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An advanced scheme for wet scavenging and liquid-phase chemistry in a regional online-coupled chemistry transport model

Clouds are reaction chambers for atmospheric trace gases and aerosols, and the associated precipitation is a major sink for atmospheric constituents. The regional chemistry-climate model COSMO-ART has been lacking a description of wet scavenging of gases and aqueous-phase chemistry. In this work we present a coupling of COSMO-ART with a wet scavenging and aqueous-phase chemistry scheme. The coupling is made consistent with the cloud microphysics scheme of the underlying meteorological model COSMO. While the choice of the aqueous-chemistry mechanism is flexible, the effects of a simple sulfur oxidation scheme are shown in the application of the coupled system in this work. We give details explaining the coupling and extensions made, then present results from idealized flow-over-hill experiments in a 2-D model setup and finally results from a full 3-D simulation. Comparison against measurement data shows that the scheme efficiently reduces SO2 trace gas concentrations by 0.3 ppbv (−30%) on average, while leaving O3 and NOx unchanged. PM10 aerosol mass was increased by 10% on average. While total PM2.5 changes only little, chemical composition is improved notably. Overestimations of nitrate aerosols are reduced by typically 0.5–1 μg m−3 (up to −2 μg m−3 in the Po Valley) while sulfate mass is increased by 1–1.5 μg m−3 on average (up to 2.5 μg m−3 in Eastern Europe). The effect of cloud processing of aerosols on its size distribution, i.e. a shift towards larger diameters, is observed. Compared against wet deposition measurements the system tends to underestimate the total wet deposited mass for the simulated case study.
The melting level stability anomaly in the tropics

On short timescales, the effect of deep convection on the tropical atmosphere is to heat the upper troposphere and cool the lower troposphere. This stratiform temperature response to deep convection gives rise to a local maximum in stability near the melting level. We use temperature measurements from five radiosonde stations in the Western Tropical Pacific, from the Stratospheric Processes and their Role in Climate (SPARC) archive, to examine the response of this mid-tropospheric stability maximum to changes in surface temperature. We find that the height of the stability maximum increases when the surface temperature increases, by an amount roughly equal to the upward displacement of the 0 °C melting level. Although this response was determined using monthly mean temperature anomalies from an 10 yr record (1999–2008), we use model results to show that a similar response should also be expected on longer timescales.
Measurements of reactive trace gases and variable O3 formation rates in some South Carolina biomass burning plumes

In October–November 2011 we measured trace gas emission factors from seven prescribed fires in South Carolina (SC), US, using two Fourier transform infrared spectrometer (FTIR) systems and whole air sampling (WAS) into canisters followed by gas-chromatographic analysis. A total of 97 trace gas species were quantified from both airborne and ground-based sampling platforms, making this one of the most detailed field studies of fire emissions to date. The measurements include the first emission factors for a suite of monoterpenes produced by heating vegetative fuels during field fires. The first quantitative FTIR observations of limonene in smoke are reported along with an expanded suite of monoterpenes measured by WAS including α-pinene, β-pinene, limonene, camphene, 4-carene, and myrcene. The known chemistry of the monoterpenes and their measured abundance of 0.4–27.9% of non-methane organic compounds (NMOCs) and ~ 21% of organic aerosol (mass basis) suggests that they impacted secondary formation of ozone (O3), aerosols, and small organic trace gases such as methanol and formaldehyde in the sampled plumes in the first few hours after emission. The variability in the initial terpene emissions in the SC fire plumes was high and, in general, the speciation of the initially emitted gas-phase NMOCs was 13–195% different from that observed in a similar study in nominally similar pine forests in North Carolina ~ 20 months earlier. It is likely that differences in stand structure and environmental conditions contributed to the high variability observed within and between these studies. Similar factors may explain much of the variability in initial emissions in the literature. The ΔHCN/ΔCO emission ratio, however, was found to be fairly consistent with previous airborne fire measurements in other coniferous-dominated ecosystems, with the mean for these studies being 0.90 ± 0.06%, further confirming the value of HCN as a biomass burning tracer. The SC results also support an earlier finding that C3-C4 alkynes may be of use as biomass burning indicators on the time-scale of hours to a day. It was possible to measure the downwind chemical evolution of the plume on four of the fires and significant O3 formation (ΔO3/ΔCO from 10–90%) occurred in all of these plumes within two hours. The slowest O3 production was observed on a cloudy day with low co-emission of NOx. The fastest O3 production was observed on a sunny day when the downwind plume almost certainly incorporated significant additional NOx by passing over the Columbia, SC metropolitan area. Due to rapid plume dilution, it was only possible to acquire high-quality downwind data for two other trace gas species (formaldehyde and methanol) during two of the fires. In all four of these cases, significant increases in formaldehyde and methanol were observed in <2 h. This is likely the first direct observation of post-emission methanol production in biomass burning plumes. Post-emission production of methanol does not always happen in young biomass burning plumes, and its occurrence in this study could have involved terpene precursors to a significant extent.
On the use of the correction factor with Japanese ozonesonde data

