Stephen D. Steenrod

Trends in Stratospheric Ozone: Lessons Learned from a 3D Chemical Transport Model

Abstract Stratospheric ozone is affected by external factors such as chlorofluorcarbons (CFCs), volcanoes, and the 11-yr solar cycle variation of ultraviolet radiation. Dynamical variability due to the quasi-biennial oscillation and other factors also contribute to stratospheric ozone variability. A research focus during the past two decades has been to quantify the downward trend in ozone due to the increase in industrially produced CFCs. During the coming decades research will focus on detection and attribution of the expected recovery of ozone as the CFCs are slowly removed from the atmosphere. A chemical transport model (CTM) has been used to simulate stratospheric composition for the past 30 yr and the next 20 yr using 50 yr of winds and temperatures from a general circulation model (GCM). The simulation includes the solar cycle in ultraviolet radiation, a representation of aerosol surface areas based on observations including volcanic perturbations from El Chichon in 1982 and Pinatubo in 1991, and t...

Quantifying errors in trace species transport modeling

One expectation when computationally solving an Earth system model is that a correct answer exists, that with adequate physical approximations and numerical methods our solutions will converge to that single answer. With such hubris, we performed a controlled numerical test of the atmospheric transport of CO2 using 2 models known for accurate transport of trace species. Resulting differences were unexpectedly large, indicating that in some cases, scientific conclusions may err because of lack of knowledge of the numerical errors in tracer transport models. By doubling the resolution, thereby reducing numerical error, both models show some convergence to the same answer. Now, under realistic conditions, we identify a practical approach for finding the correct answer and thus quantifying the advection error.

Trends and variability in surface ozone over the United States

We investigate the observed trends and interannual variability in surface ozone over the United States using the Global Modeling Initiative chemical transport model. We discuss the roles of meteorology, emissions, and transport from the stratosphere in driving the interannual variability in different regions and seasons. We demonstrate that a hindcast simulation for 1991–2010 can reproduce much of the observed variability and the trends in summertime ozone, with correlation coefficients for seasonally and regionally averaged median ozone ranging from 0.46 to 0.89. Reproducing the interannual variability in winter and spring in the western United States may require higher-resolution models to adequately represent stratosphere-troposphere exchange. Hindcast simulations with fixed versus variable emissions show that changes in anthropogenic emissions drive the observed negative trends in monthly median ozone concentrations in the eastern United States during summer, as well as the observed reduction in the amplitude of the seasonal cycle. The simulation underestimates positive trends in the western United States during spring, but excluding the first 4 years of data removes many of the statistically significant trends in this region. The reduction in the slope of the ozone versus temperature relationship before and after major emission reductions is also well represented by the model. Our results indicate that a global model can reproduce many of the important features of the meteorologically induced ozone variability as well as the emission-driven trends, lending confidence to model projections of future changes in regional surface ozone.

Biomass burning influence on high-latitude tropospheric ozone and reactive nitrogen in summer 2008: a multi-model analysis based on POLMIP simulations

Abstract. We have evaluated tropospheric ozone enhancement in air dominated by biomass burning emissions at high latitudes (> 50° N) in July 2008, using 10 global chemical transport model simulations from the POLMIP multi-model comparison exercise. In model air masses dominated by fire emissions, ΔO3/ΔCO values ranged between 0.039 and 0.196 ppbv ppbv−1 (mean: 0.113 ppbv ppbv−1) in freshly fire-influenced air, and between 0.140 and 0.261 ppbv ppbv−1 (mean: 0.193 ppbv) in more aged fire-influenced air. These values are in broad agreement with the range of observational estimates from the literature. Model ΔPAN/ΔCO enhancement ratios show distinct groupings according to the meteorological data used to drive the models. ECMWF-forced models produce larger ΔPAN/ΔCO values (4.47 to 7.00 pptv ppbv−1) than GEOS5-forced models (1.87 to 3.28 pptv ppbv−1), which we show is likely linked to differences in efficiency of vertical transport during poleward export from mid-latitude source regions. Simulations of a large plume of biomass burning and anthropogenic emissions exported from towards the Arctic using a Lagrangian chemical transport model show that 4-day net ozone change in the plume is sensitive to differences in plume chemical composition and plume vertical position among the POLMIP models. In particular, Arctic ozone evolution in the plume is highly sensitive to initial concentrations of PAN, as well as oxygenated VOCs (acetone, acetaldehyde), due to their role in producing the peroxyacetyl radical PAN precursor. Vertical displacement is also important due to its effects on the stability of PAN, and subsequent effect on NOx abundance. In plumes where net ozone production is limited, we find that the lifetime of ozone in the plume is sensitive to hydrogen peroxide loading, due to the production of HOx from peroxide photolysis, and the key role of HO2 + O3 in controlling ozone loss. Overall, our results suggest that emissions from biomass burning lead to large-scale photochemical enhancement in high-latitude tropospheric ozone during summer.

