[Show abstract][Hide abstract] ABSTRACT: Organic macromolecules constitute a high percentage of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean ecodynamics model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed for labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of proteins, polysaccharides and refractory heteropolycondensates. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally well within an order of magnitude. Global distributions are further estimated for both fractional coverage of bubble films at the air–water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant patterns. These results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.
[Show abstract][Hide abstract] ABSTRACT: To study the effect of giant cloud condensation nuclei (GCCN) on precipitation processes in stratocumulus clouds, 1–10 μm diameter salt particles (salt powder) were released from an aircraft while flying near the cloud top on 3 August 2011 off the central coast of California. The seeded area was subsequently sampled from the aircraft that was equipped with aerosol, cloud, and precipitation probes and an upward-facing cloud radar. During post-seeding sampling, made 30–60 min after seeding, the mean cloud droplet size increased, the droplet number concentration decreased, and large drop (e.g., diameter larger than 10 μm) concentration increased. Average drizzle rates increased from about 0.05 to 0.20 mm h−1, and the liquid water path decreased from about 52 to 43 g m−2. Strong radar returns associated with drizzle were observed on the post-seeding cloud-base level-leg flights and were accompanied by a substantial depletion of the cloud liquid water content. The changes were large enough to suggest that the salt particles with concentrations estimated to be 10−2 to 10-4 cm−3 resulted in a four-fold increase in the cloud-base rainfall rate and depletion of the cloud water due to rainout. In contrast, a case is shown where the cloud was already precipitating (on 10 August) and the effect of adding GCCN to the cloud was insignificant.
No preview · Article · May 2015 · Atmospheric Chemistry and Physics
[Show abstract][Hide abstract] ABSTRACT: Primary marine aerosol (PMA)‐cloud interactions off the coast of California were investigated using observations of marine aerosol, cloud condensation nuclei (CCN), and stratocumulus clouds during the Eastern Pacific Emitted Aerosol Cloud Experiment (E‐PEACE) and the Stratocumulus Observations of Los‐Angeles Emissions Derived Aerosol‐Droplets (SOLEDAD) studies. Based on recently reported measurements of PMA size distributions, a constrained lognormal‐mode‐fitting procedure was devised to isolate PMA number size distributions from total aerosol size distributions and applied to E‐PEACE measurements. During the 12 day E‐PEACE cruise on the R/V Point Sur, PMA typically contributed less than 15% of total particle concentrations. PMA number concentrations averaged 12 cm−3 during a relatively calmer period (average wind speed 12 m/s1) lasting 8 days, and 71 cm−3 during a period of higher wind speeds (average 16 m/s1) lasting 5 days. On average, PMA contributed less than 10% of total CCN at supersaturations up to 0.9% during the calmer period; however, during the higher wind speed period, PMA comprised 5–63% of CCN (average 16–28%) at supersaturations less than 0.3%. Sea salt was measured directly in the dried residuals of cloud droplets during the SOLEDAD study. The mass fractions of sea salt in the residuals averaged 12 to 24% during three cloud events. Comparing the marine stratocumulus clouds sampled in the two campaigns, measured peak supersaturations were 0.2 ± 0.04% during E‐PEACE and 0.05–0.1% during SOLEDAD. The available measurements show that cloud droplet number concentrations increased with >100 nm particles in E‐PEACE but decreased in the three SOLEDAD cloud events. New method of analyzing primary marine aerosol (PMA) number size distributionsPMA CDNC increased with increasing >100 nm particles in E-PEACE but not SOLEDAD
Full-text · Article · May 2015 · Journal of Geophysical Research Atmospheres
[Show abstract][Hide abstract] ABSTRACT: Dust variability in the climate system has been studied for several decades, yet there remains an incomplete understanding of the dynamical mechanisms controlling interannual and decadal variations in dust transport. The sparseness of multi-year observational datasets has limited our understanding of the relationship between climate variations and atmospheric dust. We use available in situ and satellite observations of dust and a century-length fully coupled Community Earth System Model (CESM) simulation to show that the El Niño-Southern Oscillation (ENSO) exerts a control on North African dust transport during boreal summer. In CESM, this relationship is stronger over the dusty tropical North Atlantic than near Barbados, one of the few sites having a multi-decadal observed record. During strong La Niña summers in CESM, a statistically significant increase in lower tropospheric easterly wind is associated with an increase in North African dust transport over the Atlantic. Barbados dust and Pacific SST variability are only weakly correlated in both observations and CESM, suggesting that other processes are controlling the cross-basin variability of dust. We also use our CESM simulation to show that the relationship between downstream North African dust transport and ENSO fluctuates on multidecadal timescales and is associated with a phase shift in the North Atlantic Oscillation. Our findings indicate that existing observations of dust over the tropical North Atlantic are not extensive enough to completely describe the variability of dust and dust transport, and demonstrate the importance of global models to supplement and interpret observational records.
