Ruth M. Doherty

Multimodel ensemble simulations of present-day and near-future tropospheric ozone

Global tropospheric ozone distributions, budgets, and radiative forcings from an ensemble of 26 state-of-the-art atmospheric chemistry models have been intercompared and synthesized as part of a wider study into both the air quality and climate roles of ozone. Results from three 2030 emissions scenarios, broadly representing optimistic, likely, and pessimistic options, are compared to a base year 2000 simulation. This base case realistically represents the current global distribution of tropospheric ozone. A further set of simulations considers the influence of climate change over the same time period by forcing the central emissions scenario with a surface warming of around 0.7K. The use of a large multimodel ensemble allows us to identify key areas of uncertainty and improves the robustness of the results. Ensemble mean changes in tropospheric ozone burden between 2000 and 2030 for the 3 scenarios range from a 5% decrease, through a 6% increase, to a 15% increase. The intermodel uncertainty (±1 standard deviation) associated with these values is about ±25%. Model outliers have no significant influence on the ensemble mean results. Combining ozone and methane changes, the three scenarios produce radiative forcings of -50, 180, and 300 mW m-2, compared to a CO 2 forcing over the same time period of 800-1100 mW m-2. These values indicate the importance of air pollution emissions in short- to medium-term climate forcing and the potential for stringent/lax control measures to improve/worsen future climate forcing. The model sensitivity of ozone to imposed climate change varies between models but modulates zonal mean mixing ratios by ±5 ppbv via a variety of feedback mechanisms, in particular those involving water vapor and stratosphere-troposphere exchange. This level of climate change also reduces the methane lifetime by around 4%. The ensemble mean year 2000 tropospheric ozone budget indicates chemical production, chemical destruction, dry deposition and stratospheric input fluxes of 5100, 4650, 1000 and 550 Tg(O 3 ) yr-1, respectively. These values are significantly different to the mean budget documented by the Intergovernmental Panel on Climate Change (IPCC) Third Assessment Report (TAR). The mean ozone burden (340 Tg(O 3 )) is 10% larger than the IPCC TAR estimate, while the mean ozone lifetime (22 days) is 10% shorter. Results from individual models show a correlation between ozone burden and lifetime, and each models ozone burden and lifetime respond in similar ways across the emissions scenarios. The response to climate change is much less consistent. Models show more variability in the tropics compared to midlatitudes. Some of the most uncertain areas of the models include treatments of deep tropical convection, including lightning NO x production; isoprene emissions from vegetation and isoprenes degradation chemistry; stratosphere-troposphere exchange; biomass burning; and water vapor concentrations. Copyright 2006 by the American Geophysical Union.

Nitrogen and sulfur deposition on regional and global scales: A multimodel evaluation

We use 23 atmospheric chemistry transport models to calculate current and future (2030) deposition of reactive nitrogen (NOy, NHx) and sulfate (SOx) to land and ocean surfaces. The models are driven by three emission scenarios: (1) current air quality legislation (CLE); (2) an optimistic case of the maximum emissions reductions currently technologically feasible (MFR); and (3) the contrasting pessimistic IPCC SRES A2 scenario. An extensive evaluation of the present-day deposition using nearly all information on wet deposition available worldwide shows a good agreement with observations in Europe and North America, where 60–70% of the model-calculated wet deposition rates agree to within ±50% with quality-controlled measurements. Models systematically overestimate NHx deposition in South Asia, and underestimate NOy deposition in East Asia. We show that there are substantial differences among models for the removal mechanisms of NOy, NHx, and SOx, leading to ±1 σ variance in total deposition fluxes of about 30% in the anthropogenic emissions regions, and up to a factor of 2 outside. In all cases the mean model constructed from the ensemble calculations is among the best when comparing to measurements. Currently, 36–51% of all NOy, NHx, and SOx is deposited over the ocean, and 50–80% of the fraction of deposition on land falls on natural (nonagricultural) vegetation. Currently, 11% of the worlds natural vegetation receives nitrogen deposition in excess of the “critical load” threshold of 1000 mg(N) m−2 yr−1. The regions most affected are the United States (20% of vegetation), western Europe (30%), eastern Europe (80%), South Asia (60%), East Asia (40%), southeast Asia (30%), and Japan (50%). Future deposition fluxes are mainly driven by changes in emissions, and less importantly by changes in atmospheric chemistry and climate. The global fraction of vegetation exposed to nitrogen loads in excess of 1000 mg(N) m−2 yr−1 increases globally to 17% for CLE and 25% for A2. In MFR, the reductions in NOy are offset by further increases for NHx deposition. The regions most affected by exceedingly high nitrogen loads for CLE and A2 are Europe and Asia, but also parts of Africa.

