Dry deposition at the Earth's surface is an important sink of atmospheric ozone. Currently, dry deposition of ozone to the ocean surface in atmospheric chemistry models has the largest uncertainty ...compared to deposition to other surface types, with implications for global tropospheric ozone budget and associated radiative forcing. Most global models assume that the dominant term of surface resistance in the parameterisation of ozone dry deposition velocity at the oceanic surface is constant. There have been recent mechanistic parameterisations for air–sea exchange that account for the simultaneous waterside processes of ozone solubility, molecular diffusion, turbulent transfer, and first-order chemical reaction of ozone with dissolved iodide and other compounds, but there are questions about their performance and consistency. We present a new two-layer parameterisation scheme for the oceanic surface resistance by making the following realistic assumptions: (a) the thickness of the top water layer is of the order of a reaction–diffusion length scale (a few micrometres) within which ozone loss is dominated by chemical reaction and the influence of waterside turbulent transfer is negligible; (b) in the water layer below, both chemical reaction and waterside turbulent transfer act together and are accounted for; and (c) chemical reactivity is present through the depth of the oceanic mixing layer. The new parameterisation has been evaluated against dry deposition velocities from recent open-ocean measurements. It is found that the inclusion of only the aqueous iodide–ozone reaction satisfactorily describes the measurements. In order to better quantify the global dry deposition loss and its interannual variability, modelled 3-hourly ozone deposition velocities are combined with the 3-hourly MACC (Monitoring Atmospheric Composition and Climate) reanalysis ozone for the years 2003–2012. The resulting ozone dry deposition is found to be 98.4 ± 30.0 Tg O3 yr−1 for the ocean and 722.8 ± 87.3 Tg O3 yr−1 globally. The new estimate of the ocean component is approximately a third of the current model estimates. This reduction corresponds to an approximately 20 % decrease in the total global ozone dry deposition, which (with all other components being unchanged) is equivalent to an increase of approximately 5 % in the modelled tropospheric ozone burden and a similar increase in tropospheric ozone lifetime.
Tropospheric ozone in CMIP6 simulations Griffiths, Paul T; Murray, Lee T; Zeng, Guang ...
Atmospheric chemistry and physics,
03/2021, Letnik:
21, Številka:
5
Journal Article
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The evolution of tropospheric ozone from 1850 to 2100 has been studied using data from Phase 6 of the Coupled Model Intercomparison Project (CMIP6). We evaluate long-term changes using coupled ...atmosphere–ocean chemistry–climate models, focusing on the CMIP Historical and ScenarioMIP ssp370 experiments, for which detailed tropospheric-ozone diagnostics were archived. The model ensemble has been evaluated against a suite of surface, sonde and satellite observations of the past several decades and found to reproduce well the salient spatial, seasonal and decadal variability and trends. The multi-model mean tropospheric-ozone burden increases from 247 ± 36 Tg in 1850 to a mean value of 356 ± 31 Tg for the period 2005–2014, an increase of 44 %. Modelled present-day values agree well with previous determinations (ACCENT: 336 ± 27 Tg; Atmospheric Chemistry and Climate Model Intercomparison Project, ACCMIP: 337 ± 23 Tg; Tropospheric Ozone Assessment Report, TOAR: 340 ± 34 Tg). In the ssp370 experiments, the ozone burden increases to 416 ± 35 Tg by 2100. The ozone budget has been examined over the same period using lumped ozone production (PO3) and loss (LO3) diagnostics. Both ozone production and chemical loss terms increase steadily over the period 1850 to 2100, with net chemical production (PO3-LO3) reaching a maximum around the year 2000. The residual term, which contains contributions from stratosphere–troposphere transport reaches a minimum around the same time before recovering in the 21st century, while dry deposition increases steadily over the period 1850–2100. Differences between the model residual terms are explained in terms of variation in tropopause height and stratospheric ozone burden.