[Show abstract][Hide abstract] ABSTRACT: The Committee on “Geoengineering Climate: Technical Evaluation and Discussion of Impacts” was charged with the task of conducting a technical evaluation of a limited number of proposed geoengineering techniques, with this talk focusing on issues related to solar radiation management (SRM) or what is also termed albedo modification. The report comments generally on the potential impacts of deploying these technologies, including possible environmental, economic, and national security concerns. The study (1) evaluates what is currently known about the science of several selected example techniques, including potential risks and consequences (both intended and unintended), such as impacts, or lack thereof, on ocean acidification, (2) describes what is known about the viability for implementation of the proposed techniques including technological and cost considerations, (3) explains other geoengineering technologies that have been proposed (beyond the selected examples), and (4) identifies future research needed to provide a credible scientific underpinning for future discussions. The study also discusses historical examples of related technologies (e.g., cloud seeding and other weather modification) for lessons that might be learned about societal reactions, examines what international agreements exist which may be relevant to the experimental testing or deployment of geoengineering technologies, and briefly explores potential societal and ethical considerations related to geoengineering. This study is intended to provide a careful, clear scientific foundation that informs ethical, legal, and political discussions surrounding geoengineering. This study was sponsored by the U.S. intelligence community, the National Oceanic and Atmospheric Administration, the National Aeronautics and Space Administration, the Department of Energy, and the National Academies.
[Show abstract][Hide abstract] ABSTRACT: This study examines multi-year climate variability associated with sea salt aerosols and their contribution to the variability of shortwave cloud forcing (SWCF) using a 150-year simulation for pre-industrial conditions of the Community Earth System Model version 1.0 (CESM1). The results suggest that changes in sea salt and related cloud and radiative properties on interannual timescales are dominated by the ENSO cycle. Sea salt variability on longer (interdecadal) timescales is associated with low-frequency variability in the Pacific Ocean similar to the interdecadal Pacific Oscillation (IPO), but does not show a statistically significant spectral peak. A multivariate regression suggests that sea salt aerosol variability may contribute to SWCF variability in the tropical Pacific, explaining up to 20-30% of the variance in that region. Elsewhere, there is only a small sea salt aerosol influence on SWCF through modifying cloud droplet number and liquid water path that contributes to the change of cloud effective radius and cloud optical depth (and hence cloud albedo), producing a multi-year aerosol-cloud-wind interaction.
[Show abstract][Hide abstract] ABSTRACT: The toxicity of carbon nanotubes (CNTs) has received significant attention due to their usage in a wide range of commercial applications. While numerous studies exist on their impacts in water and soil ecosystems, there is a lack of information on the exposure to CNTs from the atmosphere. The transformation of CNTs in the atmosphere, resulting in their functionalization, may significantly alter their toxicity. In the current study, the chemical modification of single wall carbon nanotubes (SWCNTs) via ozone and OH radical oxidation is investigated through studies that simulate a range of expected tropospheric particulate matter (PM) lifetimes, in order to link their chemical evolution to toxicological changes. The results indicate that the oxidation favors carboxylic acid functionalization, but significantly less than other studies performed under non-atmospheric conditions. Despite evidence of functionalization, neither O3 nor OH radical oxidation resulted in a change in redox activity (potentially giving rise to oxidative stress) or in cytotoxic endpoints. Conversely, both the redox activity and cytotoxicity of SWCNTs significantly decreased when exposed to ambient urban air, likely due to the adsorption of organic carbon vapors. These results suggest that the effect of gas-particle partitioning of organics in the atmosphere on the toxicity of SWCNTs should be investigated further.
