ALBERT

Description: Iron oxides compounds constitute an important component of mineral dust aerosol. Several previous studies have shown that these minerals are strong absorbers at visible wavelengths and thus that they play a critical role in the overall climate forcing caused by dust aerosol. When compiling a database of complex refractive indices of possible mineral species of iron-oxides to study their optical properties, we found that uniformly continuous optical constants for a single type of iron-oxides in the wavelength range between 0.2 and 50 μm is very scarce and that the use of hematite to represent all molecular or mineral iron-oxides types is a popular hypothesis. However, the crucial problem is that three continuous datasets for complex refractive indices of hematite are employed in climate models, but there are significant differences between them. Thus, the real role of iron-oxides in the optical properties of dust aerosols becomes a key scientific question, and we address this problem by considering different refractive indices, size distributions, and more logical weight fractions and mixing states of hematite. Based on the microscopic observations, a semi-external mixture that employs an external mixture between Fe-aggregates and other minerals and partly internal mixing between iron-oxides and aluminosilicate particles is advised as the optimal approximation. The simulations demonstrate that hematite with a spectral refractive indices from Longtin et al. (1988) shows approximately equal absorbing capacity to the mineral illite over the whole wavelength region from 0.55 to 2.5 μm, and only enhances the optical absorption of aerosol mixture at λ 〈 0.55 μm. Using the dataset from Querry (1985) may overestimate the optical absorption of hematite at both visible and near-infrared wavelengths. More laboratory measurements of the refractive index of iron-oxides, especially for hematite and goethite in the visible spectrum, should therefore be taken into account when assessing the effect of mineral dust on climate forcing.

Description: We examine the formation of nitrate and ammonium on five types of externally mixed pre-existing aerosols using the hybrid dynamic method in a global chemistry transport model. The model developed here predicts a similar spatial pattern of total aerosol nitrate and ammonium to that of several pioneering studies, but separates the effects of nitrate and ammonium on pure sulfate, biomass burning, fossil fuel, dust and sea salt aerosols. Nitrate and ammonium boost the scattering efficiency of sulfate and organic matter but lower the extinction of sea salt particles since the hygroscopicity of a mixed nitrate-ammonium-sea salt particle is less than that of pure sea salt. The direct anthropogenic forcing of particulate nitrate and ammonium at the top of the atmosphere (TOA) is estimated to be −0.12 W m−2. Nitrate, ammonium and nitric acid gas also affect aerosol activation and the reflectivity of clouds. The first aerosol indirect forcing by anthropogenic nitrate (gas plus aerosol) and ammonium is estimated to be −0.09 W m−2 at the TOA, almost all of which is due to condensation of nitric acid gas onto growing droplets (−0.08 W m−2).

Description: Time-dependent variational data assimilation allows the possibility of extracting wind information from observations of ozone or other trace gases. Since trace gas observations are not available at sufficient resolution for deriving feature-track winds, they must be combined with model background information to produce an analysis. If done with time-dependent variational assimilation, wind information may be extracted via the adjoint of the linearized tracer continuity equation. This paper presents idealized experiments that illustrate the mechanics of tracer–wind extraction and demonstrate some of the limitations of this procedure. We first examine tracer–wind extraction using a simple one-dimensional advection equation. The analytic solution for a single trace gas observation is discussed along with numerical solutions for multiple observations. The limitations of tracer–wind extraction are then explored using highly idealized ozone experiments performed with a development version of the Navy Global Environmental Model (NAVGEM) in which globally distributed hourly stratospheric ozone profiles are assimilated in a single 6 h update cycle in January 2009. Starting with perfect background ozone conditions, but imperfect dynamical conditions, ozone errors develop over the 6 h background window. Wind increments are introduced in the analysis in order to reduce the differences between background ozone and ozone observations. For "perfect" observations (unbiased and no random error), this results in root-mean-square (RMS) vector wind error reductions of up to ~4 m s−1 in the winter hemisphere and tropics. Wind extraction is more difficult in the summer hemisphere due to weak ozone gradients and smaller background wind errors. The limitations of wind extraction are also explored for observations with imposed random errors and for limited sampling patterns. As expected, the amount of wind information extracted degrades as observation errors or data voids increase. In the case of poorly specified observation error covariances, assimilation of ozone data with imposed errors may result in increased RMS wind error, since the assimilation is constrained too tightly to the noisy observations.

