  
Rate Coefficients ◽  
Atmospheric Conditions ◽  
Exchange Reactions ◽  
Mixing Ratios ◽  
High Concentrations

Abstract. The oxygen isotope composition of nitrogen oxides (NOx) in the atmosphere is a useful tool for understanding the oxidation of NOx into nitric acid / nitrate in the atmosphere. A set of experiments was conducted to examine change in isotopic composition of NOx due to NOx–O2–O3 photochemical cycling. At low NOx / O2 mixing ratios, NOx became progressively and nearly equally enriched in 17O and 18O over time until it reached a steady state with Δ17O values of 39.3 ± 1.9‰ and δ18O values of 84.2 ± 4‰, relative to the isotopic composition of the initial O2 gas. As the mixing ratios were increased, the isotopic enrichments were suppressed by isotopic exchange between O atoms, O2, and NOx. A kinetic model was developed to simulate the observed data and it showed that the isotope effects occurring during O3 formation play a dominant role in controlling NOx isotopes and, in addition, secondary kinetic isotope effects or isotope exchange reactions are also important during NOx cycling. The data and model were consistent with previous studies which showed that the NO + O3 reactions occur mainly via the transfer of the terminal atoms of O3. The model predicts that under tropospheric concentrations of NOx and O3, the timescale of NOx–O3 isotopic equilibrium ranges from hours (for ppbv NOx / O2 mixing ratios) to days (for pptv mixing ratios) and yields steady state Δ17O and δ18O values of 45‰ and 117‰ respectively (relative to Vienna Standard Mean Ocean Water (VSMOW)) in both cases. Under atmospheric conditions when O3 has high concentrations, the equilibrium between NOx and O3 should occur rapidly (h) but this equilibrium cannot be reached during polar winters and/or nights if the NOx conversion to HNO3 is faster. The experimentally derived rate coefficients can be used to model the major NOx–O3 isotopologue reactions at various pressures and in isotope modeling of tropospheric nitrate.

scholarly journals A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation

2009 ◽  
Vol 9 (2) ◽  
pp. 5679-5751 ◽  
Author(s):  
G. Pieterse ◽  
M. C. Krol ◽  
T. Röckmann
Keyword(s):  
Molecular Hydrogen ◽  
Hydrogen Isotope ◽  
Isotope Composition ◽  
Isotope Effects ◽  
Quantitative Information ◽  
Sensitivity Study ◽  
Reaction Scheme ◽  
Photochemical Oxidation ◽  
Oxidation Of Methane ◽  
The Individual

Abstract. The isotopic composition of molecular hydrogen (H2) produced by photochemical oxidation of methane (CH4) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H2). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH4 and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds – seen as reactive sites – have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH4+Cl. The same approach is applied to VOCs, which are important precursors of H2 that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. Using these concepts we implement a full hydrogen isotope scheme in a chemical box model and carry out a sensitivity study to identify those reaction steps and conditions that are most critical for the isotope composition of the final H2 product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H2 produced from CH4 and VOCs in a consistent way.

scholarly journals A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation

2009 ◽  
Vol 9 (21) ◽  
pp. 8503-8529 ◽  
Author(s):  
G. Pieterse ◽  
M. C. Krol ◽  
T. Röckmann
Keyword(s):  
Molecular Hydrogen ◽  
Hydrogen Isotope ◽  
Isotope Composition ◽  
Isotope Effects ◽  
Quantitative Information ◽  
Sensitivity Study ◽  
Reaction Scheme ◽  
Photochemical Oxidation ◽  
Oxidation Of Methane ◽  
The Individual

Abstract. The isotopic composition of molecular hydrogen (H2) produced by photochemical oxidation of methane (CH4) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H2). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH4 and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds – seen as reactive sites – have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH4+Cl. The same approach is applied to VOCs, which are important precursors of H2 that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. Using these concepts we implement a full hydrogen isotope scheme in a chemical box model and carry out a sensitivity study to identify those reaction steps and conditions that are most critical for the isotope composition of the final H2 product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H2 produced from CH4 and VOCs in a consistent way.

scholarly journals NO<sub>x</sub> cycle and tropospheric ozone isotope anomaly: an experimental investigation

