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The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

The impact of 27 volatile organic compounds (VOCs) on the regional O3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999–2001 and 2010–2012) and Auchencorth (2012). Ozone at these sites is representative of rural O3 in south-east England and northern UK, respectively. The monthly-diurnal regional O3 increment was defined as the difference between the regional and hemispheric background O3 concentrations, respectively, derived from oxidant vs. NOx correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional O3 increments than Auchencorth, variation in the regional O3 increment mirrored afternoon depletion of anthropogenic VOCs due to photochemistry (after accounting for diurnal changes in boundary layer mixing depth, and weighting VOC concentrations according to their photochemical ozone creation potential). A positive regional O3 increment occurred consistently during the summer, during which time afternoon photochemical depletion was calculated for the majority of measured VOCs, and to the greatest extent for ethene and m+p-xylene. This indicates that, of the measured VOCs, ethene and m+p-xylene emissions reduction would be most effective in reducing the regional O3 increment but that reductions in a larger number of VOCs would be required for further improvement. The VOC diurnal photochemical depletion was linked to anthropogenic sources of the VOC emissions through the integration of gridded anthropogenic VOC emission estimates over 96 h air-mass back trajectories. This demonstrated that one factor limiting the effectiveness of VOC gridded emissions for use in measurement and modelling studies is the highly aggregated nature of the 11 SNAP (Selected Nomenclature for Air Pollution) source sectors in which they are reported, as monthly variation in speciated VOC trajectory emissions did not reflect monthly changes in individual VOC diurnal photochemical depletion. Additionally, the major VOC emission source sectors during elevated regional O3 increment at Harwell were more narrowly defined through disaggregation of the SNAP emissions to 91 NFR (Nomenclature for Reporting) codes (i.e. sectors 3D2 (domestic solvent use), 3D3 (other product use) and 2D2 (food and drink)). However, spatial variation in the contribution of NFR sectors to parent SNAP emissions could only be accounted for at the country level. Hence, the future reporting of gridded VOC emissions in source sectors more highly disaggregated than currently (e.g. to NFR codes) would facilitate a more precise identification of those VOC sources most important for mitigation of the impact of VOCs on O3 formation. In summary, this work presents a clear methodology for achieving a coherent VOC, regional-O3-impact chemical climate using measurement data and explores the effect of limited emission and measurement species on the understanding of the regional VOC contribution to O3 concentrations.
Aerosol chemistry above an extended archipelago of the eastern Mediterranean basin during strong northern winds

Detailed aerosol chemical predictions by a comprehensive model system (i.e. PMCAMx, WRF, GEOS-CHEM), along with airborne and ground-based observations, are presented and analysed over a wide domain covering the Aegean Archipelago. The studied period is 10 successive days in 2011, characterized by strong northern winds, which is the most frequently prevailing synoptic pattern during summer. The submicron aerosol load in the lower troposphere above the archipelago is homogenously enriched in sulfate (average modelled and measured submicron sulfate of 5.5 and 5.8 μg m−3, respectively), followed by organics (2.3 and 4.4 μg m−3) and ammonium (1.5 and 1.7 μg m−3). Aerosol concentrations smoothly decline aloft, reaching lower values (< 1 μg m−3) above 4.2 km altitude. The evaluation criteria rate the model results for sulfate, ammonium, chloride, elemental carbon, organic carbon and total PM10 mass concentrations as "good", indicating a satisfactory representation of the aerosol chemistry and precursors. Higher model discrepancies are confined to the highest (e.g. peak sulfate values) and lowest ends (e.g. nitrate) of the airborne aerosol mass size distribution, as well as in airborne organic aerosol concentrations (model underestimation ca. 50 %). The latter is most likely related to the intense fire activity at the eastern Balkan area and the Black Sea coastline, which is not represented in the current model application. The investigation of the effect of local variables on model performance revealed that the best agreement between predictions and observations occurs during high winds from the northeast, as well as for the area confined above the archipelago and up to 2.2 km altitude. The atmospheric ageing of biogenic particles is suggested to be activated in the aerosol chemistry module, when treating organics in a sufficient nitrogen and sulfate-rich environment, such as that over the Aegean basin. More than 70 % of the predicted aerosol mass over the Aegean Archipelago during a representative Etesian episode is related to transport of aerosols and their precursors from outside the modelling domain.
Temporal variations of flux and altitude of sulfur dioxide emissions during volcanic eruptions: implications for long-range dispersal of volcanic clouds

