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Codes used for analysis in Sutherland et al. (2023)&nbsp

The printed optical particle spectrometer (POPS) is a lightweight, low-cost instrument for measurements of aerosol number concentrations and size distributions. This work reports on modifications of the Handix Scientific commercial version of the POPS to facilitate its use in multi-instrument aerosol sampling systems. The flow system is modified by replacing the internal pump with a needle valve and a vacuum pump. The instrument is integrated into closed-flow systems by routing the sheath flow from filtered inlet air. A high-precision multichannel analyzer (MCA) card is added to sample the analog pulse signal. The MCA card is polled at 10 Hz frequency using an external data acquisition system and improves upon the count-rate limitation associated with the POPS internal data acquisition system. The times required to change the concentration between 90 % and 10 % and vice versa for a step change in concentration were measured to be 0.17 and 0.41 s at a flow rate of 5 cm3 s−1. This yields a sampling frequency of ∼ 1–2 Hz, below which the amplitude of measured fluctuations is captured with > 70 % efficiency. The modified POPS was integrated into the dual tandem differential mobility analyzer system to explore the coalescence of dimer particles. Results show that the pulse-height response increases upon dimer coalescence. The magnitude of the increase is broadly consistent with the change in light-scattering amplitude predicted by the T-matrix method. It is anticipated that this modified version of the POPS will extend the utilization of the technique for a range of field and laboratory applications.

As scientists engage in research motivated by climate change and the impacts of pollution on air, water, and human health, we increasingly recognize the need for the scientific community to improve communication and knowledge exchange across disciplines to address pressing and outstanding research questions holistically. Our professional paths have crossed because our research activities focus on the chemical reactivity of Fe-containing minerals in air and water, and at the air-sea interface. (Photo)chemical reactions driven by Fe can take place at the surface of the particles/droplets or within the condensed phase. The extent and rates of these reactions are influenced by water content and biogeochemical activity ubiquitous in these systems. One of these reactions is the production of reactive oxygen species (ROS) that cause damage to respiratory organs. Another is that the reactivity of Fe and organics in aerosol particles alter surficial physicochemical properties that impact aerosol-radiation and aerosol-cloud interactions. Also, upon deposition, aerosol particles influence ocean biogeochemical processes because micronutrients such as Fe or toxic elements such as copper become bioavailable. We provide a perspective on these topics and future research directions on the reactivity of Fe in atmospheric aerosol systems, from sources to short- and long-term impacts at the sinks with emphasis on needs to enhance the predictive power of atmospheric and ocean models.

The article of record may be found at https://doi.org/10.1575/1912/27821 The Surface Ocean – Lower Atmosphere Study (SOLAS) (http://www.solas-int.org/) is an international research initiative focused on understanding the key biogeochemical-physical interactions and feedbacks between the ocean and atmosphere that are critical elements of climate and global biogeochemical cycles. Following the release of the SOLAS Decadal Science Plan (2015-2025) (Brévière et al., 2016), the Ocean-Atmosphere Interaction Committee (OAIC) was formed as a subcommittee of the Ocean Carbon and Biogeochemistry (OCB) Scientific Steering Committee to coordinate US SOLAS efforts and activities, facilitate interactions among atmospheric and ocean scientists, and strengthen US contributions to international SOLAS. In October 2019, with support from OCB, the OAIC convened an open community workshop, Ocean-Atmosphere Interactions: Scoping directions for new research with the goal of fostering new collaborations and identifying knowledge gaps and high-priority science questions to formulate a US SOLAS Science Plan. Based on presentations and discussions at the workshop, the OAIC and workshop participants have developed this US SOLAS Science Plan. The first part of the workshop and this Science Plan were purposefully designed around the five themes of the SOLAS Decadal Science Plan (2015-2025) (Brévière et al., 2016) to provide a common set of research priorities and ensure a more cohesive US contribution to international SOLAS. This report was developed with federal support of NSF (OCE-1558412) and NASA (NNX17AB17G). This report was developed with federal support of NSF (OCE-1558412) and NASA (NNX17AB17G).

Fine particulate matter (i.e., PM2.5) has gained extensive attention owing to its adverse effects. The impacts of PM2.5 may vary in time and space due to the spatiotemporal variations of PM2.5 number size distribution and chemical compositions. This research analyzed the latest PM2.5 chemical compositions measurements with an aim to better understand the dynamic changes of PM2.5 in response to emission reductions due to the new regulations. The particulate measurements from the Southeastern Aerosol Research and Characterization (SEARCH) network between 2001 and 2016 were analyzed for the spatiotemporal variations of PM2.5 and inorganic PM2.5 (iPM2.5 = SO42− + NH4+ + NO3−) chemical compositions in the Southeastern United States (U.S.). It was discovered that PM2.5 and iPM2.5 mass concentrations exhibited significant downward trends in 2001–2016. Both PM2.5 and iPM2.5 mass concentrations were higher at urban and inland sites than rural/suburban and coastal sites. The higher iPM2.5 concentrations at agricultural sites were attributed to the influences of ammonia (NH3) emissions from animal feeding operations (AFOs). The iPM2.5 was the dominant contributor to PM2.5 in 2001–2016 at the coastal sites, whereas organic carbon matter (OCM) was the major contributor to PM2.5 after 2011 at the inland sites. Our data analysis suggests that significant decrease of PM2.5 concentrations is attributed to the reductions in nitrogen oxides (NOx) and sulfur dioxide (SO2) emissions in 2001–2016. Findings from this research provide insights into the development of effective PM2.5 control strategies and assessment of air pollutants exposure.

