Index Geophysics

Items

• Evaluation of discrepancy between measured and modelled oxidized mercury species

  L. Zhang et al. (2012), in a recent report, compared model estimates with new observations of oxidized and particulate mercury species (Hg²⁺ and Hg_p) in the Great Lakes region and found that the sum of Hg²⁺ and Hg_p varied between a factor of 2 to 10 between measurements and model. They suggested too high emission inputs as Hg²⁺ and too fast oxidative conversion of Hg⁰ to Hg²⁺ and Hg_p as possible causes. This study quantitatively explores measurement uncertainties in detail. These include sampling efficiency, composition of sample, interfering species and calibration errors. Model (Global/Regional Atmospheric Heavy Metals Model – GRAHM) sensitivity experiments are used to examine the consistency between various Hg measurements and speciation of Hg near emission sources to better understand the discrepancies between modelled and measured concentrations of Hg²⁺ and Hg_p. We find that the ratio of Hg⁰, Hg²⁺ and Hg_p in the emission inventories, measurements of surface air concentrations of oxidized Hg and measurements of wet deposition are currently inconsistent with each other in the vicinity of emission sources. Current speciation of Hg emissions suggests higher concentrations of Hg²⁺ in air and in precipitation near emission sources; however, measured air concentrations of Hg²⁺ and measured concentrations of Hg in precipitation are not found to be significantly elevated near emission sources compared to the remote regions. The averaged unbiased root mean square error (RMSE) between simulated and observed concentrations of Hg²⁺ is found to be reduced by 42% and for Hg_p reduced by 40% for 21 North American sites investigated, when a ratio for Hg⁰ : Hg²⁺ : Hg_p in the emissions is changed from 50 : 40 : 10 (as specified in the original inventories) to 90 : 8 : 2. Unbiased RMSE reductions near emissions sources in the eastern United States and Canada are found to be reduced by up to 58% for Hg²⁺. Significant improvement in the model simulated spatial distribution of wet deposition of mercury in North America is noticed with the modified Hg emission speciation. Measurement-related uncertainties leading to lower estimation of Hg²⁺ concentrations are 86%. Uncertainties yielding either to higher or lower Hg²⁺ concentrations are found to be 36%. Finally, anthropogenic emission uncertainties are 106% for Hg²⁺. Thus it appears that the identified uncertainties for model estimates related to mercury speciation near sources, uncertainties in measurement methodology and uncertainties in emissions can close the gap between modelled and observed estimates of oxidized mercury found in L. Zhang et al. (2012). Model sensitivity simulations show that the measured concentrations of oxidized mercury, in general, are too low to be consistent with measured wet deposition fluxes in North America. Better emission inventories (with respect to speciation), better techniques for measurements of oxidized species and knowledge of mercury reduction reactions in different environments (including in-plume) in all phases are needed for improving the mercury models.

• CO2 dispersion modelling over Paris region within the CO2-MEGAPARIS project

  Accurate simulation of the spatial and temporal variability of tracer mixing ratios over urban areas is a challenging and interesting task needed to be performed in order to utilise CO₂ measurements in an atmospheric inverse framework and to better estimate regional CO₂ fluxes. This study investigates the ability of a high-resolution model to simulate meteorological and CO₂ fields around Paris agglomeration during the March field campaign of the CO₂-MEGAPARIS project. The mesoscale atmospheric model Meso-NH, running at 2 km horizontal resolution, is coupled with the Town Energy Balance (TEB) urban canopy scheme and with the Interactions between Soil, Biosphere and Atmosphere CO₂-reactive (ISBA-A-gs) surface scheme, allowing a full interaction of CO₂ modelling between the surface and the atmosphere. Statistical scores show a good representation of the urban heat island (UHI) with stronger urban–rural contrasts on temperature at night than during the day by up to 7 °C. Boundary layer heights (BLH) have been evaluated on urban, suburban and rural sites during the campaign, and also on a suburban site over 1 yr. The diurnal cycles of the BLH are well captured, especially the onset time of the BLH increase and its growth rate in the morning, which are essential for tall tower CO₂ observatories. The main discrepancy is a small negative bias over urban and suburban sites during nighttime (respectively 45 m and 5 m), leading to a few overestimations of nocturnal CO₂ mixing ratios at suburban sites and a bias of +5 ppm. The diurnal CO₂ cycle is generally well captured for all the sites. At the Eiffel tower, the observed spikes of CO₂ maxima occur every morning exactly at the time at which the atmospheric boundary layer (ABL) growth reaches the measurement height. At suburban ground stations, CO₂ measurements exhibit maxima at the beginning and at the end of each night, when the ABL is fully contracted, with a strong spatio-temporal variability. A sensitivity test without urban parameterisation removes the UHI and underpredicts nighttime BLH over urban and suburban sites, leading to large overestimation of nocturnal CO₂ mixing ratio at the suburban sites (bias of +17 ppm). The agreement between observation and prediction for BLH and CO₂ concentrations and urban–rural increments, both day and night, demonstrates the potential of using the urban mesoscale system in the context of inverse modelling

