Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate

The contribution of marine organics to the air quality of the western United States

The contribution of marine organic emissions to the air quality in coastal areas of the western United States is studied using the latest version of the US Environmental Protection Agency (EPA) regional-scale Community Multiscale Air Quality (CMAQv4.7) modeling system. Emissions of marine isoprene, monoterpenes, and primary organic matter (POM) from the ocean are implemented into the model to provide a comprehensive view of the connection between ocean biology and atmospheric chemistry and air pollution. Model simulations show that marine organics can increase the concentration of PM<sub>2.5</sub> by 0.1–0.3 μg m<sup>−3</sup> (up to 5%) in some coastal cities such as San Francisco, CA. This increase in the PM<sub>2.5</sub> concentration is primarily attributed to the POM emissions, with small contributions from the marine isoprene and monoterpenes. When marine organic emissions are included, organic carbon (OC) concentrations over the remote ocean are increased by up to 50% (25% in coastal areas), values consistent with recent observational findings. This study is the first to quantify the air quality impacts from marine POM and monoterpenes for the United States, and it highlights the need for inclusion of marine organic emissions in air quality models

A New Study of Sea Spray Optical Properties from Multi-Sensor Spaceborne Observations

Retrievals of aerosol optical depth (AOD) from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) satellite sensor require the assumption of an extinction-to-backscatter ratio, also known as the lidar ratio. This paper evaluates a new method to calculate lidar ratio of sea spray aerosol using two independent sources: the AOD from Synergized Optical Depth of Aerosols (SODA) and the integrated attenuated backscatter from CALIOP. The method applied in this study allows particulate lidar ratio to be calculated for individual CALIOP retrievals of single aerosol layer columns over the ocean. Analyses are carried out using CALIOP level 2, 5km sea spray aerosol layer products and collocated SODA nighttime data from December 2007 to December 2009. The global mean lidar ratio for sea spray aerosols was found to be 26 sr, roughly 30 higher than the one prescribed by CALIOP. Data analysis also showed considerable spatiotemporal variability in calculated lidar ratio over different parts of the remote oceans. The calculated aerosol lidar ratios are shown to be inversely related to the mean ocean surface wind speed: increase in ocean surface wind speed (U10) from 0 to 15 ms-1 reduces the mean lidar ratios for sea spray particles from 32 sr (for 0 U10 4 ms-1) to 22 sr (for U10 15 ms-1). Such changes in the lidar ratio are expected to have a corresponding effect on sea spray AOD. The outcomes of this study are relevant for future improvements of the SODA and CALIOP operational product and could lead to more accurate retrievals of sea spray AOD

Interpreting elevated space-borne HCHO columns over the Mediterranean Sea using the OMI sensor

Formaldehyde (HCHO) is an oxidation product of a wide range of volatile organic compounds (VOCs) and important atmospheric constituent found in both the polluted urban atmosphere and remote background sites. In this study, remotely sensed data of HCHO vertical column densities are analyzed over the Mediterranean Sea using the Ozone Monitoring Instrument (OMI). Data analysis indicates a marked seasonal cycle with a summer maximum and winter minimum confined to the marine environment during a three year period (2005–2007) examined. A possible retrieval artifact associated with Saharan dust transport over the region is explored by changing intensity of Saharan dust sources in GEOS-Chem following the recommendation of Generoso et al. (2008). Recalculated air mass factors (AMF), based on the new values of aerosol loadings, lead to a reduction of the summertime "hot spot" in OMI retrieval of HCHO vertical columns over the Mediterranean Sea; however, even after the correction, enhanced values are still present in this region. To explain these values, marine biogenic sources of VOCs are examined. Calculations indicate that emission of phytoplankton-produced isoprene is not likely to explain the enhanced HCHO vertical columns over the Mediterranean Sea. Model simulations in conjunction with measurements studies may be required to fully explore the complex mechanism of HCHO formation over the Mediterranean and its implications for the air quality in the region

Wind speed dependent size-resolved parameterization for the organic mass fraction of sea spray aerosol