Full-text · Article · Jan 2015 · Environmental Science and Technology
[Show abstract][Hide abstract] ABSTRACT: The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely-sensed chlorophyll a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel framework for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semi-labile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecules. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll a and organic fraction are similar to existing empirical parameterizations, but can vary between biologically productive and non-productive regions, and seasonally within a given region. Major uncertainties include the bubble film thickness at bursting and the variability of organic surfactant activity in the ocean, which is poorly constrained. In addition, polysaccharides may enter the aerosol more efficiently than Langmuir adsorption would suggest. Potential mechanisms for include the formation of marine colloidal particles that may be more efficiently swept up by rising particles, and cooperative adsorption of polysaccharides with proteins or lipids. These processes may make important contributions to the aerosol, but are not included here. This organic fractionation framework is an initial step towards a closer linking of ocean biogeochemistry and aerosol chemical composition in Earth system models. Future work should focus on improving constraints on model parameters through new laboratory experiments or through empirical fitting to observed relationships in the real ocean and atmosphere, as well as on atmospheric implications of the variable composition of organic matter in sea spray.
Full-text · Article · Dec 2014 · Atmospheric Chemistry and Physics
[Show abstract][Hide abstract] ABSTRACT: The sources and composition of atmospheric marine aerosol particles (aMA) have been investigated with a range of physical and chemical measurements from open-ocean research cruises. This study uses the characteristic functional group composition (from Fourier transform infrared, or FTIR, spectroscopy) of aMA from five ocean regions to show that: (i) The organic functional group composition of aMA that can be identified as mainly atmospheric primary marine (ocean-derived) aerosol particles (aPMA) is 65 ± 12% hydroxyl, 21 ± 9% alkane, 6 ± 6% amine, and 7 ± 8% carboxylic acid functional groups. Contributions from photochemical reactions add carboxylic acid groups (15%-25%), shipping effluent in seawater and ship emissions add additional alkane groups (up to 70%), and coastal or continental emissions mix in alkane and carboxylic acid groups. (ii) The organic composition of aPMA is nearly identical to model generated primary marine aerosol particles from bubbled seawater (gPMA, which has 55 ± 14% hydroxyl, 32 ± 14% alkane, and 13 ± 3% amine functional groups), indicating that its overall functional group composition is the direct consequence of the organic constituents of the seawater source. (iii) While the seawater organic functional group composition was nearly invariant across all three ocean regions studied and the ratio of organic carbon to sodium (OC/Na+) in the gPMA remained nearly constant over a broad range of chlorophyll-a concentrations, the gPMA alkane group fraction appeared to increase with chlorophyll-a concentrations (r =0.66). gPMA from productive seawater had a larger fraction of alkane functional groups (42 ± 9%) compared to gPMA from non-productive seawater (22 ± 10%), perhaps due to the presence of surfactants in productive seawater that stabilize the bubble film and lead to preferential drainage of the more soluble (lower alkane group fraction) organic components. gPMA has a hydroxyl group absorption peak location characteristic of monosaccharides and disaccharides, where the seawater OM hydroxyl group peak location is closer to that of polysaccharides. This may result from the larger saccharides preferentially remaining in the seawater during gPMA and aPMA production.
[Show abstract][Hide abstract] ABSTRACT: Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be under-pinned by a physically and chemically accurate representation of the bubble-mediated production of nascent SSA particles. Bubble bursting is sensitive to the physico-chemical properties of seawater. For a sample of seawater, any important differences in the SSA production mechanism are projected into the composition of the aerosol particles produced. Using direct chemical measurements of SSA at the single-particle level, this study presents an intercomparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging-waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than those produced by sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic-enriched particles and a different size-resolved elemental composition, especially in the 0.8–2 μm dry diameter range. Interestingly, chemical differences between the methods only emerged when the particles were chemically analyzed at the single-particle level as a function of size; averaging the elemental composition of all particles across all sizes masked the differences between the SSA samples. When dried, SSA generated by the sintered glass filters had the highest fraction of particles with spherical morphology compared to the more cubic structure expected for pure NaCl particles produced when the particle contains relatively little organic carbon. In addition to an intercomparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method on SSA composition was under-taken. In organic-enriched seawater, the continuous operation of the plunging waterfall resulted in the accumulation of surface foam and an over-expression of organic matter in SSA particles compared to those produced by a pulsed plunging waterfall. Throughout this set of experiments, comparative differences in the SSA number size distribution were coincident with differences in aerosol particle composition, indicating that the production mechanism of SSA exerts important controls on both the physical and chemical properties of the resulting aerosol with respect to both the internal and external mixing state of particles. This study provides insight into the inextricable physicochemical differences between each of the bubble-mediated SSA generation mechanisms tested and the aerosol particles that they produce, and also serves as a guideline for future laboratory studies of SSA particles.