The ocean is the most important subsystem of the Earth’s climate system and functions as its heart, regulating the energy distribution of the planet. It has absorbed more than 90% of the energy accumulated since 1971 and about 30% of the emitted anthropogenic carbon dioxide. As a result, water temperature rises and oceans acidify and deoxygenate, which lead to changes in oceanic circulation and biogeochemistry, to rising sea levels, to more extreme weather events, to shifts in the distribution of species and migratory routes, and to loss of species and habitat diversity. Awareness of the importance of oceans for the sustainability of the global human population is increasing, including the conservation of biodiversity and its legacy to future generations [1]. For instance, oceanic organisms are more vulnerable to warming than terrestrial ones, as the former are generally at temperatures near their upper thermal limits and lack of thermal refuges [2]. Half of the atmospheric carbon fixed annually in natural systems is cycled into the ocean mainly by the biological carbon pump in the open ocean, but some of the main areas capturing and storing this carbon (as mangroves, seagrasses, salt marshes, and coastal upwelling ecosystems) cover less than 3% of the world’s ocean surface [3]. Particularly, eastern boundary upwelling systems are highly productive ecosystems, with up to 40% of the reported global fish catch [4].

Improved characterization of ambient PM(2.5) mass concentration and chemical speciation is a topic of interest in air quality and climate sciences. Over the past decades, considerable efforts have been made to improve ground-level PM(2.5) using remotely sensed data. Here we present two new approaches for estimating atmospheric PM(2.5) and chemical composition based on the High Spectral Resolution Lidar (HSRL)-retrieved aerosol extinction values and types and Creating Aerosol Types from Chemistry (CATCH)-derived aerosol chemical composition. The first methodology (CMAQ-HSRL-CH) improves EPA’s Community Multiscale Air Quality (CMAQ) predictions by applying variable scaling factors derived using remotely-sensed information about aerosol vertical distribution and types and the CATCH algorithm. The second methodology (HSRL-CH) does not require regional model runs and can provide atmospheric PM(2.5) mass concentration and chemical speciation using only the remotely sensed data and the CATCH algorithm. The resulting PM(2.5) concentrations and chemical speciation derived for NASA DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality) Baltimore-Washington, D.C. Corridor (BWC) Campaign (2011) are compared to surface measurements from EPA’s Air Quality Systems (AQS) network. The analysis shows that the CMAQ-HSRL-CH method leads to considerable improvement of CMAQ’s predicted PM(2.5) concentrations (R(2) value increased from 0.37 to 0.63, the root mean square error (RMSE) was reduced from 11.9 to 7.2 μg m(−3), and the normalized mean bias (NMB) was lowered from −46.0 to 4.6%). The HSRL-CH method showed statistics (R(2)=0.75, RMSE=8.6 μgm(−3), and NMB=24.0%), which were better than the CMAQ prediction of PM(2.5) alone and analogous to CMAQ-HSRL-CH. In addition to mass concentration, HSRL-CH can also provide aerosol chemical composition without specific model simulations. We expect that the HSRL-CH method will be able to make reliable estimates of PM(2.5) concentration and chemical composition where HSRL data are available.

Data Files: EPA Air Quality System (AQS), CMAQ model results, HSRL retrievals Matlab scripts for the data analysis/plotting &nbsp

Ultrafine particles with diameters less than 100 nm suspended in the air are a topic of interest in air quality and climate sciences. Sub-10 nm particles are of additional interest due to their health effects and contribution to particle growth processes. Ambient measurements were carried out at North Carolina State University in Raleigh, NC between April to June 2019 and November 2019 to May 2020 to investigate the temporal variability of size distribution and number concentration of ultrafine particles. A mobile lab was deployed between March and May 2020 to characterize the spatial distribution of sub-10 nm particle number concentration. New particle formation and growth events were observed regularly. Also observed were direct emissions of sub-10 nm particles. Analysis against meteorological variables, gas-phase species, and particle concentrations show that the sub-10nm particles dominated number concentration during periods of low planetary boundary layer height, low solar radiation, and northeast winds. The spatial patterns observed during mobile deployments suggest that multiple temporally stable and spatially confined point sources of sub-10 nm particles are present within the city. These sources likely include the campus utility plants and the Raleigh-Durham International Airport. Additionally, the timing of data collection allowed for investigation of variations in the urban aerosol number size distribution due to reduced economic activity during the COVID-19 pandemic., Highlights • A monthly average of 8 new particle formation events contribute to the ultrafine particle number concentration. • Multiple distinct anthropogenic sources of sub-10 nm sized particles are identified. • A slight reduction in number concentration was observed during the the COVID-19 pandemic.