2013 ◽  
Vol 13 (4) ◽  
pp. 9443-9483 ◽  
Author(s):  
G. Michalski ◽  
S. K. Bhattacharya ◽  
G. Girsch
Keyword(s):  
Steady State ◽  
Isotopic Composition ◽  
Isotope Composition ◽  
Dominant Role ◽  
Isotope Effects ◽  
No Oxidation ◽  
Rate Coefficients ◽  
Mixing Ratios ◽  
Kinetic Isotope ◽  
Terminal Atom

Abstract. The oxygen isotope composition of nitrogen oxides (NOx) in the atmosphere may be a useful tool for understanding the oxidation of NOx into nitric acid/nitrate in the atmosphere. A set of experiments were conducted to examine changes in isotopic composition of NOx due to O3-NOx photochemical cycling. At low NO2/O2 mixing ratios, NO2 becomes progressively and nearly equally enriched in 17O and 18O over time until it reaches a steady state with Δ17O values of 40.6 ± 1.9‰ and δ18O values of 84.2 ± 4‰, relative to the isotopic composition of the O2 gas. As the mixing ratio increases, isotopic exchange between O atoms and O2 and NOx suppresses the isotopic enrichments. A kinetic model simulating the observed data shows that the isotope effects during ozone formation play a more dominant role compared to kinetic isotope effects during NO oxidation or exchange of NO2. The model results are consistent with the data when the NO + O3 reaction occurs mainly via the transfer of the terminal atom of O3. The model predicts that under tropospheric concentrations of the three reactants, the timescale of NOx isotopic equilibrium ranges from hours (ppbv mixing ratios) to days/weeks (pptv) and yields steady state Δ17O and δ18O values of 46‰ and 115‰ respectively with respect to Vienna Standard Mean Ocean Water. Interpretation of tropospheric nitrate isotope data can now be done with the derived rate coefficients of the major isotopologue reactions at various pressures.

scholarly journals Seasonal variations in nitrate isotope composition of three rivers draining into the North Sea

2010 ◽  
Vol 7 (4) ◽  
pp. 6051-6088 ◽  
Author(s):  
A. Deek ◽  
K. Emeis ◽  
U. Struck
Keyword(s):  
Isotopic Composition ◽  
North Sea ◽  
Isotope Composition ◽  
Atmospheric Oxygen ◽  
Isotope Effects ◽  
Nitrate Sources ◽  
Particulate Nitrogen ◽  
Soil Nitrification ◽  
Mean Values ◽  
Δ 15N

Abstract. Nitrate loading of coastal ecosystems by rivers that drain industrialised catchments continues to be a problem in the South Eastern North Sea, in spite of significant mitigation efforts over the last 2 decades. To identify nitrate sources, sinks, and turnover in three German rivers that discharge into the German Bight, we determined δ 15N-NO3- and δ18O- NO3- in nitrate and δ 15N of particulate nitrogen for the period 2006–2009 (biweekly samples). The nitrate loads of Rhine, Weser and Ems varied seasonally in magnitude and δ 15N-NO3- (6.5–21‰), whereas the δ 18O-NO3- (-0.3–5.9‰) and δ 15N-PN (4–14‰) were less variable. Overall temporal patterns in nitrate mass fluxes and isotopic composition suggest that a combination of nitrate delivery from nitrification of soil ammonia in the catchment and assimilation of nitrate in the rivers control the isotopic composition of nitrate. Nitrification in soils as a source is indicated by low δ 18O-NO3- in winter, which traces the δ 18O of river water. Mean values of δ 18O-H2O were between –9.4‰ and –7.3‰; combined in a ratio of 2:1 with the atmospheric oxygen δ 18O of 23.5‰ agrees with the found δ 18O of nitrate in the rivers. Parallel variations of δ 15N-NO3- and δ 18O-NO3- within each individual river are caused by isotope effects associated with nitrate assimilation in the water column, the extent of which is determined by residence time in the river. Assimilation is furthermore to some extent mirrored both by the δ 15N of nitrate and particulate N. Although δ 15-NO3- observed in Rhine, Weser and Ems are reflected in high average δ 15N-PN (between 6‰ and 9‰, both are uncorrelated in the time series due to lateral and temporal mixing of PN. That a larger enrichment was consistently seen in δ 15N-NO3- relative to δ 18O-NO3- is attributed to constant additional diffuse nitrate inputs deriving from soil nitrification in the catchment area. A statistically significant inverse correlation exists between increasing δ 15N-NO3- values and decreasing NO3- concentrations. This inverse relationship – observed in each seasonal cycle – together with a robust relationship between human dominated land use and δ 15N-NO3- values demonstrates a strong influence of human activities and riverine nitrate consumption efficiency on the isotopic composition of riverine nitrate.