A 3D simulation of the early winter distribution of reactive chlorine in the north polar vortex

This paper presents the results of 3D simulations of the formation of reactive chlorine on polar stratospheric clouds in the southern polar vortex. The purpose behind these simulations is to compare calculations with measurements of the microwave limb sounder (MLS) carried on the upper atmosphere research satellite (UARS), which showed regions of enhanced ClO in early December 1991, in regions south of areas where temperatures would support the formation of polar stratospheric clouds. The presently accepted model is that reactive chlorine is formed by rapid chemical reactions on the surfaces of particles in polar stratospheric clouds, from gases such as HCl and ClONO[sub 2]. It is then converted to ClO by photochemical processes. The simulations look at cyclonic and anticyclonic circulation patterns in the region of polar stratospheric cloud formation, and the impact this circulation has on the transport of reactive chlorine northward or southward from its creation to regions where it is converted to ClO.

Measuring and modeling the lifetime of nitrous oxide including its variability

Abstract The lifetime of nitrous oxide, the third‐most‐important human‐emitted greenhouse gas, is based to date primarily on model studies or scaling to other gases. This work calculates a semiempirical lifetime based on Microwave Limb Sounder satellite measurements of stratospheric profiles of nitrous oxide, ozone, and temperature; laboratory cross‐section data for ozone and molecular oxygen plus kinetics for O(1D); the observed solar spectrum; and a simple radiative transfer model. The result is 116 ± 9 years. The observed monthly‐to‐biennial variations in lifetime and tropical abundance are well matched by four independent chemistry‐transport models driven by reanalysis meteorological fields for the period of observation (2005–2010), but all these models overestimate the lifetime due to lower abundances in the critical loss region near 32 km in the tropics. These models plus a chemistry‐climate model agree on the nitrous oxide feedback factor on its own lifetime of 0.94 ± 0.01, giving N2O perturbations an effective residence time of 109 years. Combining this new empirical lifetime with model estimates of residence time and preindustrial lifetime (123 years) adjusts our best estimates of the human‐natural balance of emissions today and improves the accuracy of projected nitrous oxide increases over this century.

Wintertime Nitric Acid Chemistry: Implications from Three-Dimensional Model Calculations

Abstract A three-dimensional simulation of the evolution of HNO3 has been run for the winter of 1979. Winds and temperatures are taken from a stratospheric data assimilation analysis, and the chemistry is based on Limb Infrared Monitor of the Stratosphere (LIMS) observations. The model is compared to LIMS observations to investigate the problem of “missing” nitric acid chemistry in the winter hemisphere. Both the model and observations support the contention that a nitric acid source is needed outside of the polar vortex and north of the subtropics. Observations show that nitric acid and potential vorticity are uncorrelated in middle latitudes outside the polar vortex. This suggests that HNO3 is not dynamically controlled in middle latitudes. The model shows that given the time scales of conventional chemistry, dynamical control is expected. Therefore, an error exists in the conventional chemistry or additional processes are needed to bring the model and data into agreement. Since the polar vortex is dyna...

The Transit-Time Distribution from the Northern Hemisphere Midlatitude Surface

AbstractThe distribution of transit times from the Northern Hemisphere (NH) midlatitude surface is a fundamental property of tropospheric transport. Here, the authors present an analysis of the transit-time distribution (TTD) since air last contacted the NH midlatitude surface, as simulated by the NASA Global Modeling Initiative Chemistry Transport Model. Throughout the troposphere, the TTD is characterized by young modes and long tails. This results in mean transit times or “mean ages” Γ that are significantly larger than their corresponding modal transit times or “modal ages” τmode, especially in the NH, where Γ ≈ 0.5 yr, while τmode < 20 days. In addition, the shape of the TTD changes throughout the troposphere as the ratio of the spectral width Δ—the second temporal moment of the TTD—to the mean age decreases sharply in the NH from ~2.5 at NH high latitudes to ~0.7 in the Southern Hemisphere (SH). Decreases in Δ/Γ in the SH reflect a narrowing of the TTD relative to its mean and physically correspond ...

An observationally constrained evaluation of the oxidative capacity in the tropical western Pacific troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January–February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO + NO2) by a factor of 2, resulting in OHCOL ~30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January–February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP.

Origins of tropospheric ozone interannual variation over Réunion: A model investigation

Observations from long-term ozonesonde measurements show robust variations and trends in the evolution of ozone in the middle and upper troposphere over Réunion Island (21.1°S, 55.5°E) in June-August. Here we examine possible causes of the observed ozone variation at Réunion Island using hindcast simulations by the stratosphere-troposphere Global Modeling Initiative chemical transport model (GMI-CTM) for 1992-2014, driven by assimilated Modern-Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields. Réunion Island is at the edge of the subtropical jet, a region of strong stratospheric-tropospheric exchange (STE). Our analysis implies that the large interannual variation (IAV) of upper tropospheric ozone over Réunion is driven by the large IAV of the stratospheric influence. The IAV of the large-scale, quasi-horizontal wind patterns also contributes to the IAV of ozone in the upper troposphere. Comparison to a simulation with constant emissions indicates that increasing emissions do not lead to the maximum trend in the middle and upper troposphere over Réunion during austral winter implied by the sonde data. The effects of increasing emission over southern Africa are limited to the lower troposphere near the surface in August - September.