Multimodel simulations of carbon monoxide: Comparison with observations and projected near-future changes

We analyze present-day and future carbon monoxide (CO) simulations in 26 state-of-the-art atmospheric chemistry models run to study future air quality and climate change. In comparison with near-global satellite observations from the MOPITT instrument and local surface measurements, the models show large underestimates of Northern Hemisphere (NH) extratropical CO, while typically performing reasonably well elsewhere. The results suggest that year-round emissions, probably from fossil fuel burning in east Asia and seasonal biomass burning emissions in south-central Africa, are greatly underestimated in current inventories such as IIASA and EDGAR3.2. Variability among models is large, likely resulting primarily from intermodel differences in representations and emissions of nonmethane volatile organic compounds (NMVOCs) and in hydrologic cycles, which affect OH and soluble hydrocarbon intermediates. Global mean projections of the 2030 CO response to emissions changes are quite robust. Global mean midtropospheric (500 hPa) CO increases by 12.6 ± 3.5 ppbv (16%) for the high-emissions (A2) scenario, by 1.7 ± 1.8 ppbv (2%) for the midrange (CLE) scenario, and decreases by 8.1 ± 2.3 ppbv (11%) for the low-emissions (MFR) scenario. Projected 2030 climate changes decrease global 500 hPa CO by 1.4 ± 1.4 ppbv. Local changes can be much larger. In response to climate change, substantial effects are seen in the tropics, but intermodel variability is quite large. The regional CO responses to emissions changes are robust across models, however. These range from decreases of 10–20 ppbv over much of the industrialized NH for the CLE scenario to CO increases worldwide and year-round under A2, with the largest changes over central Africa (20–30 ppbv), southern Brazil (20–35 ppbv) and south and east Asia (30–70 ppbv). The trajectory of future emissions thus has the potential to profoundly affect air quality over most of the worlds populated areas.

Global premature mortality due to anthropogenic outdoor air pollution and the contribution of past climate change

Increased concentrations of ozone and fine particulate matter (PM2.5) since preindustrial times reflect increased emissions, but also contributions of past climate change. Here we use modeled concentrations from an ensemble of chemistry?climate models to estimate the global burden of anthropogenic outdoor air pollution on present-day premature human mortality, and the component of that burden attributable to past climate change. Using simulated concentrations for 2000 and 1850 and concentration?response functions (CRFs), we estimate that, at present, 470?000 (95% confidence interval, 140?000 to 900?000) premature respiratory deaths are associated globally and annually with anthropogenic ozone, and 2.1 (1.3 to 3.0) million deaths with anthropogenic PM2.5-related cardiopulmonary diseases (93%) and lung cancer (7%). These estimates are smaller than ones from previous studies because we use modeled 1850 air pollution rather than a counterfactual low concentration, and because of different emissions. Uncertainty in CRFs contributes more to overall uncertainty than the spread of model results. Mortality attributed to the effects of past climate change on air quality is considerably smaller than the global burden: 1500 (?20?000 to 27?000) deaths yr?1 due to ozone and 2200 (?350?000 to 140?000) due to PM2.5. The small multi-model means are coincidental, as there are larger ranges of results for individual models, reflected in the large uncertainties, with some models suggesting that past climate change has reduced air pollution mortality.