Sulfur-rich degassing, which is mostly composed of sulfur dioxide (SO2), plays a major role in the overall impact of volcanism on the atmosphere and climate. The accurate assessment of this impact is currently hampered by the poor knowledge of volcanic SO2 emissions. Here, using an inversion procedure, we show how assimilating snapshots of the volcanic SO2 load derived from the Infrared Atmospheric Sounding Interferometer (IASI) allows for reconstructing both the flux and altitude of the SO2 emissions with an hourly resolution. For this purpose, the regional chemistry-transport model CHIMERE is used to describe the dispersion of SO2 when released in the atmosphere. As proof of concept, we study the 10 April 2011 eruption of the Etna volcano (Italy), which represents one of the few volcanoes instrumented on the ground for the continuous monitoring of SO2 degassing. We find that the SO2 flux time-series retrieved from satellite imagery using the inverse scheme is in agreement with ground observations during ash-poor phases of the eruption. However, large discrepancies are observed during the ash-rich paroxysmal phase as a result of enhanced plume opacity affecting ground-based ultraviolet (UV) spectroscopic retrievals. As a consequence, the SO2 emission rate derived from the ground is underestimated by almost one order of magnitude. Altitudes of the SO2 emissions predicted by the inverse scheme are validated against an RGB image of the Moderate Resolution Imaging Spectroradiometer (MODIS) capturing the near-source atmospheric pathways followed by Etna plumes, in combination with forward trajectories from the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model. At a large distance from the source, modelled SO2 altitudes are compared with independent information on the volcanic cloud height. We find that the altitude predicted by the inverse scheme is in agreement with snapshots of the SO2 height retrieved from recent algorithms exploiting the high spectral resolution of IASI. The validity of the modelled SO2 altitude is further confirmed by the detection of a layer of particles at the same altitude by the spaceborne Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP). Analysis of CALIOP colour and depolarization ratios suggests that these particles consist of sulfate aerosols formed from precursory volcanic SO2. The reconstruction of emission altitude, through inversion procedures which assimilate volcanic SO2 column amounts, requires specific meteorological conditions, especially sufficient wind shear so that gas parcels emitted at different altitudes follow distinct trajectories. We consequently explore the possibility and limits of assimilating in inverse schemes infrared (IR) imagery of the volcanic SO2 cloud altitude which will render the inversion procedure independent of the wind shear prerequisite.
The imprint of stratospheric transport on column-averaged methane

Model simulations of column-averaged methane mixing ratios (XCH4) are extensively used for inverse estimates of methane (CH4) emissions from atmospheric measurements. Our study shows that virtually all chemical transport models (CTM) used for this purpose are affected by stratospheric model-transport errors. We quantify the impact of such model transport errors on the simulation of stratospheric CH4 concentrations via an a posteriori correction method. This approach compares measurements of the mean age of air with modeled age and expresses the difference in terms of a correction to modeled stratospheric CH4 mixing ratios. We find age differences up to ~ 3 years yield to a bias in simulated CH4 of up to 250 parts per billion (ppb). Comparisons between model simulations and ground-based XCH4 observations from the Total Carbon Column Network (TCCON) reveal that stratospheric model-transport errors cause biases in XCH4 of ~ 20 ppb in the midlatitudes and ~ 27 ppb in the arctic region. Improved overall as well as seasonal model-observation agreement in XCH4 suggests that the proposed, age-of-air-based stratospheric correction is reasonable. The latitudinal model bias in XCH4 is supposed to reduce the accuracy of inverse estimates using satellite-derived XCH4 data. Therefore, we provide an estimate of the impact of stratospheric model-transport errors in terms of CH4 flux errors. Using a one-box approximation, we show that average model errors in stratospheric transport correspond to an overestimation of CH4 emissions by ~ 40 % (~ 7 Tg yr−1) for the arctic, ~ 5 % (~ 7 Tg yr−1) for the northern, and ~ 60 % (~ 7 Tg yr−1) for the southern hemispheric mid-latitude region. We conclude that an improved modeling of stratospheric transport is highly desirable for the joint use with atmospheric XCH4 observations in atmospheric inversions.
X-ray computed microtomography of sea ice – comment on "A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow" by Bartels-Rausch et al. (2014)

This comment addresses a statement made in "A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow" by Bartels-Rausch et al. (Atmos. Chem. Phys., 14, 1587–1633, <a href="http://dx.doi.org/10.5194/acp-14-1587-2014"target="_blank"> doi:10.5194/acp-14-1587-2014</a>, 2014). Here we rebut the assertion that X-ray computed microtomography of sea ice fails to reveal liquid brine inclusions by discussing the phases present at the analysis temperature.
Corrigendum to "In situ vertical profiles of aerosol extinction, mass, and composition over the southeast United States during SENEX and SEAC4RS: observations of a modest aerosol enhancement aloft" published in Atmos. Chem. Phys., 15, 7085–7102, 2015
Two decades of water vapor measurements with the FISH fluorescence hygrometer: a review