Atmospheric aerosols are an important source of soluble iron (sol-Fe) to the global oceans. After deposition to seawater, sol-Fe will either complex with Fe-binding marine organic ligands and enter the ocean dissolved Fe (DFe) pool, or form oxyhydroxide particles (PFe) and precipitate out. Since oceanic DFe is commonly assumed to be bioavailable, the importance of atmospheric sources of sol-Fe for ocean biogeochemistry is determined by both: total fluxes of sol-Fe and the fraction of sol-Fe that is converted to DFe in the ocean. The results from these laboratory studies show that in 20 min from the time of mixing with seawater, nearly all sol-Fe gets oxidized and converted to PFe. The addition of dicarboxylic acids (oxalic and malic) had minor influence on the conversion rate of sol-Fe to PFe. However, the addition of α-hydroxy-carboxylic acids (citric and tartaric) to Fe solutions prior to mixing with seawater was found to considerably increase the concentration of seawater DFe. After 10 days of the experiment, 15% and 50% of the sol-Fe in citric and tartaric acid solutions, respectively, remained in a DFe form. Numerical simulations for sol-Fe laden dust deposition events to the ocean show that if α-hydroxy acids are present in aerosol solution upon deposition to the surface ocean, over 95% of sol-Fe can potentially bind with marine organic ligands; this fraction reduces to

Air pollution creates high Fe solubility in pyrogenic aerosols, raising the flux of biologically essential Fe to the oceans., Atmospheric deposition is a source of potentially bioavailable iron (Fe) and thus can partially control biological productivity in large parts of the ocean. However, the explanation of observed high aerosol Fe solubility compared to that in soil particles is still controversial, as several hypotheses have been proposed to explain this observation. Here, a statistical analysis of aerosol Fe solubility estimated from four models and observations compiled from multiple field campaigns suggests that pyrogenic aerosols are the main sources of aerosols with high Fe solubility at low concentration. Additionally, we find that field data over the Southern Ocean display a much wider range in aerosol Fe solubility compared to the models, which indicate an underestimation of labile Fe concentrations by a factor of 15. These findings suggest that pyrogenic Fe-containing aerosols are important sources of atmospheric bioavailable Fe to the open ocean and crucial for predicting anthropogenic perturbations to marine productivity.

Animal feeding operations (AFOs) are the largest ammonia (NH3) emission sources in the United States (U.S.). However, the impact of NH3 emissions from AFOs on the formation of secondary inorganic PM2.5 (iPM2.5) has not been well understood and systematically assessed. Under the Southeastern Aerosol Research and Characterization (SEARCH) Network, the hourly concentrations of iPM2.5 chemical compositions and its precursor gases as well as meteorological data were measured at eight urban/nonurban sites labeled as JST/YRK, BHM/CTR, GFP/OAK, and PNS/OLF during 1998–2016. Using the SEARCH data, this research investigated the spatiotemporal variations of atmospheric chemical conditions in those rural and urban areas. The spatiotemporal variations of atmospheric chemical conditions at the eight sites are characterized by four parameters, including (1) gas ratio (GR), (2) gas-phase NH3 molar fraction (NH3/NHx), (3) total available NH3 (gaseous ammonia + aerosol ammonium) to sulfate (SO42−) molar ratio (TA/TS), and (4) PM2.5 ammonium + nitrate to total PM2.5 mass ratio (AN/PM2.5). Results indicate that the NH3 emissions from AFOs may explain the greater values of GR, NH3/NHx, and TA/TS in the wind directions coming from AFOs at YRK and OAK rural sites than the other wind directions. In the wind directions coming from AFOs at YRK and OAK, NH3 was in excess of fully neutralizing acidic gases, more NH3 stayed in gas phase than those in other wind directions, and both ammonium sulfate and ammonium nitrate existed in iPM2.5. The upward trend in NH3/NHx indicates that gas-particle partitioning ofNH3–NH4+shifted toward gas phase, while the downward trend in AN/PM2.5 may implicate that smaller fraction of PM2.5 was directly NH3 sensitive. Understanding of the spatiotemporal variations of atmospheric chemical condition provides insights to improve our understanding of iPM2.5 formation under rural and urban conditions, the reduction in sulfur dioxide (SO2) and nitrogen oxides (NOx) emissions resulted in the reduction of iPM2.5 formation despite the increase in NH3 emissions in the Southeastern U.S.

Projections of future climate remain an important scientific goal for much of the Earth science community [...]