We investigated the radiative impact of recent process-based improvements to oceanic ozone (O3) dry deposition parameterisation and empirical improvements to lightning-generated oxides of nitrogen ...(LNOx) parameterisation by conducting a 5-year simulation of the Australian Community Climate and Earth System Simulator – United Kingdom Chemistry and Aerosol (ACCESS-UKCA) global chemistry–climate model, with radiative effects of O3, methane (CH4) and aerosol included. Compared to the base parameterisations, the global consequences of the two improved parameterisations on atmospheric composition are dominated by theLNOx change (which increases the LNOx production from 4.8 to 6.9 Tg N yr-1) and include (a) an increase in the O3 column of 3.75 DU, and this O3 change is centred on the tropical upper troposphere where O3 is most effective as a radiative forcer; (b) a decrease of 0.64 years in the atmospheric lifetime of CH4 due to an increase in hydroxyl radical, which corresponds to a decrease of 0.31 years in the CH4 lifetime per Tg N yr-1 change in LNOx; (c) an increase of 6.7 % in the column integrated condensation nuclei concentration; and (d) a slight increase in high-level cloud cover. The two combined parameterisation changes cause an increase of 86.3 mW m-2 in the globally-averaged all-sky net downward top-of-atmosphere (TOA) radiative flux (which is akin to instantaneous radiative forcing), and only 5 % of which is due to the dry deposition parameterisation change. Other global radiative changes from the use of the two parameterisations together include an increase in the downward longwave radiation and a decrease in the downward shortwave radiation at the earth's surface. The indirect effect of LNOx on aerosol and cloud cover can at least partly explain the differences in the downward shortwave flux at the surface. It is demonstrated that although the total global LNOx production may be the same, how LNOx is distributed spatially makes a difference to radiative transfer. We estimate that for a reported uncertainty range of 5±3 Tg N yr-1 in global estimates of LNOx, the uncertainty in the net downward TOA radiation is ±119 mW m-2. The corresponding uncertainly in the atmospheric methane lifetime is ±0.92 years. Thus, the value of LNOx used within a model will influence the effective radiative forcing (ERF) and global warming potential (GWP) of anthropogenic CH4, and influence the results of climate scenario modelling.
Schemes used to parameterise ozone dry deposition velocity at the oceanic surface mainly differ in terms of how the dominant term of surface resistance is parameterised. We examine three such schemes ...and test them in a global climate–chemistry model that incorporates meteorological nudging and monthly-varying reactive-gas emissions. The default scheme invokes the commonly used assumption that the water surface resistance is constant. The other two schemes, named the one-layer and two-layer reactivity schemes, include the simultaneous influence on the water surface resistance of ozone solubility in water, waterside molecular diffusion and turbulent transfer, and a first-order chemical reaction of ozone with dissolved iodide. Unlike the one-layer scheme, the two-layer scheme can indirectly control the degree of interaction between chemical reaction and turbulent transfer through the specification of a surface reactive layer thickness. A comparison is made of the modelled deposition velocity dependencies on sea surface temperature (SST) and wind speed with recently reported cruise-based observations. The default scheme overestimates the observed deposition velocities by a factor of 2–4 when the chemical reaction is slow (e.g. under colder SSTs in the Southern Ocean). The default scheme has almost no temperature, wind speed, or latitudinal variations in contrast with the observations. The one-layer scheme provides noticeably better variations, but it overestimates deposition velocity by a factor of 2–3 due to an enhancement of the interaction between chemical reaction and turbulent transfer. The two-layer scheme with a surface reactive layer thickness specification of 2.5 µm, which is approximately equal to the reaction-diffusive length scale of the ozone–iodide reaction, is able to simulate the field measurements most closely with respect to absolute values as well as SST and wind-speed dependence. The annual global oceanic deposition of ozone determined using this scheme is approximately half of the original oceanic deposition obtained using the default scheme, and it corresponds to a 10 % decrease in the original estimate of the total global ozone deposition. The previously reported modelled estimate of oceanic deposition is roughly one-third of total deposition and with this new parameterisation it is reduced to 12 % of the modelled total global ozone deposition. Deposition parameterisation influences the predicted atmospheric ozone mixing ratios, especially in the Southern Hemisphere. For the latitudes 45–70° S, the two-layer scheme improves the prediction of ozone observed at an altitude of 1 km by 7 % and that within the altitude range 1–6 km by 5 % compared to the default scheme.