For oceans to be a significant source of primary organic aerosol (POA), sea spray aerosol (SSA) must be highly enriched with organics relative to the bulk seawater. We propose that organic enrichment at the air-sea interface, chemical composition of seawater, and the aerosol size are three main parameters controlling the organic mass fraction of sea spray aerosol (OM<sub>SSA</sub>). To test this hypothesis, we developed a new marine POA emission function based on a conceptual relationship between the organic enrichment at the air-sea interface and surface wind speed. The resulting parameterization is explored using aerosol chemical composition and surface wind speed from Atlantic and Pacific coastal stations, and satellite-derived ocean concentrations of chlorophyll-<i>a</i>, dissolved organic carbon, and particulate organic carbon. Of all the parameters examined, a multi-variable logistic regression revealed that the combination of 10 m wind speed and surface chlorophyll-<i>a</i> concentration ([Chl-<i>a</i>]) are the most consistent predictors of OM<sub>SSA</sub>. This relationship, combined with the published aerosol size dependence of OM<sub>SSA</sub>, resulted in a new parameterization for the organic mass fraction of SSA. Global emissions of marine POA are investigated here by applying this newly-developed relationship to existing sea spray emission functions, satellite-derived [Chl-<i>a</i>], and modeled 10 m winds. Analysis of model simulations shows that global annual submicron marine organic emission associated with sea spray is estimated to be from 2.8 to 5.6 Tg C yr<sup>−1</sup>. This study provides additional evidence that marine primary organic aerosols are a globally significant source of organics in the atmosphere

Aerosol-cloud interactions in the NASA GMI: model development and indirect forcing assessments

International audienceThis study uses the NASA Global Modeling Initiative (GMI) 3-D chemical transport model (CTM) for assessments of indirect forcing and its sensitivity to the treatment of aerosol, aerosol-cloud interactions and meteorological fields. Three different meteorological datasets from NASA Data Assimilation Office (DAO), NASA finite volume GCM (FVGCM) and the Goddard Institute for Space Studies version II' (GISS II') GCM were used. GMI is ideal for this study as different model components (such as meteorological fields and chemical mechanisms) can easily be interchanged under the same model framework to capture the first aerosol indirect effect (AIE), and its sensitivity to parameterizations and meteorological fields. Cloud droplet number concentration was calculated by implementing both diagnostic and physically based droplet parameterizations. Derived cloud properties, such as cloud optical thickness and effective radius were compared with the remotely sensed data from Moderate Resolution Imaging Spectroradiometer (MODIS). GMI was able to capture the spatial variability and the land-ocean contrast observed in the satellite record. Depending on the meteorological field and droplet parameterization used, the annual mean first AIE ranged from ?0.99 to ?1.48 W m?2. It is found that, roughly 80% of the variation is attributed to changes in the meteorology (primarily from variations in liquid water path), while the remaining 20% is attributed to different cloud droplet parameterizations

Model evaluation of marine primary organic aerosol emission schemes

In this study, several marine primary organic aerosol (POA) emission schemes have been evaluated using the GEOS-Chem chemical transport model in order to provide guidance for their implementation in air quality and climate models. These emission schemes, based on varying dependencies of chlorophyll <i>a</i> concentration ([chl <i>a</i>]) and 10 m wind speed (<i>U</i><sub>10</sub>), have large differences in their magnitude, spatial distribution, and seasonality. Model comparison with weekly and monthly mean values of the organic aerosol mass concentration at two coastal sites shows that the source function exclusively related to [chl <i>a</i>] does a better job replicating surface observations. Sensitivity simulations in which the negative <i>U</i><sub>10</sub> and positive [chl <i>a</i>] dependence of the organic mass fraction of sea spray aerosol are enhanced show improved prediction of the seasonality of the marine POA concentrations. A top-down estimate of submicron marine POA emissions based on the parameterization that compares best to the observed weekly and monthly mean values of marine organic aerosol surface concentrations has a global average emission rate of 6.3 Tg yr<sup>−1</sup>. Evaluation of existing marine POA source functions against a case study during which marine POA contributed the major fraction of submicron aerosol mass shows that none of the existing parameterizations are able to reproduce the hourly-averaged observations. Our calculations suggest that in order to capture episodic events and short-term variability in submicron marine POA concentration over the ocean, new source functions need to be developed that are grounded in the physical processes unique to the organic fraction of sea spray aerosol

Exploring the differences in cloud properties observed by the Terra and Aqua MODIS Sensors

The aerosol-cloud interaction in different parts of the globe is examined here using multi-year statistics of remotely sensed data from two MODIS sensors aboard NASA's <i>Terra</i> (morning) and <i>Aqua</i> (afternoon) satellites. Simultaneous retrievals of aerosol loadings and cloud properties by the MODIS sensor allowed us to explore morning-to-afternoon variation of liquid cloud fraction (CF) and optical thickness (COT) for clean, moderately polluted and heavily polluted clouds in different seasons. Data analysis for seven-years of MODIS retrievals revealed strong temporal and spatial patterns in morning-to-afternoon variation of cloud fraction and optical thickness over different parts of the global oceans and the land. For the vast areas of stratocumulus cloud regions, the data shows that the days with elevated aerosol abundance were also associated with enhanced afternoon reduction of CF and COT pointing to the possible reduction of the indirect climate forcing. A positive correlation between aerosol optical depth and morning-to-afternoon variation of trade wind cumulus cloud cover was also found over the northern Indian Ocean, though no clear relationship between the concentration of Indo-Asian haze and morning-to-afternoon variation of COT was established. Over the Amazon region during wet conditions, aerosols are associated with an enhanced convective process in which morning shallow warm clouds are organized into afternoon deep convection with greater ice cloud coverage. Analysis presented here demonstrates that the new technique for exploring morning-to-afternoon variability in cloud properties by using the differences in data products from the two daily MODIS overpasses is capable of capturing some of the major features of diurnal variations in cloud properties and can be used for better understanding of aerosol radiative effects