Hydrogen bonding. Part 13. A new method for the characterisation of GLC stationary phases—the laffort data set

A number of equations for the correlation of retention data for a series of solutes on a given stationary phase (or solvent) have been investigated with the aim of characterising stationary phases. The two most successful equations are, SP =c+dδ2+sπ2*+aα2H+bβ2H+I log L16(a), SP =c+rR2+sπ2*+aα2H+bβ2H+I log L16(b) In the present case the dependent variable SP is log L– log LDecane and the explanatory variables are solute parameters as follows: δ2 is an empirical polarisability correction term, R2 is a polarisability parameter that reflects the ability of a solute to interact with a solvent through π and n electron pairs, α2H is the solute hydrogen–bond acidity, β2H is the solute hydrogen–bond basicity, π2* is the solute dipolarity/polarisability, and L16 is the Ostwald solubility coefficient of the solute on n-hexadecane at 298 K. The constants c, r, s, a, b, and l in the more useful equation (b) are found by the method of multiple linear regression analysis, and serve to characterise a solvent phase in terms of specific solute/solvent interactions. Application of equation (b) to the five stationary phases examined by Laffort et al. shows that the magnitude of these constants is in accord with general chemical principles, and that the present procedure constitutes a new, general method for the characterisation of gas chromatographic stationary phases.

Solubility properties in polymers and biological media. 7. An analysis of toxicant properties that influence inhibition of bioluminescence in Photobacterium phosphoreum (the Microtox test).

Inhibition of bioluminescence in Photobacterium phosphoreum (the Microtox test) has been proposed as a cost-effective prescreening procedure to eliminate the relatively more innocuous chemicals from testing programs for toxicities of organic chemicals to fish. The biological response, as a function of toxicant properties, is given by log EC/sub 50/ (in ..mu..molL) = 7.61 - 4.11 anti V100 - 1.54 ..pi..* + 3.94..beta.. - 1.51..cap alpha../sub m/ n = 38, r = 0.987, SD = 0.28 where anti V is the solute molar volume and ..pi..*, ..beta.., and ..cap alpha../sub m/ are the solvatochromic parameters that measure dipolaritypolarizability, hydrogen-bond acceptor basicity, and hydrogen-bond donor acidity of the solute (toxicant). The above equation applies to compounds that act by a nonreactive toxicity mechanism, and it is suggested that for certain compounds, which are outliers relative to the above equation, reactive toxicity properties mask the effects of the nonreactive mechanism. The above equation is compared with a correlation of log EC/sub 50/ with octanolwater partition coefficients. 25 references, 2 figures, 2 tables.

Impacts of climate change and variability on tropospheric ozone and its precursors

Two coupled climate-chemistry model experiments for the period 1990-2030 were conducted: one with a fixed climate and the other with a varying climate forced by the is92a scenario. By comparing results from these experiments we have attempted to identify changes and variations in physical climate that may have important influences upon tropospheric chemical composition. Climate variables considered include: temperature, humidity, convective mass fluxes, precipitation, and the large-scale circulation. Increases in humidity, directly related to increases in temperature, exert a major influence on the budgets of ozone and the hydroxyl radical: decreasing 03 and increasing OH. Warming enhances decomposition of PAN, releasing NOx, and increases the rate of methane oxidation. Surface warming enhances vegetation emissions of isoprene, an important ozone precursor. In the changed climate, tropical convection generally reduces, but penetrates to higher levels. Over northern continents, convection tends to increase. These changes in convection affect both vertical mixing and lightning NOx emissions. We find no global trend in lightning emissions, but significant changes in its distribution. Changes in precipitation and the large-scale circulation are less important for composition, at least in these experiments. Higher levels of the oxidants OH and H202 lead to increases in aerosol formation and concentrations. These results indicate that climate-chemistry feedbacks are dominantly negative (less 03, a shorter CH4 lifetime, and more aerosol). The major mode of inter-annual variability in the is92a climate experiment is ENSO. This strongly modulates isoprene emissions from vegetation via tropical land surface temperatures. ENSO is also clearly the dominant source of variability in tropical column ozone, mainly through changes in the distribution of convection. The magnitude of inter-annual variability in ozone is comparable to the changes brought about by emissions and climate changes between the 1990s and 2020s, suggesting that it will be difficult to disentangle the different components of near-future changes.