It is well recognized that the atmospheric deposition of iron (Fe) affects ocean productivity, atmospheric CO2 uptake, ecosystem diversity, and overall climate. Despite significant advances in measurement techniques and modeling efforts, discrepancies persist between observations and models that hinder accurate predictions of processes and their global effects. Here, we provide an assessment report on where the current state of knowledge is and where future research emphasis would have the highest impact in furthering the field of Fe atmosphere-ocean biogeochemical cycle. These results were determined through consensus reached by diverse researchers from the oceanographic and atmospheric science communities with backgrounds in laboratory and in situ measurements, modeling, and remote sensing. We discuss i) novel measurement methodologies and instrumentation that allow detection and speciation of different forms and oxidation states of Fe in deliquesced mineral aerosol, cloud/rainwater, and seawater; ii) oceanic models that treat Fe cycling with several external sources and sinks, dissolved, colloidal, particulate, inorganic, and organic ligand-complexed forms of Fe, as well as Fe in detritus and phytoplankton; and iii) atmospheric models that consider natural and anthropogenic sources of Fe, mobilization of Fe in mineral aerosols due to the dissolution of Fe-oxides and Fe-substituted aluminosilicates through proton-promoted, organic ligand-promoted, and photo-reductive mechanisms. In addition, the study identifies existing challenges and disconnects (both fundamental and methodological) such as i) inconsistencies in Fe nomenclature and the definition of bioavailable Fe between oceanic and atmospheric disciplines, and ii) the lack of characterization of the processes controlling Fe speciation and residence time at the atmosphere-ocean interface. Such challenges are undoubtedly caused by extremely low concentrations, short lifetime, and the myriad of physical, (photo)chemical, and biological processes affecting global biogeochemical cycling of Fe. However, we also argue that the historical division (separate treatment of Fe biogeochemistry in oceanic and atmospheric disciplines) and the classical funding structures (that often create obstacles for transdisciplinary collaboration) are also hampering the advancement of knowledge in the field. Finally, the study provides some specific ideas and guidelines for laboratory studies, field measurements, and modeling research required for improved characterization of global biogeochemical cycling of Fe in relationship with other trace elements and essential nutrients. The report is intended to aid scientists in their work related to Fe biogeochemistry as well as program managers at the relevant funding agencies.

Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from −79% when using the default settings to −12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of −36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

The accurate representation of aerosols in climate models requires direct ambient measurement of the size- and composition-dependent particle production fluxes. Here, we present the design, testing, and analysis of data collected through the first instrument capable of measuring hygroscopicity-based, size-resolved particle fluxes using a continuous-flow Hygroscopicity-Resolved Relaxed Eddy Accumulation (Hy-Res REA) technique. The Hy-Res REA system used in this study includes a 3D sonic anemometer, two fast-response solenoid valves, two condensation particle counters, a scanning mobility particle sizer, and a hygroscopicity tandem differential mobility analyzer. The different components of the instrument were tested inside the US Environmental Protection Agency's Aerosol Test Facility for sodium chloride and ammonium sulfate particle fluxes. The new REA system design does not require particle accumulation, and therefore avoids the diffusional wall losses associated with long residence times of particles inside the air collectors of traditional REA devices. A linear relationship was found between the sodium chloride particle fluxes measured by eddy covariance and REA techniques. The particle detection limit of the Hy-Res REA flux system is estimated to be ∼3 × 105 m−2 s−1. The estimated sodium chloride particle classification limit, for the mixture of sodium chloride and ammonium sulfate particles of comparable concentrations, is ∼6 × 106 m−2 s−1. Copyright © 2018 American Association for Aerosol Research

Retrievals of aerosol optical depth (AOD) from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) satellite sensor require the assumption of the extinction-to-backscatter ratio, also known as the lidar ratio. This paper evaluates a new method to calculate the lidar ratio of marine aerosols using two independent sources: the AOD from the Synergized Optical Depth of Aerosols (SODA) project and the integrated attenuated backscatter from CALIOP. With this method, the particulate lidar ratio can be derived for individual CALIOP retrievals in single aerosol layer, cloud-free columns over the ocean. Global analyses are carried out using CALIOP level 2, 5 km marine aerosol layer products and the collocated SODA nighttime data from December 2007 to November 2010. The global mean lidar ratio for marine aerosols was found to be 26 sr, roughly 30% higher than the current value prescribed by the CALIOP standard retrieval algorithm. Data analysis also showed considerable spatiotemporal variability in the calculated lidar ratio over the remote oceans. The calculated marine aerosol lidar ratio is found to vary with the mean ocean surface wind speed (U10). An increase in U10 reduces the mean lidar ratio for marine regions from 32 ± 17 sr (for 0 < U10 < 4 m s−1) to 22 ± 7 sr (for U10 > 15 m s−1). Such changes in the lidar ratio are expected to have a corresponding effect on the marine AOD from CALIOP. 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 marine AOD.