Description: Quasicontinuous measurements of carbon monoxide (CO) recorded over three years at Mount Waliguan (WLG), a global baseline station in remote western China, were examined using back trajectory analysis. The data include a revision to correct the working reference scale to the WMO2000 scale and corrections for drift in the reference gases. Between July 2004 and June 2007, CO exhibited large fluctuations and the 5 %, 50 % and 95 %-percentiles of relevant CO mixing ratios were 102 ppb, 126 ppb and 194 ppb. Approximately 50 % of all observed data were selected as CO background data using a mathematical procedure of robust local regression, with the remainder affected by regional-scale pollution. The monthly mean background CO mixing ratios showed a minimum in summer and a maximum in late winter, although all seasons were affected by short-term enhancements that exceeded background levels. The CO data were compared to values observed at the high alpine research station at Jungfraujoch, Switzerland. Smaller seasonal amplitudes were observed at WLG compared to the Jungfraujoch due to lower winter and spring CO levels, however, episodic enhancements of polluted air were greater at WLG. The air parcels arriving at WLG came predominately from the west, except in summer when advection from the east and southeast prevailed. Transport from the east or southeast typically brought polluted air to the site, having passed over populated urban areas upwind. A large number of elevated CO mixing ratios could also be associated with advection from the northwest of WLG via the central Xinjiang Uygur Autonomous Region (XUAR) and the Ge'ermu urban area where growing industrial activities as well as crops residue burning provide sources of CO. Air masses passing over northwestern Gansu were associated with relatively high CO values suggesting an anthropogenic influence, which was likely due to anthropogenic emissions from northwestern China (based on back-trajectory and potential source contribution analysis and on the INTEX-B: intercontinental Chemical Transport Experiment-Phase B). Background conditions were observed most frequently in air parcels from remote Tibet west of WLG. The probability that air parcels pass over regions of clean or polluted regions was further identified using potential source contribution function (PSCF) analysis.

Description: Water activity is a key factor in aerosol thermodynamics and hygroscopic growth. We introduce a new representation of water activity (aw), which is empirically related to the solute molality (μs) through a single solute specific constant, νi. Our approach is widely applicable, considers the Kelvin effect and covers ideal solutions at high relative humidity (RH), including cloud condensation nuclei (CCN) activation. It also encompasses concentrated solutions with high ionic strength at low RH such as the relative humidity of deliquescence (RHD). The constant νi can thus be used to parameterize the aerosol hygroscopic growth over a wide range of particle sizes, from nanometer nucleation mode to micrometer coarse mode particles. In contrast to other aw-representations, our νi factor corrects the solute molality both linearly and in exponent form x · ax. We present four representations of our basic aw-parameterization at different levels of complexity for different aw-ranges, e.g. up to 0.95, 0.98 or 1. νi is constant over the selected aw-range, and in its most comprehensive form, the parameterization describes the entire aw range (0–1). In this work we focus on single solute solutions. νi can be pre-determined with a root-finding method from our water activity representation using an aw−μs data pair, e.g. at solute saturation using RHD and solubility measurements. Our aw and supersaturation (Köhler-theory) results compare well with the thermodynamic reference model E-AIM for the key compounds NaCl and (NH4)2SO4 relevant for CCN modeling and calibration studies. Envisaged applications include regional and global atmospheric chemistry and climate modeling.

Description: We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 16 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 16 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has a range from −0.58 to −0.02 Wm−2, with a mean of −0.27 Wm−2 for the 16 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information from the other AeroCom models reduces the range and slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of −0.35 Wm−2. Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study. We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results.

Description: High frequency measurements of carbon monoxide (CO) recorded over three years at Mount Waliguan (WLG), a global background station in remote western China, were examined using back trajectory analysis. Corrections for the drift in reference gases were also included in the data revision. Between July 2004 and June 2007, a time series of CO exhibited large fluctuations and the 5%, 50% and 95%-percentiles of relevant CO mixing ratios were 102 ppb, 126 ppb and 194 ppb. Approximately 50% of all observed data have been selected as CO background data using a mathematical procedure of robust local regression with the remainder affected by regional-scale pollution. The monthly mean background CO mixing ratios showed a minimum in summer and a maximum in late winter, although all seasons were effected by short-term enhancements that exceeded background levels two or more times. The CO data were compared to the values observed at the high alpine research station Jungfraujoch, Switzerland. Smaller seasonal amplitudes were observed at WLG compared to the Jungfraujoch due to lower winter and spring CO levels, however, episodic enhancements of polluted air were much greater at the site in China. The air parcels arriving at WLG came predominately from the West, except in summer when advection from the East and Southeast prevailed. Transport from the East typically brought polluted air to the site, having passed over populated urban areas upwind. A large number of elevated CO mixing ratios could also be associated with advection from the Northwest of WLG via the central Xinjiang Uygur Autonomous Region (XUAR) and the Ge'ermu urban area where growing industrial activities as well as crops residue burning provide large sources of CO. These background conditions were observed most frequently when air masses originated from remote Tibet west of WLG. The probability that air parcels pass over regions of clean or polluted regions was further identified using potential source contribution function (PSCF) analysis.