scholarly journals Exploring Constraints on a Wetland Methane Emission Ensemble (WetCHARTs) using GOSAT Satellite Observations

2020 ◽  
Author(s):  
Robert J. Parker ◽  
Chris Wilson ◽  
A. Anthony Bloom ◽  
Edward Comyn-Platt ◽  
Garry Hayman ◽  
...  
Keyword(s):  
Land Surface ◽  
Seasonal Cycle ◽  
Transport Model ◽  
Global Scale ◽  
Data Driven ◽  
Emission Model ◽  
Chemical Transport Model ◽  
Mixing Ratios ◽  
The North ◽  
Gosat Satellite

Abstract. Wetland emissions contribute the largest uncertainties to the current global atmospheric CH4 budget and how these emissions will change under future climate scenarios is also still poorly understood. Bloom et al. (2017b) developed WetCHARTs, a simple, data-driven, ensemble-based model that produces estimates of CH4 wetland emissions constrained by observations of precipitation and temperature. This study performs the first detailed global and regional evaluation of the WetCHARTs CH4 emission model ensemble against 9 years of high-quality, validated atmospheric CH4 observations from the GOSAT satellite. A 3-D chemical transport model is used to estimate atmospheric CH4 mixing ratios based on the WetCHARTs emissions and other sources. Across all years and all ensemble members, the observed global seasonal cycle amplitude is typically underestimated by WetCHARTs by −7.4 ppb, but the correlation coefficient of 0.83 shows that the seasonality is well-produced at a global scale. The Southern Hemisphere has less of a bias (−1.9 ppb) than the Northern Hemisphere (−9.3 ppb) and our findings show that it is typically the North Tropics where this bias is worst (−11.9 ppb). We find that WetCHARTs generally performs well in reproducing the observed wetland CH4 seasonal cycle for the majority of wetland regions although, for some regions, regardless of the ensemble configuration, WetCHARTs does not well-reproduce the observed seasonal cycle. In order to investigate this, we performed detailed analysis of some of the more challenging exemplar regions (Parana River, Congo, Sudd and Yucatan). Our results show that certain ensemble members are more suited to specific regions, either due to deficiencies in the underlying data driving the model or complexities in representing the processes involved. In particular, incorrect definition of the wetland extent is found to be the most common reason for the discrepancy between the modelled and observed CH4 concentrations. The remaining driving data (i.e. heterotrophic respiration and temperature) are shown to also contribute to the mismatch to observations, with the details differing on a region-by-region basis but generally showing that some degree of temperature dependency is better than none. We conclude that the data-driven approach used by WetCHARTs is well-suited to produce a benchmark ensemble dataset against which to evaluate more complex process-based land surface models that explicitly model the hydrological behaviour of these complex wetland regions.

scholarly journals Exploring constraints on a wetland methane emission ensemble (WetCHARTs) using GOSAT observations

2020 ◽  
Vol 17 (22) ◽  
pp. 5669-5691
Author(s):  
Robert J. Parker ◽  
Chris Wilson ◽  
A. Anthony Bloom ◽  
Edward Comyn-Platt ◽  
Garry Hayman ◽  
...  
Keyword(s):  
Land Surface ◽  
Seasonal Cycle ◽  
Transport Model ◽  
Global Scale ◽  
Data Driven ◽  
Emission Model ◽  
Chemical Transport Model ◽  
Mixing Ratios ◽  
The North ◽  
Data Driven Approach

