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Technical Note: A simple procedure for removing temporal discontinuities in ERA-Interim upper stratospheric temperatures for use in nudged chemistry-climate model simulations

This note describes a simple procedure for removing unphysical temporal discontinuities in ERA-Interim upper stratospheric global mean temperatures in March 1985 and August 1998 that have arisen due to changes in satellite radiance data used in the assimilation. The derived temperature adjustments (offsets) are suitable for use in stratosphere-resolving chemistry-climate models that are nudged (relaxed) to ERA-Interim winds and temperatures. Simulations using a nudged version of the Canadian Middle Atmosphere Model (CMAM) show that the inclusion of the temperature adjustments produces temperature time series that are devoid of the large jumps in 1985 and 1998. Due to its strong temperature dependence, the simulated upper stratospheric ozone is also shown to vary smoothly in time, unlike in a nudged simulation without the adjustments where abrupt changes in ozone occur at the times of the temperature jumps. While the adjustments to the ERA-Interim temperatures remove significant artefacts in the nudged CMAM simulation, spurious transient effects that arise due to water vapour and persist for about 5 yr after the 1979 switch to ERA-Interim data are identified, underlining the need for caution when analysing trends in runs nudged to reanalyses.
Evaluation of the use of five laboratory-determined ozone absorption cross sections in Brewer and Dobson retrieval algorithms

The primary ground-based instruments used to report total column ozone (TOC) are Brewer and Dobson spectrophotometers in separate networks. These instruments make measurements of the UV irradiances, and through a well-defined process, a TOC value is produced. Inherent to the algorithm is the use of a laboratory-determined cross-section data set. We used five ozone cross-section data sets: three data sets that are based on measurements of Bass and Paur; one derived from Daumont, Brion and Malicet (DBM); and a new set determined by Institute of Experimental Physics (IUP), University of Bremen. The three Bass and Paur (1985) sets are as follows: quadratic temperature coefficients from the IGACO (a glossary is provided in Appendix A) web page (IGQ4), the Brewer network operational calibration set (BOp), and the set used by Bernhard et al. (2005) in the reanalysis of the Dobson absorption coefficient values (B05). The ozone absorption coefficients for Brewer and Dobson instruments are then calculated using the normal Brewer operative method, which is essentially the same as that used for Dobson instruments. Considering the standard TOC algorithm for the Brewer instruments and comparing to the Brewer standard operational calibration data set, using the slit functions for the individual instruments, we find the IUP data set changes the calculated TOC by −0.5%, the DBM data set changes the calculated TOC by −3.2%, and the IGQ4 data set at −45 °C changes the calculated TOC by +1.3%. Considering the standard algorithm for the Dobson instruments, and comparing to results using the official 1992 ozone absorption coefficients values and the single set of slit functions defined for all Dobson instruments, the calculated TOC changes by +1%, with little variation depending on which data set is used. We applied the changes to the European Dobson and Brewer reference instruments during the Izaña 2012 Absolute Calibration Campaign. With the application of a common Langley calibration and the IUP cross section, the differences between Brewer and Dobson data sets vanish, whereas using those of Bass and Paur and DBM produces differences of 1.5 and 2%, respectively. A study of the temperature dependence of these cross-section data sets is presented using the Arosa, Switzerland, total ozone record of 2003–2006, obtained from two Brewer-type instruments and one Dobson-type instrument, combined with the stratospheric ozone and temperature profiles from the Payerne soundings in the same period. The seasonal dependence of the differences between the results from the various instruments is greatly reduced with the application of temperature-dependent absorption coefficients, with the greatest reduction obtained using the IUP data set.
Temporal changes in the emissions of CH4 and CO from China estimated from CH4 / CO2 and CO / CO2 correlations observed at Hateruma Island