• The mass and number size distributions of black carbon aerosol over Europe

  Black carbon-containing aerosol particles play an important role in the direct and indirect radiative forcing of climate. However, the magnitude and sign of the net radiative effect is strongly dependent on the physical properties of the black carbon (BC) component of the particles, such as mass concentration, number size distribution and mixing state. Here we use a global aerosol model combined with aircraft measurements of BC particle number and size from the Single Particle Soot Photometer (SP2) to assess the realism with which these physical properties are predicted by global models. The comparison reveals a substantial mismatch between the measured and modelled BC size distribution over the size range of the SP2 instrument (90–400 nm BC diameter). The model predicts BC particle number concentrations a factor ~3.5–5.7 higher than measured and a mode diameter that is ~40–65 nm smaller than observed. More than ~90% of the model particles with dry diameters ≳260 nm contain BC, while the observations suggest only 14% on average. These model–observation biases in the BC properties are considerably greater than for the overall particle distribution, suggesting that the discrepancy is associated with model assumptions about the size and mixing state of the emitted carbonaceous particles. We expect the discrepancy in BC size distribution to be common among most global aerosol models, with implications for model estimates of absorption optical depth and direct radiative forcing.

• Linkages between ozone-depleting substances, tropospheric oxidation and aerosols

  Coupling between the stratosphere and the troposphere allows changes in stratospheric ozone abundances to affect tropospheric chemistry. Large-scale effects from such changes on chemically produced tropospheric aerosols have not been systematically examined in past studies. We use a composition-climate model to investigate potential past and future impacts of changes in stratospheric ozone depleting substances (ODS) on tropospheric oxidants and sulfate aerosols. In most experiments, we find significant responses in tropospheric photolysis and oxidants, with small but significant effects on methane radiative forcing. The response of sulfate aerosols is sizeable when examining the effect of increasing future nitrous oxide (N₂O) emissions. We also find that without the regulation of chlorofluorocarbons (CFCs) through the Montreal Protocol, sulfate aerosols could have increased by 2050 by a comparable amount to the decreases predicted due to relatively stringent sulfur emissions controls. The individual historical radiative forcings of CFCs and N₂O through their indirect effects on methane (−22.6 mW m⁻² for CFCs and −6.7 mW m⁻² for N₂O) and sulfate aerosols (−3.0 mW m⁻² for CFCs and +6.5 mW m⁻² for N₂O when considering the direct aerosol effect) discussed here are non-negligible when compared to known historical ODS forcing. Our results stress the importance of accounting for stratosphere-troposphere, gas-aerosol and composition-climate interactions when investigating the effects of changing emissions on atmospheric composition and climate.

• Insights into dissolved organic matter complexity in rainwater from continental and coastal storms by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry

  A series of seven rainwater samples were collected in Wilmington, North Carolina USA originating from both continental and coastal storms and analyzed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This data set is unique in that it represents a detailed comparison of the molecular level composition of DOM in rainwater collected from distinctly different air mass back trajectories by FT-ICR MS. Approximately 25% of the roughly 2000 assigned CHO molecular formulas are unique to a single storm classification indicating the importance of air mass back trajectory on the composition of rainwater dissolved organic matter (DOM). Analysis of the unique molecular formula assignments highlighted distinct groupings of various bio- and geo-molecule classes with coastal storms containing unique formulas representative of lignin and cellulose-like formulas while continental storms had lipid-like formulas. A series of 18 distinct methylene oligomers were identified in coastal storms and 13 unique methylene oligomers in continental storms, suggesting oligomer formation is ubiquitous in rainwater albeit different for each storm classification. Oligomers of small acids and C₃H₄O₂ were detected in both storm types indicating their processing may be similar in both back trajectories. Condensed aromatic hydrocarbons were detected in continental storms with phenol moieties that are not as oxidized as similar compounds detected in aquatic DOM.

• Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan

  Organosulfates are important components of atmospheric organic aerosols, yet their structures, abundances, sources and formation processes are not adequately understood. This study presents the identification and quantitation of benzyl sulfate in atmospheric aerosols, which is the first confirmed atmospheric organosulfate with aromatic carbon backbone. Benzyl sulfate was identified and quantified in fine particulate matter (PM_2.5) collected in Lahore, Pakistan, during 2007–2008. An authentic standard of benzyl sulfate was synthesized, standardized, and identified in atmospheric aerosols with quadrupole time-of-flight (Q-ToF) mass spectrometry (MS). Benzyl sulfate was quantified in aerosol samples using ultra performance liquid chromatography (UPLC) coupled to negative electrospray ionization triple quadrupole (TQ) MS. The highest benzyl sulfate concentrations were recorded in November and January 2007 (0.50 ± 0.11 ng m⁻³) whereas the lowest concentration was observed in July (0.05 ± 0.02 ng m⁻³). To evaluate matrix effects, benzyl sulfate concentrations were determined using external calibration and the method of standard addition; comparable concentrations were detected by the two methods, which ruled out significant matrix effects in benzyl sulfate quantitation. Three additional organosulfates with <i>m/z</i> 187, 201 and 215 were qualitatively identified as aromatic organosulfates with additional methyl substituents by high-resolution mass measurements and tandem MS. The observed aromatic organosulfates form a homologous series analogous to toluene, xylene, and trimethylbenzene, which are abundant anthropogenic volatile organic compounds (VOC), suggesting that aromatic organosulfates may be formed by secondary reactions. However, stronger statistical correlations of benzyl sulfate with combustion tracers (EC and levoglucosan) than with secondary tracers (SO₄^2&minus; and &alpha;-pinene-derived nitrooxy organosulfates) suggest that aromatic organosulfates may be emitted from the combustion sources or their subsequent atmospheric processing. Further studies are needed to elucidate the sources and formation pathways of aromatic organosulfates in the atmosphere.

• Effect of atmospheric organic complexation on iron-bearing dust solubility

  Recent studies reported that the effect of organic complexation may be a potentially important process to be considered by models estimating atmospheric iron flux to the ocean. In this study, we investigated this process effect by a series of dissolution experiments on iron-bearing dust in the presence or the absence of various organic compounds (acetate, formate, oxalate, malonate, succinate, glutarate, glycolate, lactate, tartrate and humic acid as an analogue of humic like substances, HULIS) typically found in atmospheric waters. Only 4 of tested organic ligands (oxalate, malonate, tartrate and humic acid) caused an enhancement of iron solubility which was associated with an increase of dissolved Fe(II) concentrations. For all of these organic ligands, a positive linear dependence of iron solubility to organic concentrations was observed and showed that the extent of organic complexation on iron solubility decreased in the following order: oxalate >malonate = tartrate > humic acid. This was attributed to the ability of electron donors of organic ligands and implies a reductive ligand-promoted dissolution. This study confirms that among the known atmospheric organic binding ligands of Fe, oxalate is the most effective ligand promoting dust iron solubility and showed, for the first time, the potential effect of HULIS on iron dissolution under atmospheric conditions.

• Modeling organic aerosol from the oxidation of α-pinene in a Potential Aerosol Mass (PAM) chamber

  A model has been developed to simulate the formation and evolution of secondary organic aerosol (SOA) and was tested against data produced in a Potential Aerosol Mass (PAM) flow reactor and a large environmental chamber. The model framework is based on the two-dimensional volatility basis set approach (2D-VBS), in which SOA oxidation products in the model are distributed on the 2-D space of effective saturation concentration (<i>C</i>_<i>i</i>*) and oxygen-to-carbon ratio (O : C). The modeled organic aerosol mass concentrations (<i>C</i>_OA) and O : C agree with laboratory measurements within estimated uncertainties. However, while both measured and modeled O : C increase with increasing OH exposure as expected, the increase of modeled O : C is rapid at low OH exposure and then slows as OH exposure increases while the increase of measured O : C is initially slow and then accelerates as OH exposure increases. A global sensitivity analysis indicates that modeled <i>C</i>_OA values are most sensitive to the assumed values for the number of <i>C</i>_<i>i</i>* bins, the heterogeneous OH reaction rate coefficient, and the yield of first-generation products. Modeled SOA O : C values are most sensitive to the assumed O : C of first-generation oxidation products, the number of <i>C</i>_<i>i</i>* bins, the heterogeneous OH reaction rate coefficient, and the number of O : C bins. All these sensitivities vary as a function of OH exposure. The sensitivity analysis indicates that the 2D-VBS model framework may require modifications to resolve discrepancies between modeled and measured O : C as a function of OH exposure.