In submitting data to the World Meteorological Organization (WMO) World Ozone and Ultraviolet Data Center (WOUDC), numerous ozonesonde stations include a correction factor (CF) that multiplies ozone concentration profile data so that the columns computed agree with column measurements from co-located ground-based and/or overpassing satellite instruments. We evaluate this practice through an examination of data from four Japanese ozonesonde stations: Kagoshima, Naha, Sapporo, and Tsukuba. While agreement between the sonde columns and Total Ozone Mapping Spectrometer (TOMS) or Ozone Mapping Instrument (OMI) is improved by use of the CF, agreement between the sonde ozone concentrations reported near the surface and data from surface monitors near the launch sites is negatively impacted. In addition, we find the agreement between the mean sonde columns without the CF and the ground-based Dobson instrument columns is improved by ~1.5 % by using the McPeters et al. (1997) balloon burst climatology rather than the constant mixing ratio assumption (that has been used for the data in the WOUDC archive) for the above burst height column estimate. Limited comparisons of coincident ozonesonde profiles from Hokkaido University with those in the WOUDC database suggest that while the application of the CFs in the stratosphere improves agreement, it negatively impacts the agreement in the troposphere. Finally and importantly, unexplained trends and changing trends in the CFs appear over the last 20 years. The overall trend in the reported CFs for the four Japanese ozonesonde stations from 1990–2010 is (−0.264 &pm; 0.036) × 10−2 yr−1; but from 1993–1999 the trend is (−2.18 &pm; 0.14) × 10−2 yr−1 and from 1999–2009 is (1.089 &pm; 0.075) × 10−2 yr−1, resulting in a statistically significant difference in CF trends between these two periods of (3.26 &pm; 0.16) × 10−2 yr−1. Repeating the analysis using CFs derived from columns computed using the balloon-burst climatology, the trends are somewhat reduced, but remain statistically significant. Given our analysis, we recommend the following: (1) use of the balloon burst climatology is preferred to a constant mixing ratio assumption for determining total column ozone with sonde data; (2) if CFs are applied, their application should probably be restricted to altitudes above the tropopause; (3) only sondes that reach at least 32 km (10.5 hPa) before bursting should be used in data validation and/or ozone trend studies if the constant mixing ratio assumption is used to calculate the above burst column (as is the case for much of the data in the WOUDC archive). Using the balloon burst climatology, sondes that burst above 29 km (~16 hPa), and perhaps lower, can be used; and (4) all ozone trend studies employing Japanese sonde data should be revisited after a careful examination of the impact of the CF on the calculated ozone trends.
High temporal resolution Br2, BrCl and BrO observations in coastal Antarctica