Although lightning-generated oxides of nitrogen (LNOx) account for only approximately 10 % of the global NOx source, they have a disproportionately large impact on tropospheric photochemistry due to ...the conducive conditions in the tropical upper troposphere where lightning is mostly discharged. In most global composition models, lightning flash rates used to calculate LNOx are expressed in terms of convective cloud-top height via the Price and Rind (1992) (PR92) parameterisations for land and ocean, where the oceanic parameterisation is known to greatly underestimate flash rates. We conduct a critical assessment of flash-rate parameterisations that are based on cloud-top height and validate them within the Australian Community Climate and Earth System Simulator – United Kingdom Chemistry and Aerosol (ACCESS-UKCA) global chemistry–climate model using the Lightning Imaging Sensor and Optical Transient Detector (LIS/OTD) satellite data. While the PR92 parameterisation for land yields satisfactory predictions, the oceanic parameterisation, as expected, underestimates the observed flash-rate density severely, yielding a global average over the ocean of 0.33 flashes s-1 compared to the observed 9.16 flashes s-1 and leading to LNOx being underestimated proportionally. We formulate new flash-rate parameterisations following Boccippio's (2002) scaling relationships between thunderstorm electrical generator power and storm geometry coupled with available data. The new parameterisation for land performs very similarly to the corresponding PR92 one, as would be expected, whereas the new oceanic parameterisation simulates the flash-rate observations much more accurately, giving a global average over the ocean of 8.84 flashes s-1. The use of the improved flash-rate parameterisations in ACCESS-UKCA changes the modelled tropospheric composition – global LNOx increases from 4.8 to 6.6 Tg N yr-1; the ozone (O3) burden increases by 8.5 %; there is an increase in the mid- to upper-tropospheric NOx by as much as 40 pptv, a 13 % increase in the global hydroxyl radical (OH), a decrease in the methane lifetime by 6.7 %, and a decrease in the lower-tropospheric carbon monoxide (CO) by 3 %–7 %. Compared to observations, the modelled tropospheric NOx and ozone in the Southern Hemisphere and over the ocean are improved by this new flash-rate parameterisation.
The biogenic emissions of isoprene and monoterpenes are one of the main drivers of atmospheric photochemistry, including oxidant and secondary organic aerosol production. In this paper, the emission ...rates of isoprene and monoterpenes from Australian vegetation are investigated for the first time using the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGANv2.1); the CSIRO chemical transport model; and atmospheric observations of isoprene, monoterpenes and isoprene oxidation products (methacrolein and methyl vinyl ketone). Observations from four field campaigns during three different seasons are used, covering urban, coastal suburban and inland forest areas. The observed concentrations of isoprene and monoterpenes were of a broadly similar magnitude, which may indicate that southeast Australia holds an unusual position where neither chemical species dominates. The model results overestimate the observed atmospheric concentrations of isoprene (up to a factor of 6) and underestimate the monoterpene concentrations (up to a factor of 4). This may occur because the emission rates currently used in MEGANv2.1 for Australia are drawn mainly from young eucalypt trees (< 7 years), which may emit more isoprene than adult trees. There is no single increase/decrease factor for the emissions which suits all seasons and conditions studied. There is a need for further field measurements of in situ isoprene and monoterpene emission fluxes in Australia.