• Aerosol mixing state, hygroscopic growth and cloud activation efficiency during MIRAGE 2006

  Observations of aerosol hygroscopic growth and CCN activation spectra for submicron particles are reported for the T1 ground site outside of Mexico City during the MIRAGE 2006 campaign. <i>κ</i>-Köhler theory is used to evaluate the characteristic hygroscopicity parameter, &kappa;*, for the CCN active aerosol population using both size-resolved HTMDA and size-resolved CCNc measurements. Organic mass fractions (<i>f</i>_org) are evaluated from size-resolved aerosol mass spectrometer (AMS) measurements, from which predictions of the hygroscopicity parameter are compared against &kappa;*. <br></br> Strong diurnal changes in aerosol water uptake parameters and aerosol composition are observed. We find that new particle formation (NPF) events are correlated with an increased &kappa;* and CCN-active fraction during the daytime, with greater impact on smaller particles. During NPF events, the number concentration of 40 nm particles acting as CCN at 0.51% ± 0.06% supersaturation can surpass by more than a factor of two the corresponding concentrations of 100 nm particles. We also find that at 06:00–08:00 LT throughout the campaign, fresh traffic emissions result in substantial changes to the chemical distribution of the aerosol, with on average 65% externally mixed fraction for 40 nm particles and 30% externally mixed fraction for 100 nm particles, whereas at midday nearly all particles of both sizes can be described as "internally mixed". <br></br> Average activation spectra and growth factor distributions are analyzed for different time periods characterizing the daytime (with and without NPF events), the early morning "rush hour" and the entire campaign. We show that &kappa;* derived from CCNc measurements decreases as a function of size during all time periods, while the CCN-active fraction increases as a function of size. Size-resolved AMS measurements do not predict the observed trend for &kappa;* versus particle size, which can be attributed to unresolved mixing state and the presence of refractory material not measured by the AMS. Measured &kappa;* typically ranges from 0.2 to 0.35, and organics typically make up 60–85 % of the aerosol mass in the size range studied. We show that &kappa;_AMS is able to describe CCN concentrations reasonably well, provided mixing-state information is available, especially at the highest CCN concentrations. This is consistent with other CCN studies carried out in urban environments, and is partly due to the fact that the highest CCN concentrations occur during the daytime when the aerosol is internally mixed. During the early morning rush hour, however, failing to account for the aerosol mixing state results in systematic overestimation of CCN concentrations by as much as 50–100% on average.

• Singular vector decomposition for sensitivity analyses of tropospheric chemical scenarios

  Observations of the chemical state of the atmosphere typically provide only sparse snapshots of the state of the system due to their insufficient temporal and spatial density. One possibility for optimisation of the state estimate is to target the observation of those parameters that have the largest potential of resulting in forecast improvements. In the present work, the technique of singular vector analysis is applied to atmospheric chemical modelling in order to identify the most sensitive chemical compounds during a given time period and prioritise them for measurement. Novel to the current work is the fact that, in the application of singular vector analysis, not only the initial values but also the emissions are considered as target variables for adaptive observation strategies. This specific application of singular vector analysis is studied in the context of a chemistry box model allowing for validation of its new features for two chemical regimes. The time and regime dependence of the ozone (O₃) and peroxyacetyl nitrate (PAN) formation potential of individual volatile organic compounds (VOCs) is investigated. Results show that the combined sensitivity of O₃ and PAN to individual VOCs is strongly dependent on the photochemical scenario and simulation interval used. Particularly the alkanes show increasing sensitivities with increasing simulation length. Classifying the VOCs as being of high, medium, little or negligible importance for the formation of O₃ and PAN allows for the identification of those VOCs that may be omitted from measurement. We find that it is possible to omit 6 out of 18 VOCs considered for initial value measurement and 4 out of 12 VOCs considered for emission measurement. The omission of these VOCs is independent of photochemical regime and simulation length. The VOCs selected for measuring account for more than 96% and 90% of the O₃ and PAN sensitivity to VOCs, respectively.