In situ observation of the atmospheric CO2, CH4, and CO mixing ratios at Hateruma Island (HAT, 24.05° N, 123.80° E) often show synoptic-scale variations with correlative elevations during winter, associated with air transport from the East Asian countries. We examine winter (November– March) trends in ΔCH4 / ΔCO2, ΔCO / ΔCO2, and ΔCO / ΔCH4 observed at Hateruma over the period 1999 to 2010. To investigate the relationship between the East Asian emissions and the short-term variations in the atmospheric mixing ratios, we use the FLEXPART Lagrangian particle dispersion model (LPDM). The observed ratios ΔCH4 / ΔCO2 and ΔCO / ΔCO2 both show an overall gradual decrease over the study period due to a recent rapid increase in fossil fuel consumption in China. We note, however, that the decreasing rates of ΔCH4 / ΔCO2 and ΔCO / ΔCO2 show gradual decrease and increase, respectively, during the entire observation periods used in this study. The ΔCO / ΔCH4 slope, on the other hand, shows an increasing trend during 1999–2004 but a decrease during 2005–2010. Calculation of the concentration footprint for the atmospheric observation at HAT by using the FLEXPART LPDM indicates that most of the short-term variations are caused by emission variations from northern and eastern China. Combined with a set of reported emission maps, we have estimated the temporal changes in the annual CH4 and CO emissions from China under the assumption that the estimate of the fossil-fuel-derived CO2 emissions based on the energy statistics are accurate. The estimated annual CH4 emissions, corresponding to nonseasonal sources or anthropogenic sources without rice fields, show a nearly constant value of 39 ± 7 TgCH4 yr−1 during 1998–2002, and then gradually increase to 46 ± 8 TgCH4 yr−1 in 2009/2010. The estimated annual CO emissions increase from 134 ± 32 TgCO yr−1 in 1998/1999 to 182 ± 42 TgCO yr−1 in 2004/2005, level off after 2005, and then slightly decrease to less than 160 TgCO yr−1 in 2008–2010.
The role of low volatile organics on secondary organic aerosol formation

Large-scale atmospheric models, which typically describe secondary organic aerosol (SOA) formation based on chamber experiments, tend to systematically underestimate observed organic aerosol burdens. Since SOA constitutes a significant fraction of atmospheric aerosol, this discrepancy translates into an underestimation of SOA contribution to radiative forcing of atmospheric aerosol. Here we show that the underestimation of SOA yields can be partly explained by wall losses of SOA forming compounds during chamber experiments. We present a chamber experiment where α-pinene and ozone are injected into a Teflon chamber. When these two compounds react, we observe rapid formation and growth of new particles. Theoretical analysis of this formation and growth event indicates rapid formation of oxidized volatile organic compounds (OVOC) of very low volatility in the chamber. If these oxidized organic compounds form in the gas phase, their wall losses will have significant implications on their partitioning between the gas and particle phase. Although these OVOCs of very low volatility contribute to the growth of new particles, their mass will almost completely be depleted to the chamber walls during the experiment, while the depletion of OVOCs of higher volatilities is less efficient. According to our model simulations, the volatilities of OVOC contributing to the new particle formation event can be of the order of 10−5 μg m−3.
Profile information on CO from SCIAMACHY observations using cloud slicing and comparison with model simulations

We apply a cloud slicing technique (CST), originally developed for Total Ozone Mapping Spectrometer (TOMS) ozone observations, to CO vertical column densities retrieved from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). CST makes use of the shielding effect of clouds and combines trace gas column measurements of cloudy pixels with different cloud heights to retrieve fractional columns aloft. Here we determine seasonal mean tropospheric CO profiles at a vertical resolution of about 1 km, which is much finer than what can be obtained from thermal infrared (IR) instruments. However, since both the atmospheric CO profiles and the effective cloud heights depend systematically on meteorology, and in addition part of the retrieved signal originates from the clear part of the satellite ground pixel, the profiles retrieved from the CST have to be interpreted with care. We compare the seasonal mean SCIAMACHY CO profiles with the output from two atmospheric models sampled in the same way as the satellite observations. We find in general good agreement of the spatial patterns, but systematic differences in the absolute values are observed in both hemispheres (more strongly in the Northern Hemisphere), indicating that the source strengths in the emission inventories are probably underestimated.
Assessment of the effect of air pollution controls on trends in shortwave radiation over the United States from 1995 through 2010 from multiple observation networks