For almost two decades, the airborne Fast In-situ Stratospheric Hygrometer (FISH) has stood for accurate and precise measurements of total water mixing ratios (WMR, gas phase + evaporated ice) in the upper troposphere and lower stratosphere (UT/LS). Here, we present a comprehensive review of the measurement technique (Lyman-α photofragment fluorescence), calibration procedure, accuracy and reliability of FISH. Crucial for FISH measurement quality is the regular calibration to a water vapor reference, namely the commercial frost-point hygrometer DP30. In the frame of this work this frost-point hygrometer is compared to German and British traceable metrological water standards and its accuracy is found to be 2–4 %. Overall, in the range from 4 to 1000 ppmv, the total accuracy of FISH was found to be 6–8 %, as stated in previous publications. For lower mixing ratios down to 1 ppmv, the uncertainty reaches a lower limit of 0.3 ppmv. For specific, non-atmospheric conditions, as set in experiments at the AIDA chamber – namely mixing ratios below 10 and above 100 ppmv in combination with high- and low-pressure conditions – the need to apply a modified FISH calibration evaluation has been identified. The new evaluation improves the agreement of FISH with other hygrometers to ± 10 % accuracy in the respective mixing ratio ranges. Furthermore, a quality check procedure for high total water measurements in cirrus clouds at high pressures (400–500 hPa) is introduced. The performance of FISH in the field is assessed by reviewing intercomparisons of FISH water vapor data with other in situ and remote sensing hygrometers over the last two decades. We find that the agreement of FISH with the other hygrometers has improved over that time span from overall up to ± 30 % or more to about ± 5–20 % @ < 10 ppmv and to ± 0–15 % @ > 10 ppmv. As presented here, the robust and continuous calibration and operation procedures of the FISH instrument over the last two decades establish the position of FISH as one of the core instruments for in situ observations of water vapor in the UT/LS.
On the use of satellite-derived CH4 : CO2 columns in a joint inversion of CH4 and CO2 fluxes

We present a method for assimilating total column CH4 : CO2 ratio measurements from satellites for inverse modeling of CH4 and CO2 fluxes using the variational approach. Unlike conventional approaches, in which retrieved CH4 : CO2 are multiplied by model-derived total column CO2 and only the resulting CH4 is assimilated, our method assimilates the ratio of CH4 and CO2 directly and is therefore called the ratio method. It is a dual tracer inversion, in which surface fluxes of CH4 and CO2 are optimized simultaneously. The optimization of CO2 fluxes turns the hard constraint of prescribing model-derived CO2 fields into a weak constraint on CO2, which allows us to account for uncertainties in CO2. The method has been successfully tested in a synthetic inversion setup. We show that the ratio method is able to reproduce assumed true CH4 and CO2 fluxes starting from a prior, which is derived by perturbing the true fluxes randomly. We compare the performance of the ratio method with that of the traditional proxy approach and the use of only surface measurements for estimating CH4 fluxes. Our results confirm that the optimized CH4 fluxes are sensitive to the treatment of CO2, and that hard constraints on CO2 may significantly compromise results that are obtained for CH4. We find that the relative performance of ratio and proxy methods have a regional dependence. The ratio method performs better than the proxy method in regions where the CO2 fluxes are most uncertain. However, both ratio and proxy methods perform better than the surface-measurement-only inversion, confirming the potential of spaceborne measurements for accurately determining fluxes of CH4 and other greenhouse gases (GHGs).
Relationships between photosynthesis and formaldehyde as a probe of isoprene emission

Atmospheric oxidation of isoprene emission from land plants affects radiative forcing of global climate change. There is an urgent need to understand the factors that control isoprene emission variability on large spatiotemporal scales but such direct observations of isoprene emission do not exist. Two readily available global-scale long-term observation-based data sets hold information about surface isoprene activity: gross primary productivity (GPP) and tropospheric formaldehyde column variability (HCHOv). We analyze multi-year seasonal linear correlations between observed GPP and HCHOv. The observed GPP–HCHOv correlation patterns are used to evaluate a global Earth system model that embeds three alternative leaf-level isoprene emission algorithms. GPP and HCHOv are decoupled in the summertime in the southeast US (r=−0.03). In the Amazon, GPP and HCHOv are weakly correlated in March-April-May (MAM), correlated in June-July-August (JJA) and weakly anticorrelated in September-October-November (SON). Isoprene emission algorithms that include soil moisture dependence demonstrate greater skill in reproducing the observed interannual seasonal GPP–HCHOv correlations in the southeast US and the Amazon. In isoprene emission models that include soil moisture dependence, isoprene emission is correlated with photosynthesis and anticorrelated with HCHOv. In an isoprene emission model without soil moisture dependence, isoprene emission is anticorrelated with photosynthesis and correlated with HCHOv. Long-term monitoring of isoprene emission, soil moisture and meteorology is required in water-limited ecosystems to improve understanding of the factors controlling isoprene emission and its representation in global Earth system models.
Improvement of climate predictions and reduction of their uncertainties using learning algorithms

Simulated climate dynamics, initialized with observed conditions, is expected to be synchronized, for several years, with the actual dynamics. However, the predictions of climate models are not sufficiently accurate. Moreover, there is a large variance between simulations initialized at different times and between different models. One way to improve climate predictions and to reduce the associated uncertainties is to use an ensemble of climate model predictions, weighted according to their past performances. Here, we show that skillful predictions, for a decadal time scale, of the 2 m temperature can be achieved by applying a sequential learning algorithm to an ensemble of decadal climate model simulations. The predictions generated by the learning algorithm are shown to be better than those of each of the models in the ensemble, the better performing simple average and a reference climatology. In addition, the uncertainties associated with the predictions are shown to be reduced relative to those derived from an equally weighted ensemble of bias-corrected predictions. The results show that learning algorithms can help to better assess future climate dynamics.