We report here production rates of isoprene and monoterpene compounds (α-pinene, β-pinene, camphene and d-limonene) from six phytoplankton monocultures as a function of irradiance and temperature. Irradiance experiments were carried out for diatom strains (Thalassiosira weissflogii and Thalassiosira pseudonana), prymnesiophyte strains (Pleurochrysis carterae), dinoflagellate strains (Karenia brevis and Prorocentrum minimum), and cryptophyte strains (Rhodomonas salina), while temperature experiments were carried out for diatom strains (Thalassiosira weissflogii and Thalassiosira pseudonana). Phytoplankton species, incubated in a climate-controlled room, were subject to variable light (90 to 900 μmol m−2 s−1) and temperature (18 to 30 °C) regimes. Compared to isoprene, monoterpene emissions were an order of magnitude lower at all light and temperature levels. Emission rates are normalized by cell count and Chlorophyll a (Chl a) content. Diatom strains were the largest emitters, with ~ 2 × 10−17 g(cell)−1h−1 (~ 35 μg (g Chl a)−1 h−1) for isoprene and ~ 5 × 10−19 g (cell)−1 h−1 (~ 1 μg (g Chl a)−1) h−1) for α-pinene. The contribution to the total monoterpene production was ~ 70% from α-pinene, ~ 20% for d-limonene, and < 10% for camphene and β-pinene. Phytoplankton species showed a rapid increase in production rates at low irradiance (< 150 μmol m−2 s−1) and a gradual increase at high (> 250 μmol m−2 s−1) irradiance. Measurements revealed different patterns for time-averaged emissions rates over two successive days. On the first day, most of the species showed a distinct increase in production rates within the first 4 h while, on the second day, the emission rates were overall higher, but less variable. The data suggest that enhanced amounts of isoprene and monoterpenes are emitted from phytoplankton as a result of perturbations in environmental conditions that cause imbalance in chloroplasts and force primary producers to acclimate physiologically. This relationship could be a valuable tool for development of dynamic ecosystem modeling approaches for global marine isoprene and monoterpene emissions based on phytoplankton physiological responses to a changing environment.

To realistically simulate the impacts of marine isoprene and primary organic aerosols (POA) on atmospheric chemistry, a unified model framework with online emissions, comprehensive treatment of gas-phase chemistry, and advanced aerosol microphysics is required. In this work, the global-through-urban WRF/Chem model (GU-WRF/Chem) implemented with the online emissions of marine isoprene and size-resolved marine POA is applied to examine such impacts. The net effect of these emissions was increased surface concentrations of isoprene and organic aerosols and decreased surfaced concentrations of hydroxyl radical and ozone over most marine regions. With the inclusion of these emissions, GU-WRF/Chem better predicted the surface concentrations of isoprene and organic aerosols and the aerosol number size distribution when compared to measurements in clean marine conditions.

Current remote sensing methods can identify aerosol types within an atmospheric column, presenting an opportunity to incrementally bridge the gap between remote sensing and models. Here a new algorithm was designed for Creating Aerosol Types from CHemistry (CATCH). CATCH-derived aerosol types—dusty mix, maritime, urban, smoke, and fresh smoke—are based on first-generation airborne High Spectral Resolution Lidar (HSRL-1) retrievals during the Ship-Aircraft Bio-Optical Research (SABOR) campaign, July/August 2014. CATCH is designed to derive aerosol types from model output of chemical composition. CATCH-derived aerosol types are determined by multivariate clustering of model-calculated variables that have been trained using retrievals of aerosol types from HSRL-1. CATCH-derived aerosol types (with the exception of smoke) compare well with HSRL-1 retrievals during SABOR with an average difference in aerosol optical depth (AOD)

Over forty scientists from six countries convened in Raleigh, NC on June 4-6 2012 to review the status and prospects of sea spray aerosol research. Participants were researchers from the oceanography and atmospheric science communities, including academia, private industry, and government agencies. The recommendations from the working groups are summarized in a science prioritization matrix that is meant to prioritize the research agenda and identify areas of investigation by the magnitude of their impact on proposed science questions. Str

Knowledge of the physical characteristics and chemical composition of marine organic aerosols is needed for the quantification of their effects on solar radiation transfer and cloud processes. This review examines research pertinent to the chemical composition, size distribution, mixing state, emission mechanism, photochemical oxidation and climatic impact of marine primary organic aerosol (POA) associated with sea-spray. Numerous measurements have shown that both the ambient mass concentration of marine POA and size-resolved organic mass fraction of sea-spray aerosol are related to surface ocean biological activity. Recent studies have also indicated that fine mode (smaller than 200 nm in diameter) marine POA can have a size distribution independent from sea-salt, while coarse mode aerosols (larger than 1000 nm in diameter) are more likely to be internally mixed with sea-salt. Modelling studies have estimated global submicron marine POA emission rates of ~10 ± 5 Tg yr−1, with a considerable fraction of these emissions occurring over regions most susceptible to aerosol perturbations. Climate studies have found that marine POA can cause large local increases in the cloud condensation nuclei concentration and have a non-negligible influence on model assessments of the anthropogenic aerosol forcing of climate. Despite these signs of climate-relevance, the source strength, chemical composition, mixing state, hygroscopicity, cloud droplet activation potential, atmospheric aging and removal of marine POA remain poorly quantified. Additional laboratory, field, and modelling studies focused on the chemistry, size distribution and mixing state of marine POA are needed to better understand and quantify their importance.