GCM simulations of the Indian Ocean dipole influence on East African rainfall: Present and future

Six coupled GCMs are assessed in terms of their ability to simulate observed characteristics of East African rainfall, the Indian Ocean dipole and their temporal correlation. Model results are then used to analyze the future behaviour of rainfall and the DMI. All models simulate reasonably well the spatial distribution and variability of annual and seasonal rainfall over the 1961–1990 period. Model simulation of observed DMI characteristics is less consistent with observations, however, five models reproduce similar correlations to those observed between the DMI and East African short rains (SON). In the future, there are no clear inter-model patterns of rainfall or DMI behaviour. In this sample of models four (two) out of six simulate modest increases (decreases) in annual rainfall by the 2080s. For SON, three of the six models indicate a trend towards increasingly positive phase of the DMI, two indicate a decrease and one shows no substantial change.

A multi‐model study of the hemispheric transport and deposition of oxidised nitrogen

Fifteen chemistry-transport models are used to quantify, for the first time, the export of oxidised nitrogen (NOy) to and from four regions (Europe, North America, South Asia, and East Asia), and to estimate the uncertainty in the results. Between 12 and 24% of the NOx emitted is exported from each region annually. The strongest impact of each source region on a foreign region is: Europe on East Asia, North America on Europe, South Asia on East Asia, and East Asia on North America. Europe exports the most NOy, and East Asia the least. East Asia receives the most NOy from the other regions. Between 8 and 15% of NOx emitted in each region is transported over distances larger than 1000 km, with 3–10% ultimately deposited over the foreign regions.

Ozone, heat and mortality: acute effects in 15 British conurbations

Background Acute associations between mortality and ozone are largely accepted, though recent evidence is less conclusive. Evidence on ozone–heat interaction is sparse. We assess effects of ozone, heat, and their interaction, on mortality in Britain. Methods Acute effects of summer ozone on mortality were estimated using data from 15 conurbations in England and Wales (May–September, 1993–2003). 2-day means of daily maximum 8-h ozone were entered into case series analyses, controlling for particulate matter with aerodynamic diameter of <10 μm, natural cubic splines of temperature, and other factors. Heat effects were estimated, comparing adjusted mortality rates at 97.5th and 75th percentiles of 2-day mean temperature. A separate model employed interaction terms to assess whether ozone effects increased on ‘hot days’ (where 2-day mean temperature exceeded the whole-year 95th percentile). Other heat metrics, and non-linear ozone effects, were also examined. Results Adverse ozone and heat effects occurred in nearly all conurbations. The mean mortality rate ratio for heat effect across conurbations was 1.071 (1.050–1.093). The mean ozone rate ratio was 1.003 per 10 μg/m3 ozone increase (95% CI 1.001 to 1.005). On ‘hot days’ the mean ozone effect reached 1.006 (1.002–1.009) per 10 μg/m3, though ozone–heat interaction was significant in London only. On substituting maximum for mean temperature, the overall ozone effect reduced to null, though evidence remained of effects on hot days, particularly in London. An estimated ozone effect threshold was below current guidelines in ‘mean temperature’ models. Conclusion While heat showed robust effects on summer mortality, estimates for ozone depended upon the modelling of temperature. However, there was some evidence that ozone effects were worse on hot days, whichever temperature measure was used.