Abstract. Wetland emissions contribute the largest uncertainties to the current global atmospheric CH4 budget, and how these emissions will change under future climate scenarios is also still poorly understood. Bloom et al. (2017b) developed WetCHARTs, a simple, data-driven, ensemble-based model that produces estimates of CH4 wetland emissions constrained by observations of precipitation and temperature. This study performs the first detailed global and regional evaluation of the WetCHARTs CH4 emission model ensemble against 9 years of high-quality, validated atmospheric CH4 observations from GOSAT (the Greenhouse Gases Observing Satellite). A 3-D chemical transport model is used to estimate atmospheric CH4 mixing ratios based on the WetCHARTs emissions and other sources. Across all years and all ensemble members, the observed global seasonal-cycle amplitude is typically underestimated by WetCHARTs by −7.4 ppb, but the correlation coefficient of 0.83 shows that the seasonality is well-produced at a global scale. The Southern Hemisphere has less of a bias (−1.9 ppb) than the Northern Hemisphere (−9.3 ppb), and our findings show that it is typically the North Tropics where this bias is the worst (−11.9 ppb). We find that WetCHARTs generally performs well in reproducing the observed wetland CH4 seasonal cycle for the majority of wetland regions although, for some regions, regardless of the ensemble configuration, WetCHARTs does not reproduce the observed seasonal cycle well. In order to investigate this, we performed detailed analysis of some of the more challenging exemplar regions (Paraná River, Congo, Sudd and Yucatán). Our results show that certain ensemble members are more suited to specific regions, due to either deficiencies in the underlying data driving the model or complexities in representing the processes involved. In particular, incorrect definition of the wetland extent is found to be the most common reason for the discrepancy between the modelled and observed CH4 concentrations. The remaining driving data (i.e. heterotrophic respiration and temperature) are shown to also contribute to the mismatch with observations, with the details differing on a region-by-region basis but generally showing that some degree of temperature dependency is better than none. We conclude that the data-driven approach used by WetCHARTs is well-suited to producing a benchmark ensemble dataset against which to evaluate more complex process-based land surface models that explicitly model the hydrological behaviour of these complex wetland regions.

scholarly journals Nitrogen isotope effects can be used to diagnose N transformations in wastewater anammox systems

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Paul M. Magyar ◽  
Damian Hausherr ◽  
Robert Niederdorfer ◽  
Nicolas Stöcklin ◽  
Jing Wei ◽  
...  
Keyword(s):  
Isotope Effect ◽  
Isotope Composition ◽  
Isotope Effects ◽  
Nitrogen Isotope ◽  
Anammox Bacteria ◽  
Ammonium Oxidation ◽  
Experimental Conditions ◽  
N Transformations ◽  
Natural Systems ◽  
Inverse Isotope Effect

AbstractAnaerobic ammonium oxidation (anammox) plays an important role in aquatic systems as a sink of bioavailable nitrogen (N), and in engineered processes by removing ammonium from wastewater. The isotope effects anammox imparts in the N isotope signatures (15N/14N) of ammonium, nitrite, and nitrate can be used to estimate its role in environmental settings, to describe physiological and ecological variations in the anammox process, and possibly to optimize anammox-based wastewater treatment. We measured the stable N-isotope composition of ammonium, nitrite, and nitrate in wastewater cultivations of anammox bacteria. We find that the N isotope enrichment factor 15ε for the reduction of nitrite to N2 is consistent across all experimental conditions (13.5‰ ± 3.7‰), suggesting it reflects the composition of the anammox bacteria community. Values of 15ε for the oxidation of nitrite to nitrate (inverse isotope effect, − 16 to − 43‰) and for the reduction of ammonium to N2 (normal isotope effect, 19–32‰) are more variable, and likely controlled by experimental conditions. We argue that the variations in the isotope effects can be tied to the metabolism and physiology of anammox bacteria, and that the broad range of isotope effects observed for anammox introduces complications for analyzing N-isotope mass balances in natural systems.

scholarly journals Impact of a new condensed toluene mechanism on air quality model predictions in the US

2010 ◽  
Vol 3 (4) ◽  
pp. 2291-2314
Author(s):  
G. Sarwar ◽  
K. W. Appel ◽  
A. G. Carlton ◽  
R. Mathur ◽  
K. Schere ◽  
...  
Keyword(s):  
Air Quality ◽  
Los Angeles ◽  
Production Efficiency ◽  
Sensitivity Study ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Daily Maximum ◽  
Air Quality Model ◽  
Quality Model ◽  
Mixing Ratios

Abstract. A new condensed toluene mechanism is incorporated into the Community Multiscale Air Quality Modeling system. Model simulations are performed using the CB05 chemical mechanism containing the existing (base) and the new toluene mechanism for the western and eastern US for a summer month. With current estimates of tropospheric emission burden, the new toluene mechanism increases monthly mean daily maximum 8-h ozone by 1.0–3.0 ppbv in Los Angeles, Portland, Seattle, Chicago, Cleveland, northeastern US, and Detroit compared to that with the base toluene chemistry. It reduces model mean bias for ozone at elevated observed ozone mixing ratios. While the new mechanism increases predicted ozone, it does not enhance ozone production efficiency. Sensitivity study suggests that it can further enhance ozone if elevated toluene emissions are present. While changes in total fine particulate mass are small, predictions of in-cloud SOA increase substantially.

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