Long-term data sets of all-sky and clear-sky downwelling shortwave (SW) radiation, cloud cover fraction, and aerosol optical depth (AOD) were analyzed together with surface concentrations from several networks (e.g., Surface Radiation Budget Network (SURFRAD), Clean Air Status and Trend Network (CASTNET), Interagency Monitoring of Protection Visual Environments (IMPROVE) and Atmospheric Radiation Measurement (ARM)) in the United States (US). Seven states with varying climatology were selected to better understand the effects of aerosols and clouds on SW radiation. This analysis aims to assess the effects of reductions in anthropogenic aerosol burden resulting from substantial reductions in emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) over the past 16 yr across the US, based on trends in SW radiation. The SO2 and NOx emission data show decreasing trends from 1995 to 2010, which indirectly validates the effects of the Clean Air Act (CAA) in the US. Meanwhile, the total column AOD and surface total PM2.5 observations also show decreasing trends in the eastern US but slightly increasing trends in the western US. Moreover, measured surface concentrations of several other pollutants (i.e., SO2, SO4 and NOx) have similar behavior to AOD and total PM2.5. Analysis of the observed data shows strong increasing trends in all-sky downwelling SW radiation with decreasing trends in cloud cover. However, since observations of both all-sky direct and diffuse SW radiation show increasing trends, there may be other factors contributing to the radiation trends in addition to the decreasing trends in overall cloud cover. To investigate the role of direct radiative effects of aerosols, clear-sky downwelling radiation is analyzed so that cloud effects are eliminated. However, similar increasing trends in clear-sky total and diffuse SW radiation are observed. While significantly decreasing trends in AOD and surface PM2.5 concentrations along with increasing SW radiation (both all-sky and clear-sky) in the eastern US during 1995–2010 imply the occurrence of direct aerosol mediated "brightening", the increasing trends of both all-sky and clear-sky diffuse SW radiation contradicts this conclusion since diffuse radiation would be expected to decrease as aerosols direct effects decrease and cloud cover decreases. After investigating several confounding factors, the increasing trend in clear-sky diffuse SW may be due to more high-level cirrus from increasing air traffic over the US. The clear-sky radiation observations in the western US also show indications of "brightening" even though the AOD, PM2.5 and surface concentration do not vary drastically. This outcome was not unexpected because the CAA controls were mainly aimed at reducing air pollutant emissions in the eastern US and air pollutant levels in the western US were much lower at the onset. This suggests other factors affect the "brightening" especially in the western US.
Role of ozone in SOA formation from alkane photooxidation

Long-chain alkanes, which can be categorized as intermediate volatility organic compounds, are an important source of secondary organic aerosol (SOA). Mechanisms for the gas-phase OH-initiated oxidation of long-chain alkanes have been well documented; particle-phase chemistry, however, has received less attention. The δ-hydroxycarbonyl, which is generated from the isomerization of alkoxy radicals, can undergo heterogeneous cyclization and dehydration to form substituted dihydrofuran. Due to the presence of C=C bonds, the substituted dihydrofuran is predicted to be highly reactive with OH, and even more so with O3 and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. This work focuses on the role of substituted dihydrofuran formation and its subsequent reaction with OH, and more importantly ozone, in SOA formation from the photooxidation of long-chain alkanes. Experiments were carried out in the Caltech Environmental Chamber using dodecane as a representative alkane to investigate the difference in aerosol composition generated from "OH-oxidation-dominating" vs. "ozonolysis-dominating" environments. A detailed mechanism incorporating the specific gas-phase photochemistry, together with the heterogeneous formation of substituted dihydrofuran and its subsequent gas-phase OH/O3 oxidation, is used to evaluate the importance of this reaction channel in dodecane SOA formation. We conclude that (1) the formation of δ-hydroxycarbonyl and its subsequent heterogeneous conversion to substituted dihydrofuran is significant in the presence of NOx; (2) the ozonolysis of substituted dihydrofuran dominates over the OH-initiated oxidation under conditions prevalent in urban and rural air; and (3) a spectrum of highly oxygenated products with carboxylic acid, ester, and ether functional groups are produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the SOA.
One-year observations of carbonaceous and nitrogenous components and major ions in the aerosols from subtropical Okinawa Island, an outflow region of Asian dusts