Description: Water is a main component of atmospheric aerosols and its amount depends on the particle chemical composition. We introduce a new parameterization for the aerosol hygroscopic growth factor (HGF), based on an empirical relation between water activity (aw) and solute molality (μs) through a single solute specific coefficient νi. Three main advantages are: (1) wide applicability, (2) simplicity and (3) analytical nature. (1) Our approach considers the Kelvin effect and covers ideal solutions at large relative humidity (RH), including CCN activation, as well as concentrated solutions with high ionic strength at low RH such as the relative humidity of deliquescence (RHD). (2) A single νi coefficient suffices to parameterize the HGF for a wide range of particle sizes, from nanometer nucleation mode to micrometer coarse mode particles. (3) In contrast to previous methods, our analytical aw parameterization depends not only on a linear correction factor for the solute molality, instead νi also appears in the exponent in form x · ax. According to our findings, νi can be assumed constant for the entire aw range (0–1). Thus, the νi based method is computationally efficient. In this work we focus on single solute solutions, where νi is pre-determined with the bisection method from our analytical equations using RHD measurements and the saturation molality μssat. The computed aerosol HGF and supersaturation (Köhler-theory) compare well with the results of the thermodynamic reference model E-AIM for the key compounds NaCl and (NH4)2SO4 relevant for CCN modeling and calibration studies. The equations introduced here provide the basis of our revised gas-liquid-solid partitioning model, i.e. version 4 of the EQuilibrium Simplified Aerosol Model (EQSAM4), described in a companion paper.

Description: Time-dependent variational data assimilation allows the possibility of extracting wind information from observations of long-lived trace gases. Since trace gas observations are not available at sufficient resolution for deriving feature-track winds, they must be combined with model background information to produce an analysis. If done with time-dependent variational assimilation, wind information may be extracted via the adjoint of the linearized tracer continuity equation. This paper presents idealized experiments that illustrate the mechanics of tracer-wind extraction and demonstrate some of the limitations of this procedure. We first examine tracer-wind extraction using a simple one-dimensional advection equation. The analytic solution for a single trace gas observation is discussed along with numerical solutions for multiple observations. The limitations of tracer-wind extraction are then explored using highly idealized ozone experiments performed with a development version of the Navy Global Environmental Model (NAVGEM) in which stratospheric globally-distributed hourly stratospheric ozone profiles are assimilated in a single 6-h update cycle in January 2009. Starting with perfect background ozone conditions, but imperfect dynamical conditions, ozone errors develop over the 6-h background window. Wind increments are introduced in the analysis in order to reduce the differences between background ozone and ozone observations. For "perfect" observations (unbiased and no random error), this results in root mean square (RMS) vector wind error reductions of up to ∼ 3 m s−1 in the winter hemisphere and tropics. Wind extraction is more difficult in the summer hemisphere due to weak ozone gradients and smaller background wind errors. The limitations of wind extraction are also explored for observations with imposed random errors and for limited sampling patterns. As expected, the amount of wind information extracted degrades as observation errors or data voids increase. In the case of poorly specified observation error covariances, assimilation of ozone data with imposed errors may result in erroneous wind increments, since the assimilation is constrained too tightly to the noisy observations.

Description: We examine the formation of nitrate and ammonium on five types of externally mixed pre-existing aerosols using the hybrid dynamic method in a global chemistry transport model. The model developed here predicts a similar spatial pattern of total aerosol nitrate and ammonium to that of several pioneering studies, but separates the effects of nitrate and ammonium on pure sulfate, biomass burning, fossil fuel, dust and sea salt aerosols. Nitrate and ammonium boost the scattering efficiency of sulfate and organic matter but lower the extinction of sea salt particles since the hygroscopicity of a mixed nitrate-ammonium-sea salt particle is less than that of pure sea salt. The direct anthropogenic forcing of particulate nitrate and ammonium at the top of atmosphere (TOA) is estimated to be −0.12 W m−2. Nitrate, ammonium and nitric acid gas also affect aerosol activation and the reflectivity of clouds. The first aerosol indirect forcing by anthropogenic nitrate (gas plus aerosol) and ammonium is estimated to be −0.09 W m−2 at TOA, almost all of which is due to nitric acid gas (−0.08 W m−2).