Full-text · Article · Nov 2014 · Atmospheric Measurement Techniques
[Show abstract][Hide abstract] ABSTRACT: The dual-carbon isotope signatures and optical properties of carbonaceous aerosols have been investigated simultaneously for the first time in the South Asian outflow during an intensive campaign at the Maldives Climate Observatory on Hanimaadhoo (MCOH) (February-March 2012). As one component of the Cloud Aerosol Radiative Forcing Dynamics Experiment (CARDEX), this paper reports on the sources and the atmospheric processing of elemental carbon (EC) and water-soluble organic carbon (WSOC) as examined by a dual carbon isotope approach. The radiocarbon (Δ14C) data show that WSOC has a significantly higher biomass/biogenic contribution (86 ± 5%) compared to EC (59 ± 4%). The more 13C-enriched signature of MCOH-WSOC (−20.8 ± 0.7‰) compared to MCOH-EC (−25.8 ± 0.3‰) and megacity Delhi WSOC (−24.1 ± 0.9‰) suggests that WSOC is significantly more affected by aging during long-range transport than EC. The δ13C-Δ14C signal suggests that the wintertime WSOC intercepted over the Indian Ocean largely represents aged primary biomass-burning aerosols. Since light-absorbing organic carbon aerosols (‘Brown Carbon’, BrC) have recently been identified as potential contributors to positive radiative forcing, optical properties of WSOC were also investigated. The mass absorption cross section of WSOC (MAC365) was 0.5 ± 0.2 m2g−1 which is lower than what has been observed at near-source sites, indicating a net decrease of WSOC light-absorption character during long-range transport. Near-surface WSOC at MCOH accounted for ~1% of the total direct solar absorbance relative to EC, which is lower than the BrC absorption inferred from solar spectral observations of ambient aerosols, suggesting that a significant portion of BrC might be included in the water-insoluble portion of organic aerosols.
[Show abstract][Hide abstract] ABSTRACT: The dual carbon isotope signatures and optical properties of carbonaceous aerosols have been
investigated simultaneously for the first time in the South Asian outflow during an intensive campaign
at the Maldives Climate Observatory on Hanimaadhoo (MCOH) (February and March 2012). As one
component of the Cloud Aerosol Radiative Forcing Dynamics Experiment, this paper reports on the sources
and the atmospheric processing of elemental carbon (EC) and water-soluble organic carbon (WSOC) as
examined by a dual carbon isotope approach. The radiocarbon (Δ14C) data show that WSOC has a significantly
higher biomass/biogenic contribution (86 ± 5%) compared to EC (59 ± 4%). Themore 13C-enriched signature
of MCOH-WSOC (�20.8 ± 0.7‰) compared to MCOH-EC (�25.8 ± 0.3‰) and megacity Delhi WSOC
(�24.1 ± 0.9‰) suggests that WSOC is significantly more affected by aging during long-range transport
than EC. The δ13C-Δ14C signal suggests that the wintertime WSOC intercepted over the Indian Ocean
largely represents aged primary biomass burning aerosols. Since light-absorbing organic carbon aerosols
(Brown Carbon (BrC)) have recently been identified as potential contributors to positive radiative forcing,
optical properties of WSOC were also investigated. The mass absorption cross section of WSOC (MAC365) was
0.5 ± 0.2 m2 g�1 which is lower than what has been observed at near-source sites, indicating a net decrease
of WSOC light-absorption character during long-range transport. Near-surface WSOC at MCOH accounted
for ~1% of the total direct solar absorbance relative to EC, which is lower than the BrC absorption inferred
from solar spectral observations of ambient aerosols, suggesting that a significant portion of BrC might be
included in the water-insoluble portion of organic aerosols.