Ambient aerosol samples (TSP, n = 50) were collected for 12 months at subtropical Okinawa Island, Japan, an outflow region of Asian dusts in the western North Pacific and analysed for organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), water-soluble total nitrogen (WSTN), water-soluble organic nitrogen (WSON) and major ions to better understand the formation and transformation of East Asian aerosols during long-range atmospheric transport. Concentration ranges of these components are; OC: 0.76–7.1 μg m−3 (av. 1.7 ± 1.0 μg m−3), EC: 0.07–0.96 μg m−3 (0.28 ± 0.19 μg m−3), WSOC: 0.27–1.9 μg m−3 (0.73 ± 0.38 μg m−3), WSTN: 0.77 to 3.0 μg m−3 (0.58 ± 0.46 μg m−3) and WSON: 0.0–2.2 μg m−3 (0.12 ± 0.23 μg m−3). Higher OC concentrations were obtained in active biota seasons; spring (av. 2.4 μg m−3) and summer (1.8 μg m−3). EC and WSOC concentrations maximized in spring (av. 0.41 μg m−3 and 0.95 μg m−3, respectively) followed by winter (0. 70 and 0.90 μg m−3) whereas they became lowest in summer (0.19 and 0.52 μg m−3). In contrast, WSTN concentrations were highest in winter (0.86 μg m−3) and lowest in summer (0.37 μg m−3) and autumn (0.34 μg m−3). Concentrations of WSON are higher in early summer (av. 0.26 μg m−3) due to the emission from marine biota. The high ratios of OC / EC (av. 7.6) and WSOC / OC (44%) suggest a secondary formation of organic aerosols. Strong correlation between OC and MSA- (0.81) in spring suggests that springtime aerosols are influenced by additional marine and terrestrial biogenic sources. The positive correlation of Ca2+ and TSP in spring (r = = 0.81) demonstrates a significant contribution of Asian dust whereas high abundances of NO3- and nss-SO42- in winter suggest an important contribution from anthropogenic sources including biomass burning, vehicular emission and coal combustion. NH4-N/WSTN ratios peaked in winter (0.56), indicating a significant contribution of biomass burning to WSTN in cold season. In contrast, higher NO3-N/WSTN ratio in spring than winter suggests that the atmospheric transport of vehicular emissions maximizes in spring. Correlation analyses of major ions suggest that NH4+ and Ca2+ play major role in the neutralization of acidic aerosols forming NH4HSO4, (NH4)2SO4 and CaSO4.
Retrieval of the Eyjafjallajökull volcanic aerosol optical and microphysical properties from POLDER/PARASOL measurements