In the first part of this paper series (Meskhidze et al., 2011), a treatment of marine organic aerosols (including primary organic aerosol, secondary organic aerosols, and methane sulfonate) was implemented into the Community Atmosphere Model version 5 (CAM5) with a 7-mode Modal Aerosol Module. A series of simulations was conducted to quantify the changes in aerosol and cloud condensation nuclei concentrations in the marine boundary layer. In this study, changes in the cloud microphysical properties and radiative forcing resulting from marine organic aerosols are assessed. Model simulations show that the anthropogenic aerosol indirect forcing (AIF) predicted by CAM5 is decreased in absolute magnitude by up to ~0.10 W m−2 (8%) when marine organic aerosols are included. Changes in the AIF from marine organic aerosols are associated with small global increases in low-level in-cloud droplet number concentration and liquid water path of ~1.3 cm−3 (~1.6%) and 0.2 g m−2 (0.5%), respectively. Areas especially sensitive to changes in cloud properties due to marine organic aerosol include the Southern Ocean, North Pacific Ocean, and North Atlantic Ocean, all of which are characterized by high marine organic emission rates. As climate models are particularly sensitive to the background aerosol concentration, this small but non-negligible change in the AIF due to marine organic aerosols provides a notable link for ocean-ecosystem marine low-level cloud interactions and may be a candidate for consideration in future earth system models.

Global WRF (GWRF) is an extension of the mesoscale Weather Research and Forecasting (WRF) model that was developed for global weather research and forecasting applications. GWRF is being expanded to simulate atmospheric chemistry and its interactions with meteorology on a global scale. In this work, the ability of GWRF to reproduce major boundary layer meteorological variables that affect the fate and transport of air pollutants is assessed using observations from surface networks and satellites. The model evaluation shows an overall good performance in simulating global shortwave and longwave radiation, temperature, and specific humidity, despite large biases at high latitudes and over-Arctic and Antarctic areas. Larger biases exist in wind speed and precipitation predictions. These results are generally consistent with the performance of most current general circulation models where accuracies are often limited by a coarse grid resolution and inadequacies in sub-filter-scale parameterizations and errors in the specification of external forcings. The sensitivity simulations show that a coarse grid resolution leads to worse predictions of surface temperature and precipitation. The combinations of schemes that include the Dudhia shortwave radiation scheme or the Purdue Lin microphysics module, or the Grell-Devenyi cumulus parameterization lead to a worse performance for predictions of downward shortwave radiation flux, temperature, and specific humidity, as compared with those with respective alternative schemes. The physical option with the Purdue Lin microphysics module leads to a worse performance for precipitation predictions. The projected climate in 2050 indicates a warmer and drier climate, which may have important impacts on the fate and lifetime of air pollutants.

The relationship between "clean marine" aerosol optical properties and ocean surface wind speed is explored using remotely sensed data from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) on board the CALIPSO satellite and the Advanced Microwave Scanning Radiometer (AMSR-E) on board the AQUA satellite. Detailed data analyses are carried out over 15 regions selected to be representative of different areas of the global ocean for the time period from June 2006 to April 2011. Based on remotely sensed optical properties the CALIPSO algorithm is capable of discriminating "clean marine" aerosols from other types often present over the ocean (such as urban/industrial pollution, desert dust and biomass burning). The global mean optical depth of "clean marine" aerosol at 532 nm (AOD532) is found to be 0.052 ± 0.038 (mean plus or minus standard deviation). The mean layer integrated particulate depolarization ratio of marine aerosols is 0.02 ± 0.016. Integrated attenuated backscatter and color ratio of marine aerosols at 532 nm were found to be 0.003 ± 0.002 sr−1 and 0.530 ± 0.149, respectively. A logistic regression between AOD532 and 10-m surface wind speed (U10) revealed three distinct regimes. For U10 ≤ 4 m s−1 the mean CALIPSO-derived AOD532 is found to be 0.02 ± 0.003 with little dependency on the surface wind speed. For 4 < U10 ≤ 12 m s−1, representing the dominant fraction of all available data, marine aerosol optical depth is linearly correlated with the surface wind speed values, with a slope of 0.006 s m−1. In this intermediate wind speed region, the AOD532 vs. U10 regression slope derived here is comparable to previously reported values. At very high wind speed values (U10 > 18 m s−1), the AOD532-wind speed relationship showed a tendency toward leveling off, asymptotically approaching value of 0.15. The conclusions of this study regarding the aerosol extinction vs. wind speed relationship may have been influenced by the constant lidar ratio used for CALIPSO-derived AOD532. Nevertheless, active satellite sensor used in this study that allows separation of maritime wind induced component of AOD from the total AOD over the ocean could lead to improvements in optical properties of sea spray aerosols and their production mechanisms.