Full-text · Article · Oct 2014 · Journal of Geophysical Research Atmospheres
[Show abstract][Hide abstract] ABSTRACT: Although isocyanic acid (HNCO) may cause a variety of health issues via protein carbamylation and has been proposed as a key compound in smoke related health issues, our understanding of the atmospheric sources and fate of this toxic compound is currently incomplete. To address these issues, a field study was conducted at Mt. Soledad, La Jolla, CA to investigate partitioning of HNCO to clouds and fogs using an Acetate Chemical Ionization Mass Spectrometer (Acid-CIMS) coupled to a ground-based Counterflow Virtual Impactor (CVI). The first field evidence of cloud partitioning of HNCO is presented, demonstrating that HNCO is dissolved in cloudwater more efficiently than expected based on the effective Henry's law solubility. The measurements also indicate evidence for a secondary, photochemical source of HNCO in ambient air at this site.
[Show abstract][Hide abstract] ABSTRACT: The performance of the Weather Research and Forecasting regional model with chemistry (WRF-Chem) in simulating the spatial and temporal variations in aerosol mass, composition, and size over California is quantified using the extensive meteorological, trace gas, and aerosol measurements collected during the California Nexus of Air Quality and Climate Experiment (CalNex) and the Carbonaceous Aerosol and Radiative Effects Study (CARES) conducted during May and June of 2010. The overall objective of the field campaigns was to obtain data needed to better understand processes that affect both climate and air quality, including emission assessments, transport and chemical aging of aerosols, aerosol radiative effects. Simulations were performed that examined the sensitivity of aerosol concentrations to anthropogenic emissions and to long-range transport of aerosols into the domain obtained from a global model. The configuration of WRF-Chem used in this study is shown to reproduce the overall synoptic conditions, thermally driven circulations, and boundary layer structure observed in region that controls the transport and mixing of trace gases and aerosols. Reducing the default emissions inventory by 50% led to an overall improvement in many simulated trace gases and black carbon aerosol at most sites and along most aircraft flight paths; however, simulated organic aerosol was closer to observed when there were no adjustments to the primary organic aerosol emissions. We found that sulfate was better simulated over northern California whereas nitrate was better simulated over southern California. While the overall spatial and temporal variability of aerosols and their precursors were simulated reasonably well, we show cases where the local transport of some aerosol plumes were either too slow or too fast, which adversely affects the statistics quantifying the differences between observed and simulated quantities. Comparisons with lidar and in situ measurements indicate that long-range transport of aerosols from the global model was likely too high in the free troposphere even though their concentrations were relatively low. This bias led to an over-prediction in aerosol optical depth by as much as a factor of 2 that offset the under-predictions of boundary-layer extinction resulting primarily from local emissions. Lowering the boundary conditions of aerosol concentrations by 50% greatly reduced the bias in simulated aerosol optical depth for all regions of California. This study shows that quantifying regional-scale variations in aerosol radiative forcing and determining the relative role of emissions from local and distant sources is challenging during `clean' conditions and that a wide array of measurements are needed to ensure model predictions are correct for the right reasons. In this regard, the combined CalNex and CARES data sets are an ideal test bed that can be used to evaluate aerosol models in great detail and develop improved treatments for aerosol processes.
[Show abstract][Hide abstract] ABSTRACT: This study uses a century length pre-industrial climate simulation by the Community Earth System Model (CESM 1.0) to explore statistical relationships between dust, clouds and atmospheric circulation, and to suggest a semi-direct dynamical mechanism linking subtropical North Atlantic lower tropospheric cloud cover with North African dust transport. The length of the run allows us to account for interannual variability of North African dust emissions and transport in the model. CESM's monthly climatology of both aerosol optical depth and surface dust concentration at Cape Verde and Barbados, respectively, agree well with available observations, as does the aerosol size distribution at Cape Verde. In addition, CESM shows strong seasonal cycles of dust burden and lower tropospheric cloud fraction, with maximum values occurring during boreal summer, when a strong correlation between these two variables exists over the subtropical North Atlantic. Calculations of Estimated Inversion Strength (EIS) and composites of EIS on high and low downstream North Africa dust months during boreal summer reveal that dust is likely increasing inversion strength over this region due to both solar absorption and reflection. We find no evidence for a microphysical link between dust and lower tropospheric clouds in this region. These results yield new insight over an extensive period of time into the complex relationship between North African dust and North Atlantic lower tropospheric clouds, which has previously been hindered by spatiotemporal constraints of observations. Our findings lay a framework for future analyses using different climate models and sub-monthly data over regions with different underlying dynamics.