Total and polarized radiances provided by the Polarization and Directionality of Earth Reflectances (POLDER) satellite sensor are used to retrieve the microphysical and optical properties of the volcanic plume observed during the Eyjafjallajökull volcano eruption in 2010, over cloud-free and cloudy ocean scenes. We selected two plume conditions, fresh aerosols near the sources (three cases) and a downwind volcanic plume observed over the North Sea 30 h after its injection into the atmosphere (aged aerosols). In the near-source conditions, the aerosol properties depend on the distance to the plume. Within the near-source plume, aerosols are mainly non-spherical and in the coarse mode with an effective radius equal to 1.75 (±0.25) μm and an Ångström exponent (AE) close to 0.0. Far from the plume, in addition to the coarse mode, there are particles retrieved in the accumulation mode, suggesting a mixture of sulfate aerosols and volcanic dust, resulting in an AE around 0.8. The properties of the aerosols also depend on whether the plume is fresh or aged. For the downwind (aged) plume, if non-spherical coarse particles as well as some fine mode particles are retrieved, the AE is higher, around ~0.4. In addition, rather low values for the real part of the refractive index (RR) were retrieved for the fresh plume (1.38 < RR < 1.48). Single scattering albedo (SSA) values ranging between 0.92 and 0.98 were retrieved over some parts of the near-source plume; despite the low accuracy of our retrievals, the derived SSA values suggest that the ash particles are rather absorbing. To consider the particle shape, a combination of spheroid models was used. Although the employed model enabled accurate modeling of the POLDER signal in the case of non-spherical ash, our approach failed to model the signal over the optically thickest parts of the near-source plume. The most probable reason for this is the presence of ice crystals within the plume. For the aerosol above clouds (AAC) scenes, polarized measurements allowed the retrieval of the optical thickness (OT) and the AE of optically thin volcanic ash. We found that all the cloud parameters retrieved by passive sensors were biased due to the presence of the elevated volcanic plumes. Finally, thermal infrared measurements were used to identify the type of multilayer scene (cirrus clouds or volcanic dust above liquid clouds) and the retrieval method also provided the OT of thin cirrus layers above the clouds near Iceland.
Multi-year objective analyses of warm season ground-level ozone and PM2.5 over North America using real-time observations and Canadian operational air quality models

Multi-year objective analyses (OA) on a high spatiotemporal resolution for the warm season period (1 May to 31 October) for ground-level ozone and for fine particulate matter (diameter less than 2.5 microns (PM2.5)) are presented. The OA used in this study combines model outputs from the Canadian air quality forecast suite with US and Canadian observations from various air quality surface monitoring networks. The analyses are based on an optimal interpolation (OI) with capabilities for adaptive error statistics for ozone and PM2.5 and an explicit bias correction scheme for the PM2.5 analyses. The estimation of error statistics has been computed using a modified version of the Hollingsworth–Lönnberg (H–L) method. The error statistics are "tuned" using a χ2 (chi-square) diagnostic, a semi-empirical procedure that provides significantly better verification than without tuning. Successful cross-validation experiments were performed with an OA setup using 90% of data observations to build the objective analyses and with the remainder left out as an independent set of data for verification purposes. Furthermore, comparisons with other external sources of information (global models and PM2.5 satellite surface-derived or ground-based measurements) show reasonable agreement. The multi-year analyses obtained provide relatively high precision with an absolute yearly averaged systematic error of less than 0.6 ppbv (parts per billion by volume) and 0.7 μg m−3 (micrograms per cubic meter) for ozone and PM2.5, respectively, and a random error generally less than 9 ppbv for ozone and under 12 μg m−3 for PM2.5. This paper focuses on two applications: (1) presenting long-term averages of OA and analysis increments as a form of summer climatology; and (2) analyzing long-term (decadal) trends and inter-annual fluctuations using OA outputs. The results show that high percentiles of ozone and PM2.5 were both following a general decreasing trend in North America, with the eastern part of the United States showing the most widespread decrease, likely due to more effective pollution controls. Some locations, however, exhibited an increasing trend in the mean ozone and PM2.5, such as the northwestern part of North America (northwest US and Alberta). Conversely, the low percentiles are generally rising for ozone, which may be linked to the intercontinental transport of increased emissions from emerging countries. After removing the decadal trend, the inter-annual fluctuations of the high percentiles are largely explained by the temperature fluctuations for ozone and to a lesser extent by precipitation fluctuations for PM2.5. More interesting is the economic short-term change (as expressed by the variation of the US gross domestic product growth rate), which explains 37% of the total variance of inter-annual fluctuations of PM2.5 and 15% in the case of ozone.