From the earliest observations of ozone in the lower atmosphere in the 19th century, both measurement methods and the portion of the globe observed have evolved and changed. These methods have ...different uncertainties and biases, and the data records differ with respect to coverage (space and time), information content, and representativeness. In this study, various ozone measurement methods and ozone datasets are reviewed and selected for inclusion in the historical record of background ozone levels, based on relationship of the measurement technique to the modern UV absorption standard, absence of interfering pollutants, representativeness of the well-mixed boundary layer and expert judgement of their credibility. There are significant uncertainties with the 19th and early 20th-century measurements related to interference of other gases. Spectroscopic methods applied before 1960 have likely underestimated ozone by as much as 11% at the surface and by about 24% in the free troposphere, due to the use of differing ozone absorption coefficients. There is no unambiguous evidence in the measurement record back to 1896 that typical mid-latitude background surface ozone values were below about 20 nmol mol–1, but there is robust evidence for increases in the temperate and polar regions of the northern hemisphere of 30–70%, with large uncertainty, between the period of historic observations, 1896–1975, and the modern period (1990–2014). Independent historical observations from balloons and aircraft indicate similar changes in the free troposphere. Changes in the southern hemisphere are much less. Regional representativeness of the available observations remains a potential source of large errors, which are difficult to quantify. The great majority of validation and intercomparison studies of free tropospheric ozone measurement methods use ECC ozonesondes as reference. Compared to UV-absorption measurements they show a modest (~1–5% ±5%) high bias in the troposphere, but no evidence of a change with time. Umkehr, lidar, and FTIR methods all show modest low biases relative to ECCs, and so, using ECC sondes as a transfer standard, all appear to agree to within one standard deviation with the modern UV-absorption standard. Other sonde types show an increase of 5–20% in sensitivity to tropospheric ozone from 1970–1995. Biases and standard deviations of satellite retrieval comparisons are often 2–3 times larger than those of other free tropospheric measurements. The lack of information on temporal changes of bias for satellite measurements of tropospheric ozone is an area of concern for long-term trend studies.
Marine boundary layer ozone seasonal cycles have been quantified by fitting the sum of two sine curves through monthly detrended observations taken at three stations: Mace Head, Ireland, and Trinidad ...Head, California, in the Northern Hemisphere and Cape Grim, Tasmania, in the Southern Hemisphere. The parameters defining the sine curve fits at these stations have been compared with those from a global Lagrangian chemistry‐transport model and from 14 Atmospheric Chemistry Coupled Climate Model Intercomparison Project chemistry‐climate models. Most models substantially overestimated the long‐term average ozone levels at Trinidad Head, while they performed much better for Mace Head and Cape Grim. This led to an underestimation of the observed (North Atlantic inflow‐North Pacific inflow) difference. The models generally underpredicted the magnitude of the fundamental term of the fitted seasonal cycle, most strongly at Cape Grim. The models more accurately reproduced the observed second harmonic terms compared to the fundamental terms at all stations. Significant correlations have been identified between the errors in the different models' estimates of the seasonal cycle parameters; these correlations may yield further insights into the causes of the model‐measurement discrepancies.
Key Points
Observed and modeled ozone seasonal cycles can be quantified by fitting sine curves
Models tend to overestimate ozone in Northern Hemisphere midlatitude marine boundary layers
Fundamental and second harmonic terms are not always well simulated by models
One of the key challenges in atmospheric chemistry is to reduce the uncertainty of biogenic volatile organic compound (BVOC) emission estimates from vegetation to the atmosphere. In Australia, ...eucalypt trees are a primary source of biogenic emissions, but their contribution to Australian air sheds is poorly quantified. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) has performed poorly against Australian isoprene and monoterpene observations. Finding reasons for the MEGAN discrepancies and strengthening our understanding of biogenic emissions in this region is our focus. We compare MEGAN to the locally produced Australian Biogenic Canopy and Grass Emissions Model (ABCGEM), to identify the uncertainties associated with the emission estimates and the data requirements necessary to improve isoprene and monoterpene emissions estimates for the application of MEGAN in Australia. Previously unpublished, ABCGEM is applied as an online biogenic emissions inventory to model BVOCs in the air shed overlaying Sydney, Australia. The two models use the same meteorological inputs and chemical mechanism, but independent inputs of leaf area index (LAI), plant functional type (PFT) and emission factors. We find that LAI, a proxy for leaf biomass, has a small role in spatial, temporal and inter-model biogenic emission variability, particularly in urban areas for ABCGEM. After removing LAI as the source of the differences, we found large differences in the emission activity function for monoterpenes. In MEGAN monoterpenes are partially light dependent, reducing their dependence on temperature. In ABCGEM monoterpenes are not light dependent, meaning they continue to be emitted at high rates during hot summer days, and at night. When the light dependence of monoterpenes is switched off in MEGAN, night-time emissions increase by 90–100 % improving the comparison with observations, suggesting the possibility that monoterpenes emitted from Australian vegetation may not be as light dependent as vegetation globally. Targeted measurements of emissions from in situ Australian vegetation, particularly of the light dependence issue are critical to improving MEGAN for one of the world's major biogenic emitting regions.
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