There are few observations of speciated inorganic bromine in polar regions against which to test current theory. Here we report the first high temporal resolution measurements of Br2, BrCl and BrO in coastal Antarctica, made at Halley during spring 2007 using a Chemical Ionisation Mass Spectrometer (CIMS). We find indications for an artefact in daytime BrCl measurements arising from conversion of HOBr, similar to that already identified for observations of Br2 made using a similar CIMS method. Using the MISTRA model, we estimate that the artefact represents a conversion of HOBr to Br2 of the order of several tens of percent, while that for HOBr to BrCl is less but non-negligible. If the artefact is indeed due to HOBr conversion, then nighttime observations were unaffected. It also appears that all daytime BrO observations were artefact-free. Mixing ratios of BrO, Br2 and BrCl ranged from instrumental detection limits to 13 pptv (daytime), 45 pptv (nighttime), and 6 pptv (nighttime), respectively. We see considerable variability in the Br2 and BrCl observations over the measurement period which is strongly linked to the prevailing meteorology, and thus air mass origin. Higher mixing ratios of these species were generally observed when air had passed over the sea-ice zone prior to arrival at Halley, than from over the continent. Variation in the diurnal structure of BrO is linked to previous model work where differences in the photolysis spectra of Br2 and O3 is suggested to lead to a BrO maximum at sunrise and sunset, rather than a noon-time maxima. This suite of Antarctic data provides the first analogue to similar measurements made in the Arctic, and of note is that our maximum measured BrCl (nighttime) is less than half of the maximum measured during a similar period (spring-time) in the Arctic (also nighttime). This difference in maximum measured BrCl may also be the cause of a difference in the Br2 : BrCl ratio between the Arctic and Antarctic. An unusual event of trans-continental air mass transport appears to have been responsible for severe surface ozone depletion observed at Halley over a 2-day period. The halogen source region appears to be the Bellingshausen Sea, to the west of the Antarctic Peninsula, with the air mass having spent 3 1/2 days in complete darkness crossing the continent prior to arrival at Halley.
A new method for measuring optical scattering properties of atmospherically relevant dusts using the Cloud and Aerosol Spectrometer with Polarization (CASPOL)

Atmospheric aerosols have major impacts on regional and global climate through scattering and absorption of solar radiation. A new instrument, the Cloud and Aerosol Spectrometer with Polarization (CASPOL) from Droplet Measurement Technologies measures light scattered by aerosols in the forward (4° to 12°) and backward (168° to 176°) directions, with an additional polarized detector in the backward direction. Scattering by a single particle can be measured by all three detectors for aerosols in a broad range of sizes, 0.6 μm < diameter < 50 μm. The CASPOL is a unique measurement tool, since unlike most in-situ probes, it can measure optical properties on a particle-by-particle basis. In this study, single particle CASPOL measurements for thirteen atmospherically relevant dusts were obtained and their optical scattering signatures were evaluated. In addition, Scanning Electron Microscopy (SEM) was used to characterize the shape and morphology of each type of dust. The total and polarized backscatter intensities varied with particle size for all dust types. Using a new optical signature technique all but one dust type could be categorized into one of three optical scattering groups. Additionally, a composite method was used to derive the optical signature of Arizona Test Dust (ATD) by combining the signatures of its major components. The derived signature was consistent with the measured signature of ATD. Finally, calculated backscattering cross sections for representative dust from each of the three main groups were found to vary by as much as a factor of 7, the difference between the backscattering cross sections of white quartz (5.3 × 10−10 cm−2) and hematite (4.1 × 10−9 cm−2).
Air pollution and associated human mortality: the role of air pollutant emissions, climate change and methane concentration increases from the preindustrial period to present