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−) 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−1, for the Gantt et al. (2011) and Vignati et al. (2010) emission parameterizations, respectively. Marine sources of SOA and particulate MS− (containing both sulfur and carbon atoms) contribute an additional 0.2 and 5.1 Tg yr−1, 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−3, with values up to 400 ng m−3 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 (S) 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.

Under the 11th Five Year Plan (FYP, 2006e2010) for national environmental protection by the Chinese government, the overarching goal for sulfur dioxide (SO2) controls is to achieve a total national emissions level of SO2 in 2010 10% lower than the level in 2005. A similar nitrogen oxides (NOx) emissions control plan is currently under development and could be enforced during the 12th FYP (2011e2015). In this study, the U.S. Environmental Protection Agency (U.S.EPA)’s Community Multi-Scale Air Quality (Models3/CMAQ) modeling system was applied to assess the air quality improvement that would result from the targeted SO2 and NOx emission controls in China. Four emission scenarios d the base year 2005, the 2010 Business-As-Usual (BAU) scenario, the 2010 SO2 control scenario, and the 2010 NOx control scenariodwere constructed and simulated to assess the air quality change from the national control plan. The Fifth-Generation NCAR/Penn State Mesoscale Model (MM5) was applied to generate the meteorological fields for the CMAQ simulations. In this Part I paper, the model performance for the simulated meteorology was evaluated against observations for the base case in terms of temperature, wind speed, wind direction, and precipitation. It is shown that MM5 model gives an overall good performance for these meteorological variables. The generated meteorological fields are acceptable for using in the CMAQ modeling.

Following the meteorological evaluation in Part I, this Part II paper presents the statistical evaluation of air quality predictions by the U.S. Environmental Protection Agency (U.S. EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) model for the four simulated months in the base year 2005. The surface predictions were evaluated using the Air Pollution Index (API) data published by the China Ministry of Environmental Protection (MEP) for 31 capital cities and daily fine particulate matter (PM2.5, particles with aerodiameter less than or equal to 2.5 mm) observations of an individual site in Tsinghua University (THU). To overcome the shortage in surface observations, satellite data are used to assess the column predictions including tropospheric nitrogen dioxide (NO2) column abundance and aerosol optical depth (AOD). The result shows that CMAQ gives reasonably good predictions for the air quality. The air quality improvement that would result from the targeted sulfur dioxide (SO2) and nitrogen oxides (NOx) emission controls in China were assessed for the objective year 2010. The results show that the emission controls can lead to significant air quality benefits. SO2 concentrations in highly polluted areas of East China in 2010 are estimated to be decreased by 30e60% compared to the levels in the 2010 Business-As-Usual (BAU) case. The annual PM2.5 can also decline by 3e15 mgm �3 (4e25%) due to the lower SO2 and sulfate concentrations. If similar controls are implemented for NOx emissions, NOx concentrations are estimated to decrease by 30e60% as compared with the 2010 BAU scenario. The annual mean PM2.5 concentrations will also decline by 2e14 mgm �3 (3e12%). In addition, the number of

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 PM2.5 by 0.1–0.3 μg m−3 (up to 5%) in some coastal cities such as San Francisco, CA. This increase in the PM2.5 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.

The impact of marine isoprene emissions on summertime surface concentrations of isoprene, secondary organic aerosols (SOA), and ozone (O3) in the coastal areas of the continental United States is studied using the U.S. Environmental Protection Agency regional-scale Community Multiscale Air Quality (CMAQ) modeling system. Marine isoprene emission rates are based on the following five parameters: laboratory measurements of isoprene production from phytoplankton under a range of light conditions, remotelysensed chlorophyll-a concentration ([Chl–a]), incoming solar radiation, surface wind speed, and sea-water optical properties. Model simulations show that marine isoprene emissions are sensitive to meteorology and ocean ecosystem productivity, with the highest rates simulated over the Gulf of Mexico. Simulated offshore surface layer marine isoprene concentration is less than 10 ppt and significantly dwarfed by terrestrial emissions over the continental United States. With the isoprene reactions included in this study, the average contribution of marine isoprene to SOA and O3 concentrations is predicted to be small, up to 0.004 m gm �3 for SOA and 0.2 ppb for O3 in coastal urban areas. The light-sensitivity of isoprene production from phytoplankton results in a midday maximum for marine isoprene emissions and a corresponding daytime increase in isoprene and O3 concentrations in coastal locations. The potential impact of the daily variability in [Chl-a ]o n O 3 and SOA concentrations is simulated in a sensitivity study with [Chl-a] increased and decreased by a factor of five. Our results indicate that marine emissions of isoprene cause minor changes to coastal SOA and O3 concentrations. Comparison of model simulations with few available measurements shows that the model underestimates marine boundary layer isoprene concentration. This underestimation is likely due to the limitations in current treatment of marine isoprene emission and a coarse spatial resolution used in the model simulations.