Global distribution and climate forcing of marine organic aerosol: 1. Model improvements and evaluation

Marine organic aerosol emissions have been implemented and evaluated within the National Center of Atmospheric Research (NCAR)'s Community Atmosphere Model (CAM5) with the Pacific Northwest National Laboratory's 7-mode Modal Aerosol Module (MAM-7). Emissions of marine primary organic aerosols (POA), phytoplankton-produced isoprene- and monoterpenes-derived secondary organic aerosols (SOA) and methane sulfonate (MS<sup>−</sup>) are shown to affect surface concentrations of organic aerosols in remote marine regions. Global emissions of submicron marine POA is estimated to be 7.9 and 9.4 Tg yr<sup>−1</sup>, for the Gantt et al. (2011) and Vignati et al. (2010) emission parameterizations, respectively. Marine sources of SOA and particulate MS<sup>−</sup> (containing both sulfur and carbon atoms) contribute an additional 0.2 and 5.1 Tg yr<sup>−1</sup>, respectively. Widespread areas over productive waters of the Northern Atlantic, Northern Pacific, and the Southern Ocean show marine-source submicron organic aerosol surface concentrations of 100 ng m<sup>−3</sup>, with values up to 400 ng m<sup>−3</sup> over biologically productive areas. Comparison of long-term surface observations of water insoluble organic matter (WIOM) with POA concentrations from the two emission parameterizations shows that despite revealed discrepancies (often more than a factor of 2), both Gantt et al. (2011) and Vignati et al. (2010) formulations are able to capture the magnitude of marine organic aerosol concentrations, with the Gantt et al. (2011) parameterization attaining better seasonality. Model simulations show that the mixing state of the marine POA can impact the surface number concentration of cloud condensation nuclei (CCN). The largest increases (up to 20%) in CCN (at a supersaturation (<i>S</i>) of 0.2%) number concentration are obtained over biologically productive ocean waters when marine organic aerosol is assumed to be externally mixed with sea-salt. Assuming marine organics are internally-mixed with sea-salt provides diverse results with increases and decreases in the concentration of CCN over different parts of the ocean. The sign of the CCN change due to the addition of marine organics to sea-salt aerosol is determined by the relative significance of the increase in mean modal diameter due to addition of mass, and the decrease in particle hygroscopicity due to compositional changes in marine aerosol. Based on emerging evidence for increased CCN concentration over biologically active surface ocean areas/periods, our study suggests that treatment of sea spray in global climate models (GCMs) as an internal mixture of marine organic aerosols and sea-salt will likely lead to an underestimation in CCN number concentration

Wind-driven emissions of coarse-mode particles in an urban environment

Quantifying surface–atmosphere exchange rates of particles is important for understanding the role of suspended particulate matter in radiative transfer, clouds, precipitation, and climate change. Emissions of coarse-mode particles with a diameter greater than 0.5 µm provide giant cloud condensation nuclei and ice nuclei. These emissions are critical for understanding the evolution of cloud microphysical properties yet remain poorly understood. Here we introduce a new method that uses lidar retrievals of the elastic backscatter and Doppler velocity to obtain surface number emissions of particles with a diameter greater than 0.53 µm. The technique is applied to study particle number fluxes over a 2-month period from 1 June to 10 August 2022 during the TRACER campaign at an urban site near Houston, TX, USA. We found that all the observed fluxes were positive (upwards), indicating particle emission from the surface. The fluxes followed a diurnal pattern and peaked near noon local time. Flux intensity varied through the 2 months with multi-day periods of strong fluxes and multi-day periods of weak fluxes. Emission particle number fluxes peaked near ∼ 100 cm−2 s−1. The daily averaged emission fluxes correlated with friction velocity and were anticorrelated with surface relative humidity. The emission flux can be parameterized as F= 3000 u*4, where u* is the friction velocity in m s−1 and the emission flux F is in cm−2 s−1. The u* dependence is consistent with emission from wind-driven erosion. Estimated values for the mass flux are in the lower range of literature values from non-urban sites. These results demonstrate that urban environments may play an important role in supplying coarse-mode particles to the boundary layer. We anticipate that quantification of these emissions will help constrain aerosol–cloud interaction models that use prognostic aerosol schemes.</p