Increases in surface ozone (O3) and fine particulate matter (≤2.5 μm aerodynamic diameter, PM2.5) are associated with excess premature human mortalities. We estimate changes in surface O3 and PM2.5 from pre-industrial (1860) to present (2000) and the global present-day (2000) premature human mortalities associated with these changes. We extend previous work to differentiate the contribution of changes in three factors: emissions of short-lived air pollutants, climate change, and increased methane (CH4) concentrations, to air pollution levels and associated premature mortalities. We use a coupled chemistry-climate model in conjunction with global population distributions in 2000 to estimate exposure attributable to concentration changes since 1860 from each factor. Attributable mortalities are estimated using health impact functions of long-term relative risk estimates for O3 and PM2.5 from the epidemiology literature. We find global mean surface PM2.5 and health-relevant O3 (defined as the maximum 6-month mean of 1-h daily maximum O3 in a year) have increased by 8 ± 0.16 μg m−3 and 30 ± 0.16 ppbv (results reported as annual average ±standard deviation of 10-yr model simulations), respectively, over this industrial period as a result of combined changes in emissions of air pollutants (EMIS), climate (CLIM) and CH4 concentrations (TCH4). EMIS, CLIM and TCH4 cause global population-weighted average PM2.5 (O3) to change by +7.5 ± 0.19 μg m−3 (+25 ± 0.30 ppbv), +0.4 ± 0.17 μg m−3 (+0.5 ± 0.28 ppbv), and 0.04 ± 0.24 μg m−3 (+4.3 ± 0.33 ppbv), respectively. Total global changes in PM2.5 are associated with 1.5 (95% confidence interval, CI, 1.2–1.8) million cardiopulmonary mortalities and 95 (95% CI, 44–144) thousand lung cancer mortalities annually and changes in O3 are associated with 375 (95% CI, 129–592) thousand respiratory mortalities annually. Most air pollution mortality is driven by changes in emissions of short-lived air pollutants and their precursors (95% and 85% of mortalities from PM2.5 and O3 respectively). However, changing climate and increasing CH4 concentrations also contribute to premature mortality associated with air pollution globally (by up to 5% and 15%, respectively). In some regions, the contribution of climate change and increased CH4 together are responsible for more than 20% of the respiratory mortality associated with O3 exposure. We find the interaction between climate change and atmospheric chemistry has influenced atmospheric composition and human mortality associated with industrial air pollution. Our study highlights the benefits to air quality and human health of CH4 mitigation as a component of future air pollution control policy.
Daily and hourly chemical impact of springtime transboundary aerosols on Japanese air quality

The regular eastward drift of transboundary aerosol intrusions from the Asian mainland into the NW Pacific region has a pervasive impact on air quality in Japan, especially during springtime. Analysis of 24-h filter samples with Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Mass Spectrometry (ICP-MS), and hourly Streaker with Particle Induced X-ray Emission (PIXE) samples collected continuously for six weeks reveal the chemistry of successive waves of natural mineral desert dust ("Kosa") and metalliferous sulphatic pollutants arriving in western Japan during spring 2011. The main aerosol sources recognised by Positive Matrix Factorization (PMF) analysis of Streaker data are mineral dust and fresh sea salt (both mostly in the coarser fraction PM2.5–10), As-bearing sulphatic aerosol (PM0.1–2.5), metalliferous sodic particulate matter (PM) interpreted as aged, industrially contaminated marine aerosol, and ZnCu-bearing aerosols. Whereas mineral dust arrivals are typically highly transient, peaking over a few hours, sulphatic intrusions build up and decline more slowly, and are accompanied by notable rises in ambient concentrations of metallic trace elements such as Pb, As, Zn, Sn and Cd. The magnitude of the loss in regional air quality due to the spread and persistence of pollution from mainland Asia is especially clear when cleansing oceanic air advects westward across Japan, removing the continental influence and reducing concentrations of the undesirable metalliferous pollutants by over 90%. Our new chemical database, especially the Streaker data, demonstrates the rapidly changing complexity of ambient air inhaled during these transboundary events, and implicates Chinese coal combustion as the main source of the anthropogenic aerosol component.
African dust outbreaks over the Mediterranean Basin during 2001–2011: PM10 concentrations, phenomenology and trends, and its relation with synoptic and mesoscale meteorology