The global marine sources of organic carbon (OC) are estimated here using a physically-based parameterization for the emission of marine isoprene and primary organic matter. The marine isoprene emission model incorporates new physical parameters such as light sensitivity of phytoplankton isoprene production and dynamic euphotic depth to simulate hourly marine isoprene emissions totaling 0.92 Tg C yr−1. Sensitivity studies using different schemes for the euphotic zone depth and ocean phytoplankton speciation produce the upper and the lower range of marine-isoprene emissions of 0.31 to 1.09 Tg C yr−1, respectively. Established relationships between sea spray fractionation of water-insoluble organic carbon (WIOC) and chlorophyll-a concentration are used to estimate the total primary sources of marine sub- and super-micron OC of 2.9 and 19.4 Tg C yr−1, respectively. The consistent spatial and temporal resolution of the two emission types allow us, for the first time, to explore the relative contributions of sub- and super-micron organic matter and marine isoprene-derived secondary organic aerosol (SOA) to the total OC fraction of marine aerosol. Using a fixed 3% mass yield for the conversion of isoprene to SOA, our emission simulations show minor (

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 Terra (morning) and Aqua (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.

The atmospheric supply of dust iron (Fe) plays a crucial role in the Earth's biogeochemical cycle and is of specific importance as a micronutrient in the marine environment. Observations show several orders of magnitude variability in the fractional solubility of Fe in dust aerosols, making it hard to assess the role of mineral dust for global ocean biogeochemical Fe cycle. In this study we compare the operational solubility of dust aerosol Fe associated with one of the flow-through leaching protocols to the results of the global 3-D chemical transport model GEOS-Chem. In the protocol aerosol Fe is defined soluble by first deionized water leaching of mineral dust through a 0.45 μm pore size membrane followed by acidification and storage of the leachate over a long period of time prior to the analysis. To assess the concentrations of soluble Fe inferred by this flow-through leaching protocol we are using in situ measurements of dust size distribution with the prescribed of 50 % fractional solubility of Fe in less than 0.45 μm sized dust particles collected in the leachate. In the model, the fractional solubility of Fe is either explicitly calculated using complex dust Fe dissolution module, or prescribed to be 1 and 4 %. Calculations show that the fractional solubility of Fe derived through the flow-through leaching is typically higher compared to the model results. The largest differences (>30 %) are predicted to occur farther away from the dust source regions, over the areas where sub-0.45 μm sized mineral dust particles contribute a larger fraction of the total dust mass. This study suggests that inconsistences in the operational definition of soluble Fe could contribute to the wide range of the fractional solubility of dust aerosol Fe reported in the literature.

Fast response tracer flux measurements are compared against flux footprint predictions from both a Lagrangian stochastic simulation and an analytical solution to the equation of diffusion over a canopy of intermediate roughness. A turbulent tracer flux experiment was conducted over a peach orchard for a range of mildly unstable to very unstable conditions. For this purpose, a line source was used to release sulfur hexafluoride at treetop and fast response tracer flux instrumentation placed in the roughness sub-layer was mounted on four towers perpendicular to the line source to measure the vertical tracer flux. There was excellent agreement between Lagrangian simulated fluxes and their experimental counterparts. The analytical solution to the advection–diffusion equation used also shows a good agreement with the tracer fluxes particularly far from the tracer source. These results suggest that for canopies of intermediate roughness, the flux footprint predictions from both models presented work very well, despite their simplifying assumptions.

The impact of anthropogenic aerosol on climate forcing remains uncertain largely due to inadequate representation of natural aerosols in climate models. The marine boundary layer (MBL) might serve as a model location to study natural aerosol processes. Yet source and sink mechanisms controlling the MBL aerosol number, size distribution, chemical composition, and hygroscopic properties remain poorly constrained. Here aerosol size distribution and water uptake measurements were made aboard the R/V Hi'ialakai from 27 June to 3 July 2016 in the subtropical North Pacific Ocean. Size distributions were predominantly bimodal with an average integrated number concentration of 197 ± 98 cm−3. Hygroscopic growth factors were measured using the tandem differential mobility analyzer technique for dry 48, 96, and 144 nm particles. Mode kappa values for these were 0.57 ± 0.12, 0.51 ± 0.09, and 0.52 ± 0.08, respectively. To better understand remote MBL aerosol sources, a new algorithm was developed which decomposes hygroscopicity distributions into three classes: carbon-containing particles, sulfate-like particles, and sodium-containing particles. Results from this algorithm showed low and steady sodium-containing particle concentrations while the sulfate-like and carbon-containing particle concentrations varied during the cruise. According to the classification scheme, carbon-containing particles contributed at least 3–7%, sulfate-like particles contributed at most 77–88% and sodium-containing particles at least contributed 9–16% to the total aerosol number concentration. Size distribution and hygroscopicity data, in conjunction with air mass back trajectory analysis, suggested that the aerosol budget in the subtropical North Pacific MBL may be controlled by aerosol entrainment from the free troposphere.