The occurrence of African dust outbreaks over the whole Mediterranean Basin has been studied on an 11-yr period (2001–2011). In order to evaluate the impact of such mineral dust outbreaks on ambient concentrations of particulate matter, PM10 data from regional and suburban background sites across the Mediterranean area were compiled. After identifying the daily influence of African dust, a methodology for the estimation of the natural dust contributions on daily PM10 concentrations was applied. Our findings point out that African dust outbreaks are sensibly more frequent in southern sites across the Mediterranean, from 30 to 37% of the annual days, whereas they occur less than 20% of the annual days in northern sites. The central Mediterranean emerges as a transitional area, with slightly higher frequency of dust episodes in its lower extreme when compared to similar latitudinal positions in western and eastern sides of the Basin. A decreasing south to north gradient of African dust contribution to PM10, driven by the latitudinal position of the monitoring sites at least 25° E westwards across the Basin, is patent across the Mediterranean. As a result of this, an experimental equation for the estimation of annual African dust contributions based on the latitudinal position was obtained. From 25° E eastwards, higher annual dust contributions are encountered due to the elevated annual occurrence of severe episodes of dust but also because of inputs from Negev and Middle Eastern deserts. The slightly higher frequency of African dust episodes observed over southern sites in the central Mediterranean Basin is compensated by its moderately lower intensity. Concerning seasonality patterns and intensity characteristics, a clear summer prevalence is observed in the western part, with low occurrence of severe episodes (daily dust averages over 100 μg m−3 in PM10); no seasonal trend is detected in the central region, with moderate-intensity episodes; and significantly higher contributions are common in autumn-spring in the eastern side, with occurrence of various severe episodes throughout the year. Overall, African dust emerges as the largest PM10 source in regional background southern sites of the Mediterranean (35–50% of PM10), with seasonal peak contributions to PM10 up to 80% of the total mass. The multi-year study of African dust episodes and their contributions to PM10 concentrations reveals a consistent decreasing trend in the period 2006/2007 to 2011 in 4 of the 17 studied regions, all of them located in the NW of the Mediterranean. Such decrease is almost parallel to that of the NAO (North Atlantic Oscillation) index for the summer period, progressively more negative since 2006. Therefore, a sharp change in the atmospheric circulation over the last 5 yr (a similar negative NAO period occurred in the 1950 decade) have affected the number of African dust episodes and consequently the annual dust inputs to PM10 observed in the NW part of the Mediterranean. By investigating mean temperatures and geopotential height maps at 850 hPa it is evident a displacement of warm air masses accomplishing African dust towards the central Mediterranean in the 2007–2008 biennium, and towards the NW African coast and the Canary Islands in the 2009–2011 triennium.
Modelling the global atmospheric transport and deposition of radionuclides from the Fukushima Dai-ichi nuclear accident

We modeled the global atmospheric dispersion and deposition of radionuclides released from the Fukushima Dai-ichi nuclear power plant accident. The EMAC atmospheric chemistry – general circulation model was used, with circulation dynamics nudged towards ERA-Interim reanalysis data. We applied a resolution of approximately 0.5 degrees in latitude and longitude (T255). The model accounts for emissions and transport of the radioactive isotopes 131I and 137Cs, and removal processes through precipitation, particle sedimentation and dry deposition. In addition, we simulated the release of 133Xe, a noble gas that can be regarded as a passive transport tracer of contaminated air. The source terms are based on Chino et al. (2011) and Stohl et al. (2012); especially the emission estimates of 131I are associated with a high degree of uncertainty. The calculated concentrations have been compared to station observations by the Comprehensive Nuclear-Test-Ban Treaty Organisation (CTBTO). We calculated that about 80% of the radioactivity from Fukushima which was released to the atmosphere deposited into the Pacific Ocean. In Japan a large inhabited land area was contaminated by more than 40 kBq m-2. We also estimated the inhalation and 50-year dose by 137Cs, 134Cs and 131I to which the people in Japan are exposed.